3 Oral PresentationsA reversed phase high performance liquid chromatographic method has been...

Abstract Book innc.conf.2012

15

ORAL PRESENTATIONS


16

Linoleic Acid as Substrate for the Production of Conjugated Linoleic Acid using whole Cell Biocatalysts

Abid Ali Khaskheli*1, Farah N. Talpur

1, Ayhan S. Demir

2, Aysun C. Aydin

3

1National Center of Excellence in Analytical Chemistry, University of Sindh, 76080, Jamshoro,

Pakistan 2Department of Chemistry, Middle East Technical University, Ankara, Turkey

3Department of Food Engineering, Abdullah Gul University, Kayseri, Turkey

Abstract: Whole cell biocatalysis is an environment-friendly synthetic method for selective synthesis of bioactive isomers of conjugated linoleic acid (CLA), the potential anticarcinogenic, antiatherogenic and a number of other therapeutic qualities bearing substance. In our present study we have isolated Lactobacillus Plantarum from local dairy milk and used as a biocatalyst for selective CLA production from linoleic acid (LA). The product formation was monitored by spectrophotometric method and the individual isomers quantitation was done with GC-FID. After optimization of whole cell culture conditions such as pH, LA concentration, effect of pre-inubation, time and temperature; maximum yield of CLA 220 mg/L was obtained in 120 h. The results revealed that the bacterium is a good biocatalyst for the production of CLA using LA as a substrate.

Peach Nut Shell: A Green and Economical Adsorbent for the Removal of Carbofuran Pesticide from Water

G. Zuhra Memon, M. Mudassir Arain

Dr. M. A. Kazi Institute of Chemistry, University of Sindh, University of Sindh,

Jamshoro-76080- Pakistan Abstract: In developing countries like Pakistan, the use of pesticides has turned out to be so important that they are connected with growth of human welfare. About 600,000 tonnes of pesticides are used in developing countries from which only less than 0.1% of applied pesticides reach the targeted pests and residual 99.9% have the possibility to move into soil, water and in atmosphere. In the present study low cost adsorbent material is prepared from peach nut shell after chemical and steam activation for the removal of carbofuran pesticide from water. The adsorption parameters i.e. pH, contact time, shaking speed and initial concentration have been studied. The adsorption was found to be rapid 98-99% within 30 min. The activated adsorbent material was characterized by scanning electron microscopy (SEM) analysis. Methanol was found suitable solvent to elute the adsorbed pesticide from the surface of adsorbent. The Freundlich, Langmuir, and D-R models were used to study the adsorption behavior along with kinetic and thermodynamic studies. The proposed method was employed to remove carbofuran pesticide from real water samples. The adsorption capacity of adsorbent was found practically constant after repeated use of more than 6 times. It is, consequently, recommended that expensive synthetic adsorbents may be reinstating by these low-cost adsorbents for the removal of toxic pesticides from water streams on large scale.


17

A Comparative Transportation of Cr(VI) Through Calix[4]arene Based Supported Liquid Membrane

Imam Bakhsh Solangi*1,2

, Mustafa Ersoz1, Shahabuddin Memon

1,2

1Department of Chemistry, Selçuk University, 42031, Campus, Konya, Turkey 2National Center of Excellence in Analytical Chemistry, University of Sindh,

Jamshoro-76080, Pakistan

Abstract:

The present study describes a comparative transportation of chromium (VI) across supported liquid membranes (SLMs) containing p-tert-butylcalix[4]arene diamide derivatives bearing pyridinium unit (2-aminomethyl pyridine, 3-aminomethyl pyridine). These carriers were immobilized onto the supported surface i.e. Celgard® 2500. The membrane surfaces were characterized by using various analytical techniques such as Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), Atomic Force Microscopy (AFM) and contact angle measurements. The transport efficiency of p-tert-butylcalix[4]arene based 2-aminomethyl pyridine, 3-aminomethyl pyridine for Cr(VI) from the feed to stripping phase has been evaluated. The experiments have been conducted involving the effect of pH, role of NaOH in stripping phase, concentration of Cr(VI), amount of carrier and contact time. Moreover, from the results of stability test, effect of other co-existing metal ions and field study confirmed the applicability of p-tert-butylcalix[4]arene diamide derivative bearing 3-aminomethyl pyridine for the selective recovery of Cr(VI) in the acidic medium. The study also confers its impact on human health, reinstate of polluted sites and other fields of material science.

Preparation and Characterization of Uniform Molecularly Imprinted Polymer Beads for Separation of Triazine Herbicides

Behisht Ara*a,b

, ZhiyongChena, Jasmin Shah

b, M. Rasul Jan

b, Lei Ye

a

aDivision of Pure and Applied Biochemistry, Lund University, Box 124, 22100 Lund, Sweden

bInstitute of Chemical Sciences, University of Peshawar, KPK, Pakistan

Abstract: Uniform molecularly imprinted polymer beads were synthesized by precipitation polymerization for separation of triazine herbicides. A series of imprinted polymers were prepared using ametryn as template and divinylbenzene as crosslinking monomer, in combination with three different functional monomers under different solvent conditions. Under optimized reaction conditions, we obtained uniform molecularly imprinted polymer microspheres that display favorable molecular binding selectivity for trazine herbicides. The imprinted polymer beads synthesized using methacrylic acid as functional monomer in a mixture of methyl ethyl ketone and heptane showed the best results in terms of particle size distribution and molecular selectivity. Compared to non-imprinted polymer microspheres, the imprinted microspheres displayed significantly higher binding for a group of triazine herbicides including atrazine, simazine, propazine, ametryn, prometryn and terbutryn.


18

Simultaneous Preconcentration/Removal of Nickel, Copper, Lead and Cadmium using Okra Leaves (Abelmoschus esculentus)

Mazhar I. Khaskheli1*

, Saima Q. Memon1, M.Y. Khuhawar

1

1Institute of Advance Research Studies in Chemical Sciences, University of Sindh,

Jamshoro, Pakistan

Abstract: In this study, the potential of okra leaves for the preconcentration of Ni, Cu, Pb and Cd from mixed metal aqueous solution was evaluated. Batch and column studies were carried out. The data was analyzed by Freundlich, Langmuir, D-R, Flory-Huggin and Halsey adsorption models. The order of maximum metal uptakes calculated by D-R isotherm was Cu2+>Pb2+>Cd2+ and Ni2+, 453 mg/g, 81 mg/g, 13.82 mg/g and 1 mg/g respectively with the energy of adsorption in the range of 9-15 for Ni and Cd expected for the ion exchange nature of adsorption and 7-8 for Cu and Pb showing the physical nature of adsorption. All four metal ions could be preconcnetrated at pH 7 with detection limits of 0.04-0.1 µg/mL. The method was successfully applied for the removal/preconcnetration of all four metal ions from ground, tape and waste water samples collected from different areas of Pakistan.

Development and Validation of HPLC Method for Simultaneous Determination of Ceftriaxone and Cefaclor in Commercial Formulations

and Biological Samples

Jasmin Shah, M. Rasul Jan, Sultan Shah*

Institute of Chemical Sciences, University of Peshawar, Pakistan

Abstract:

A reversed phase high performance liquid chromatographic method has been developed for the simultaneous determination of cefaclor (second generation, oral) and ceftriaxone (third generation, parenteral) cephalosporin antibiotic. The developed method has been validated and applied to mixtures of the commercial formulation and spiked human plasma. A mediterranea C18 column (4.6mm x 250mm) was used with isocratic solvent delivery system and UV-visible

detector. Different experimental parameters like flow rate of mobile phase (0.6 mL.min‒1), pH of the buffer (7), wavelength (260), and solvent composition (acetonitrile: methanol: triethyl amine buffer 1:1:2(v/v)) were optimized for effective separation and resolution of the analyte peaks. The separation is achieved in 6 min with retention times of 4.94±0.056 min and 3.39±0.022 min for cefaclor and ceftriaxone respectively.The linear range for both the studied drugs was found to be

0.5-250 µg mL‒1 with r2of 0.9949 (cefaclor) and 0.9988 (ceftriaxone). The limit of detection

(3.3σ/s) and limit of quantification (10σ/s) were calculated for both the drugs. The developed chromatographic procedure has been applied to commercial formulations and spiked human plasma for the simultaneous quantification of ceftriaxone and cefaclor. The percent recoveries were 98.36%±4.85 to 103.01%±3.79 for cefaclor and 97.68%±4.49 to 102.61%±3.88 for ceftriaxone in case of commercial formulations while excellent percent recoveries (98.03%±4.30 to 101.74%±4.48 for cefaclorand99.62%±2.87 to 103.85%±1.89 for ceftriaxone) were obtained in case of spiked human plasma. The developed method has good interday and intraday precision. The results of the developed method were compared with literature HPLC method and evaluated statistically using student t-test and variance ration f-test.


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O

O

NH2

NH S

O

O

S

O

OO Na

OS

O

OO Na

NH

S

O

O

Na ON

N

-

-

S

O

O

Na OS

O

OO Na

OH NH N

N N

Cl

Cl

-

NN

SNa O

O

O

S

O

OO Na

OH NH

NN

N Cl

Cl

Reactive Blue 19 (RB-19)

+-

+-

+

+

Reactive Black 5 (RB-5)

+ - +-

Reactive Red 45 (RR-45)

+

Effective Extraction of Reactive Blue-19 Dye by Calix[4]arene Derivative

Fakhar N. Memon*, Shahabuddin Memon

National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro

Abstract: Reactive dyes are water soluble and anionic in nature, which are extensively used in textile industries due to their favorable characteristics of water-fast, bright color, simple and low energy consumption and their ability to bind with cellulosic fiber by covalent bonding. However, they are an important class of pollutants that enter into the environment through various sources such as textile dyeing, shoe polish, plastic, lather, paper printing. The process of dyeing in the textile industries produces large amount of colored wastewater, which is drained out into the streams without its proper treatment, which is harmful not only for visual nature but also retards the proper transmission of sunlight to the aquatic life. They are toxic, mutagenic and carcinogenic. Once they enter into the aquatic system their biodegradation is very difficult due to their complex aromatic molecular structure. Therefore, the strategy to remove the color and to decrease its impact into the wastewater of textile environment has found to be of significant importance. In this regard present work demonstrates the comparative extraction efficiency of p-tert-

butylcalix[4]arene and its derivatives toward a series of some selected reactive dyes such as Reactive Black-5 (RB-5), Reactive Blue-19 (RB-19) and Reactive Red-45 (RR-45) from aqueous to organic phase. In addition, the process of complexation has also been investigated through UV-visible spectroscopy. The study will be discussed in detail.

Determination of Unsaponifiable Constituents of Deodorizer Distillates by GC–MS

Farah. N. Talpur1* ,

Saba. Naz

1. S.T.H. Sherazi

1, Huseyin Kara

2

1National Center of Excellence in Analytical Chemistry, University of Sindh,

Jamshoro, Pakistan 2Selcuk University, Fen-Edebiyat Fakültesi, Kimya Bölümü, Kampus, 42075 Konya, Turkey

Abstract: Deodorizer distillate is an important by-product obtained during deodorization in the edible oil industries. It is a complex mixture of many health beneficial constituents like phytosterols, tocopherols and squalene. In the present study a simple gas chromatographic method with mass spectrometry was used for the separation, detection and quantification of different components present in the deodorizer distillate in a very short analysis time of 18 min. A simple saponification procedure without derivatization was used for their analysis followed by GC–MS analysis. Phytosterols concentration (21.27–25.53%) was the most abundant in canola and palm


20

distillate samples whereas; squalene and tocopherol were present in concentration ranges of 2.89–13.21% and 1.29–5.81%, respectively. The present study revealed that the unsaponifiable fraction of deodorizer distillate could be used in cosmetic preparations due to its appreciable amount of bioactive constituents.

Chemistry and Superoxide Dismutase Activity of Palladium(II) Complexes of Hydrazides

Uzma Ashiq

1*, Qurratul ain

1, Rifat Ara Jamal

1, Khalid M. Khan

2

1Department f Chemistry, University of Karachi, Karachi-75270, Pakistan

2H.E.J. Research Institute of Chemistry, International Center for Chemical Sciences,

University of Karachi, Karachi-75270, Pakistan

Abstract: Biologically relevant hydrazides and their analogues have been synthesized and complexed with Palladium (II) and evaluated for superoxide scavenging activity. Expected structures of these complexes have been proposed on the basis of elemental analyses, conductivity measurements, magnetic moments, and NMR and IR spectral data. The free hydrazide ligands are inactive against superoxide free radical whereas, Palladium (II) complexes of these ligands showed varying degrees of inhibition. Structure-activity relationship studies indicate that the electronic and/or steric factors that change the geometry of the complexes play an important role in their inhibitory potential against free radicals.

Synthesis and In vivo Anti-diabetic Activities of

3-arylsulfonylimidazolidine-2,4-diones

Abid Hussain, Muhammad K. Kashif and Shahid Hameed*

Department of Chemistry, Quaid-i-Azam University, Islamabad-45320, Pakistan

Abstract:

The synthesis of 3-arylsulfonylimidazolidine-2,4-diones (2a-p) was achieved by the reaction of imidazolidine-2,4-diones (1a-e) with arylsulfonyl chlorides in presence of triethyl amine. Imidazolidine-2,4-diones were synthesized from the corresponding ketones. The synthesized compounds were characterized using spectroanalytical techniques. The hypoglycemic activity of compounds 2a-c,e,f was evaluated using alloxanized diabetic rats model. The hypoglycemic activity of compound 2b was comparable to the standard drug (glipizide) whereas moderate activity was observed for compounds 2a and 2e.

(i) Et3N

(ii) DMAPR

H3C

NH

HN

O

Ar S

O

O

Cl

O

R

H3C

N

HN

O

O

S

OO

Ar

R = CH3, C6H5, 4-FC6H5, 4-BrC6H5, 4-ClC6H5

Ar = 4-ClC6H5. 4-CH3C6H5, 4-CH3OC6H5, 4-BrC6H5, 2-Naphthyl


21

Synthesis and Characterization of New Naphthoyl based Iminothiazolidinones

Aamer Saeed* and Saba Ashraf

Quaid-I-Azam University, Islamabad

Abstract: The use of thioureas in organic synthesis has become a versatile strategy for the synthesis of several biologically active compounds including thiazolidines, thiazoles, thiazolines, thiazolidinones. Synthesis of some new Naphthoyl based thioureas was carried out and these were efficiently converted into iminothiazolidinone acetates. The structures of all new compounds were confirmed by spectroscopic (IR, 1H NMR, 13C NMR) data and in some cases using single crystal X-ray data.

New Picolylamine Template Organo-Catalyst for Enantioselective Aldol Reactions

M.Naveed Umar

1,2, Thomas Nugent

2, Ahtaram Bibi

2

1 University of Malakand Pakistan,

2 Jacobs University Bremen Germany

Abstract: Picolylamine template organocatalyst containing only one stereogenic center has been identified for fast aldol reactions (16–48 h). Using 2–5 mol% of (R)- or (S)-PicAm-2, cyclohexanone (3.3 equiv) readily undergoes aldol reactions with o-, m-, and p-substituted aromatic aldehyde partners (limiting reagent), including the poor electrophile 4-methylbenzaldehyde (95–99% ee). Furthermore, functionalized cyclic ketone substrates have been converted into four aldol products 9–12 using the lowest catalyst loading (5.0 mol%) to date with the highest yield and enantioselectivity.

PicAm-2


22

Phytochemical, Physiochemical and Anti-fungal Activity of Eclipta rostrat

Iqbal Hussain1*, Shabir Ahmad, Riaz Ullah

1, Shafiq Ur Rehman

3, Shanzeb

1, G A Marwat

4 Sultan

Ayaz2

1Department of Chemistry, Kohat University of Science & Technology, Kohat 26000, Kohat,

Khyber Pakhtunkhwa, Pakistan 3Department of Plant Sciences, Kohat University of Science & Technology, Kohat 26000, Kohat,

Khyber Pakhtunkhwa, Pakistan 2Department of Zoology, Kohat University of Science & Technology, Kohat 26000, Kohat, Khyber

Pakhtunkhwa, Pakistan 4PCSIR Labs complex Jamrud Road Peshawar, Khyber Pakhtunkhwa, Pakistan

Abstract: Eclipta prostrata, is an important medicinal plant and their different parts are used for different health disorders. The triterpenoids isolated E. prostrata displayed antiproliferative and antimicrobial potentials. Phytochemically, E. prostrata is rich in wadeoloctone, eclalbasaponin, b-amyrin, stigmasterol and luteolin-7-glucoside. Keeping in view the importance of E prostrata, it was analyzed quantitatively, qualitatively for the phytochemicals (alkaloids, flavonoids, saponins, tannins, glycosides, terpenoids, reducing sugars, anthraquinones, and cardiacglycoside) Physiochemicals, and anti-fungal activity. For anti-fungal activity four different strains including Aspergillus niger, Aspergillus fumigatus, Fusarium solani and Aspergillus flavus used has shown very promising results against the fungal strain

A new Approach towards the Synthesis of Self-Catalyzed Phthalonitrile Resins

Amir Badshah

1,2, Michael R. Kessler

2, Zhou Heng

3, Aurangzeb Hasan

1,4*

1Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan

2Department of Materials Science and Engineering, Iowa State University, Ames,

Iowa 50011, United States 3Laboratory of Advanced Polymer Materials, Institute of Chemistry, The Chinese Academy of

Sciences, Beijing 100190, P. R. China 4Department of Chemistry, University of Malaya, Lembah Pentai, Kuala Lumpur 50603 Malysia

Abstract: Phthalonitrile polymers with amide and ortho-, meta-, and para- substituted ether linkages in the backbone were synthesized and their thermal properties investigated. The monomer building blocks for these polymers were cured without the addition of catalysts due to the self-catalyzing nature of the monomer’s amino group. The ether and amide functionalities in the chain enhanced their processability without compromising thermal stability. Analyses of the cure behavior and processing properties of the monomers were carried out by differential scanning calorimetry and rheometric analyses. The resins exhibited a low complex viscosity over a wide processing window between the monomer melting temperature and the polymer cure temperature, with the processing temperature range varying significantly for para-, ortho-, and meta- substituted polymer architectures. The monomer 3a (the ortho-substituted configuration) exhibited a lower melting point and high curing temperature than the other two isomers and thus allowed for a wider processing window. The 5 % weight loss temperature for all three cured


23

polymers was near 500 °C in air and 520 °C in nitrogen, with more than 70 % residual mass at 900 °C. None of the polymers exhibit a Tg below 500 °C when fully cured. The outstanding thermal stability of all synthesized polymers and the broad processing window of 3a are very promising for high temperature polymer and polymer matrix composites applications.

Determination of Iodine in Water Samples for the Assessment of Goiter using Ion Selective Electrode Method

Muhammad Rafi Awan*, Muhammad Mansha Chaudhry**, Abdullah***

*Department of Physics & Applied Mathematics, Pakistan Institute of Engineering and Applied

Sciences Nilore, Islamabad, Pakistan

**Department of Chemical & Materials Engineering, Pakistan Institute of Engineering and

Applied Sciences Nilore, Islamabad, Pakistan

***Department of Nuclear Engineering, Pakistan Institute of Engineering and Applied Sciences

Nilore, Islamabad, Pakistan

Abstract: Iodine is a part of thyroxine, a hormone produced by thyroid gland that controls the body’s rate of physical and mental development. Goiter is a disease due to iodine deficiency. To prevent goiter, the concentration of iodide in water samples was monitored. For this purpose water samples were collected from plain (Hyderabad and its adjoining) and hilly (Islamabad and its adjoining) areas. Ion selective electrode method was used for the determination of concentration of iodide in water samples. From the results, it was concluded that the concentration of iodine in hilly areas was less than 0.003 ppm (3 ppb) while in plain areas it is about ten times higher of this value. The results were compared with those from catalytic reduction method. For a series of water samples, the results obtained by the two techniques were in good agreement. Hence iodine deficiency is not the problem in plain areas. It is suggested that to find out the cause of goiter in plain areas, other goitrogenic factors like thiocyanate, perchlorate, nitrate, excess use of iodide and selenium deficiency may be studied. However, in hilly areas, iodized salt is advised for the population living in these areas to fight against goiter.

An Evaluation of Antioxidant Potential, Cytotoxicity and Characterization of Artemisia vulgaris Extract and Fractions

Muhammad Riaza, Nasir Rasool

a*, Komal Rizwan

a, Shafqat Ali

c, Muhammad Tayyab Razzaq

c,

Fatima Javedc and Hafiz Muhammad Abdul Qayyumc, Shabbir Hussaina aDepartment of Chemistry, Government College University, Faisalabad-38000, Pakistan

bDepartment of Chemistry and Biochemistry, University of Agriculture, Faisalabad-38040.

cDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan

Abstract: In the present study Artemisia vulgaris belongs to family Asteraceae, leaves were evaluated for antioxidant potential, antimicrobial activity and cytotoxicity studies. The leaves were extracted with absolute methanol and further fractionated with increasing polarity based absolute solvents. The phenolic contents were analyzed by spectroscopic technique. The DPPH scavenging and linoleic acid oxidation assays were carried out and the IC50 and % inhibition by


24

linoleic acid oxidation was evaluated. The ethyl acetate fraction purified over column chromatography over silica gel. The structures of the compounds were identified by 1D and 2D NMR techniques along with other spectral evidences and by comparison with the published data of closely related compounds. The cytotoxicity of the plant extract and fractions were assayed against human blood erythrocytes (RBCs).

4-Chloro-3-(2,2,2-trifluoroacetyl)-coumarin as a Novel Building Block for the Synthesis of 7-(trifluoromethyl)-6H-chromeno[4,3-b]quinolin-6-ones

Sajid Ali

a,b, Viktor O. Iaroshenko

b*, Tariq Mahmood Babar

b, Sergii Dudkin

b, Satenik Mkrtchyan

b,

Nasim Hasan Ramac, Alexander Villinger

b, Peter Langer

b,d*

aInstitute of chemical sciences, University of Peshawar, Peshawar, Pakistan,

bInstitut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany,

cDepartment of Chemistry, Quaid-i-Azam University, Islamabad-45320, Pakistan

dLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059

Rostock, Germany

Abstract: 4-Chloro-3-(2,2,2-trifluoroacetyl)coumarin was synthesized for the first time via direct TMSCl–mediated acylation of 4-hydroxycoumarin with TFAA followed by the treatment with POCl3. The reaction of 4-chloro-3-(2,2,2-trifluoroacetyl)coumarin with commercially available anilines is a two-step method, which affords a set of 7-(trifluoromethyl)-6H-chromeno[4,3-b] quinolin-6-ones in good to excellent yields

Synthesis and Structural Characterization of Cobalamin-Analogues

1*Shahzad Murtaza,

1Raja Summe Ullah,

2Bernhard Kraeutler

1Department of Chemistry, University of Gujrat, 50700 Gujrat. Pakistan,

2Institute of Organic Chemistry, University of Innsbruck, 6020 Innsbruck, Austria

Abstract: Cyanocobalamin (CNCbl, vitamin B12) a vitamin, is crucial for the survival of most living organisms. Bacteria produce B12 and all B12-dependent species must acquire the vitamin through their diet. Minute doses of the complex vitamin B12 are essential for metabolism. Vitamin B12 may divide into two major parts: the corrin ring with cobalt ion; and the lower nucleotide loop coordinating to cobalt making another macro-ring. The discovery of new type of analogue of cyanocobalamin, 176-Norpseudovitamin B12, lacking the characteristic methyl group at C-176 of the linker to the nucleotide loop, has generated new attention in cyanocobalmin analogues with a tailored linker. For future biological aspect, we are keen to synthesis such artificial derivatives of B12. Here we will present a balanced approach for the synthesis of cobalamin analogues with a modified amino-propanol linker and on their spectral characterization.


25

Redox Behavior of a Novel Menadiol Derivative at Glassy Carbon Electrode

Shamsa Munir1, Afzal Shah*

1, Abdur-Rauf

1, Suzanne K Lunsford

2and Zia-ur-Rehman

1

1Department of Chemistry, Quaid-i-Azam University, 45320, Islamabad, Pakistan

2Wright State University, 466 Oelman Hall Dayton, Ohio 45435

Abstract:

The redox behavior of a menadiol derivative, 4-hydroxy-5-methoxynaphthalene-1-yl

acetate (HMNA) was investigated in a wide pH range by using modern electrochemical techniques. The techniques utilized in this study were cyclic voltammetry, square wave voltammetry and differential pulse voltammetry (CV, SWV and DPV). A sharp anodic signal in the forward scan followed by a cathodic peak (associated with the reduction of the oxidation product of HMNA) in the reverse scan produced a counter oxidation signal in the positive realm of glassy carbon electrode. Physical parameters like diffusion coefficient and heterogeneous electron transfer rate constant were determined from scan rate and concentration effects. Square wave voltammetry evidenced the quasi-reversible nature of the electrochemical process. The involvement of protons in the redox mechanism was determined from the peak potential shift as a function of the pH. The redox mechanism of HMNA proposed on the base of CV and DPV results was supported by theoretical calculations. Moreover, a detailed UV-Vis spectroscopy was carried out in a wide pH range for characterization and pKa determination of HMNA.

Adsorption of Methyl Orange on Polymer of Intrinsic Microporosity (PIM-1)

Khalid Mahmood1, Muhammad Shakeel2 1Department of Chemistry Hazara University, Mahsehra, Pakistan

2Govt. Postgraduate College Mandian, Abbottabad, Pakistan

Abstract: The adsorption of Methyl Orange from aqueous solution on Polymer of Intrinsic Microporosity was studied at 300K. It was found that the adsorption increased with increase in concentration of solution. The adsorption process followed Langmuir’s adsorption isotherm to greater extent than Freundlich’s adsorption isotherm. For kinetic study five temperatures (288 – 313K) were selected. It was found that rate of adsorption increased with temperature increase. Low activation energy value showed the process was physical adsorption. From the positive ∆H, positive ∆G and positive ∆S values it was concluded that process was endothermic, non-spontaneous and resulted in increase in entropy


26

Synthesis, Electrical and Dielectric Properties of Cerium Doped Nano Copper Ferrites

Muhammad Aslam Malana, Raheela Beenish Qureshi, Naeem Ashiq, Zafar Iqbal Zafar

Department of Chemistry, Bahauddin Zakariya University, Multan

Abstract: The nanosized CuFe2-xCexO4 (x = 0.0, 0.2, 0.4, 0.6, 0.8) ferrites doped with cerium are synthesized by chemical co-precipitation method. The synthesized materials are characterized by x-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry and scanning electon microscopy. X-ray diffraction analysis of cerium substituted copper ferrites confirms the cubic spinel structure. The average crystallite size calculated by using Sherrer’s formula ranges from 37-53nm. The values of cell constant and cell volume vary with the dopant concentration. These variations can be explained in terms of their ionic radii. The electrical resistivity (measured by two probe method) increases with dopant concentration and decreases with temperature showing semiconductor behavior. Energy of activation for the samples is calculated by using Arrhenius type resistivity plots. Result of dielectric measurements for these samples show that dielectric constant and loss factor decrease exponentially with increase in frequency. This indicates the normal dielectric behavior of ferrites.

Use of Coconut Coir for the Removal of Copper Ions from Aqueous Media

Fahmida kausara, Nasir Khalid

b* and Muhammad Latif Mirza

a

aDepartment of Chemistry, The Islamia University of Bahawalpur, Pakistan bChemistry Division, Pakistan Institute of Nuclear Science and Technology,

P.O. Nilore, Islamabad, Pakistan

Department of Chemistry, The Islamia University of Bahawalpur

Abstract: The sorption behavior of copper ions on coconut coir has been studied as a function of nature of electrolytes (HNO3, HCl, H2SO4 and HClO4)), contact time, weight of adsorbent, amount of adsorbate and temperature, using batch method. The quantification of copper was made by atomic absorption spectrometric technique. Maximum adsorption was observed at 0.0001 mol

L−1 of HNO3 acid solution, using 0.25 g of adsorbent for 10 mL of 3.15 × 10−4 mol L−1 copper concentration within 15 minutes equilibration time. The adsorption of copper was decreased with the increase in the concentrations of all the acids used. The kinetic data indicated the sorption process being pseudo-second order. The adsorption data obeyed the Freundlich, Langmuir and

Dubinin-Radushkevich isotherms over the copper concentration range of 4.72 × 10−4 to 2.36 ×

10−3 mol L−1. The characteristic Freundlich constants i.e. 1/n = 0.324 and K = 0.509 m mol g−1

whereas the Langmuir constants Q = 5.69 × 10−2 m mol g−1 and b = 9.72 × 102 dm3 mol−1 have been computed for the sorption system. The sorption mean free energy from the Dubinin-

Radushkevich isotherm is 13.13 kJ mol−1 indicating ion-exchange mechanism of chemisorption.

The uptake of copper was increased with the rise in temperature (283−333 K). Thermodynamic

quantities i.e. ∆G, ∆S and ∆H have also been calculated for the system. The sorption process was found to be endothermic. Effect of other cations and anions on the adsorption of copper has also been studied.


27

Kinetic and Equilibrium Isotherms Modeling of Cr(VI) Adsorption onto Low Cost Adsorbent Developed from Phosphoric Acid Activation of

Date Stone

Rahmat Ali, Zeid A. AL-Othman

Advanced material Research Chair, Department of Chemistry, College of Science, Building -5,

King Saud University, Riyadh, Saudi Arabia

Abstract: In this work, a low cost activated carbon was prepared from waste dates’ stone (DS) by chemical activation with H3PO4. The prepared carbon was characterized for various physiochemical properties and utilized for the removal of Cr(VI) from aqueous solution. Batch mode experiments were conducted to study the effects of pH, contact time, initial concentration of adsorbate and temperature on the adsorption of Cr(VI). Cr(VI) adsorption was significantly depended on the solution pH and the optimum adsorption was observed at pH 2. The adsorption kinetic data were described very well by the pseudo-second order model. Equilibrium isotherm data was analyzed by the Langmuir, Freundlich and Temkin models. The results showed that the Langmuir model fitted the data better in the temperature range studied. The adsorption capacity was found to increase with temperature, showed endothermic nature of Cr(VI) adsorption. The thermodynamic parameters such as Gibb’s Free energy change (∆Go), standard enthalpy change (∆Ho) and standard entropy change (∆So) were evaluated.

Microelectrodes in Neurosciences- An Overview

Riaz Ahmed

Department of Chemistry, Quaid-i-Azam University, Islamabad

Abstract: Implanting of microelectrodes in the nervous system and their electrochemical studies provides useful information for the treatment of neural diseases. Using microelectrodes several neurochemical transmitters can be electrochemically detected, such as dopamine and many others and molecules derived from the amino-acids. Coating of microelectrodes with nanotubes and conducting polymers improves the contact with neural tissues and enhances the recording and electrical simulation of neurons by decreasing the electrode impedance and increasing the charge transfer. Magnetic resonance imaging (MRI) can be used for accurate implantation of microelectrodes in the relevant portions of the brain. Implanted electrodes can be used for electrochemical studies and can also be used for providing relevant potential pulses to the brain. Microelectrodes have been used to characterize neuronal action potentials and develop neuronal prosthetics. Through these microelectrodes appropriate patterns of electrical simulation can be provided to the brain and certain ailments can be cured and restoring vision to the blind has met with some success. These developments hold promise for the restoration of limb mobility in paralyzed subjects. Many other brain related diseases can also be cured. In this work fabrication and coating of microelectrodes, their implantation in brain, in vivo voltammetry and their performance for different studies in neurosciences are discussed and reviewed. Microelectrodes act as an interface to develop neuroprosthetic devices that could provide useful vision to the blind which are discussed and reviewed.


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Oxidative Degradation of Atrazine in Aqueous Solution by Hydroxyl and Sulfate Radical-based Advanced Oxidation Technologies:

A Comparative Study

Javed Ali Khan1, Hasan M. Khan

1, Noor S. Shah

1, Dionysios D. Dionysiou

2

1Radiation Chemistry Laboratory, National Centre of Excellence in Physical Chemistry,

University of Peshawar, Peshawar 25120, Pakistan 2Environmental Engineering and Science Program, University of Cincinnati, Cincinnati,

Ohio 45221-0012, USA

Abstract: The degradation of atrazine, a widely used endocrine disrupting, carcinogenic and persistent herbicide, was investigated by photo-Fenton and photo-Fenton-like advanced oxidation technologies (AOTs): UV/H2O2/Fe2+, UV/S2O8

2−/Fe2+ and UV/HSO5−/Fe2+. The study was carried

out at two pH value conditions, i.e., pH 3 and pH 5.8. At pH 3, UV/ HSO5−/Fe2+ was found to be

the most efficient technology whereas UV/ S2O82−

/Fe2+ was observed to be the most effective at pH 5.8. The initial concentration of atrazine had very little influence on its degradation rate when the molar ratio of oxidant/atrazine was kept constant; however, it had a pronounced effect when the oxidant concentration was fixed. The degradation of atrazine followed pseudo-first order reaction with the highest observed rate constant of 2.00 x 10−2 cm2/mJ in UV/ HSO5

−/Fe2+ system at the initial concentrations of 4.64 µM, 46.4 µM and 2.0 mg/L of atrazine, HSO5

− (PMS) and Fe2+, respectively. The effect of initial Fe2+ concentration on atrazine degradation was found to be much more prominent than that of initial oxidant concentration. Humic and fulvic acids were found to negatively impact the degradation of atrazine. The removal of TOC was not significant unless a high UV fluence was applied, with a 62.94 %, 47.10 % and 44.09 % decrease in TOC, in UV/PS/Fe2+, UV/PMS/Fe2+ and UV/H2O2/Fe2+ systems, respectively, at a UV fluence of 6000 mJ/cm2 when 18.56 µM atrazine, 1856 µM of oxidant and 1.0 mg/L of Fe2+ were used initially. Nevertheless, it is suggested in this study that photo-Fenton and photo-Fenton-like technologies are capable of removing atrazine from water environment efficiently.

On the Theory of Time Dilation in Chemical Kinetics

Mirza Wasif Baig

Department of Chemistry, Quaid-i-Azam University, 45320, Islamabad, Pakistan

Abstract: The rates of chemical reactions are not absolute but their magnitude depends upon the relative speeds of the moving observers. This has been proved by unifying theories of chemical kinetics, which are transition state theory, collision theory and Marcus theory, with the special theory of relativity. Boltzmann constant and energy spacing between permitted quantum levels of molecules are quantum mechanically proved to be Lorentz variant. The relativistic statistical thermodynamics has been developed to explain quasiequilibrium existing between reactants and activated complex. The newly formulated Lorentz transformation of the rate constant from Arrhenius Equation, of the collision frequency and of the Eyring and Marcus equations renders the rate law also Lorentz variant. For an observer moving at fractions of the speed of light along the reaction coordinate the transition state possesses less kinetic energy to sweep translation over


29

it. This results in the slower transformation of reactants into products and in a stretched time frame for the chemical reaction. Lorentz transformation of the half life equation explains time dilation of the half life period of chemical reactions and proves special theory of relativity and present theory of relativistic chemical kinetics in accord with each other. To demonstrate the effectiveness of the present theory, the enzymatic reaction of methylamine dehydrogenase and radioactive disintegration of Astatine are considered as numerical examples.

Influence of Non-ionic Surfactants on Emulsion Polymerization

1Ziarat Shah 2Fernando Galembeck and 2Maria do Carmo 1Institute of Chemical Sciences University of Peshawar

2 Instituto de Química Universidade Estadual de Campinas, Caixa Postal 6154 Campinas,

SP 13083-862

Abstract: Non-ionic surfactants are organic compounds often use to stabilize the emulsion polymers particles. Latexes are dispersion and their properties are dependent on the use of surfactants concentration and type. However there is not a comprehensive model allowing precise predictions on the effect of surfactants on latex properties. Different latexes of poly[styrene-co-(butyl acrylate)-co-(acrylic acid)], were synthesized under similar experimental conditions and monomer composition by changing the surfactants only. Low-Tg poly[styrene-co-(butyl acrylate)-co-(acrylic acid)] terpolymer latexes were prepared by using a semi-continuous pre-emulsion method carried out at 75˚C under a nitrogen atmosphere and using sodium persulfate as a free-radical initiator. The latexes were characterized using atomic force (AFM), scanning electron microscope (SEM), and transmission electron microscope (TEM), particle size and zeta potential was determined using photon correlation spectroscopy (PCS). Changing the surfactant causes important changes in particle diameter, zeta potential. The IR spectra of the latex films also show definite differences that are assigned to changes in the polymer chain configuration. By using mixtures of nonionic surfactants, it was possible to produce latex with bimodal particle size distribution in a single step. The results of film surface show a great difference in the particles formed, surface properties and in the distribution pattern of stiffness on the film surfaces.

Occurrence and Distribution of Fluoride-Rich Groundwater in Chachro Sub-district, Thar Desert, Pakistan

Tahir Rafique1*, Shahid Naseem2, Tanzil Haider Usmani1 and Muhammad Iqbal Bhanger3

1Applied Chemistry Research Center, PCSIR Laboratories Complex, Karachi

2Department of Geology, University of Karachi, Karachi

3National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro

Abstract: An integrated study with inclusive focus on fluoride (F-) ion contamination was carried out in order to determine its presence and spatial distribution in the groundwater of Chachro sub-district, Thar Desert of Sindh Province. The variation in fluoride content in the groundwater has been illustrated on map of the area, showing that the whole region is affected by this ion contaminant. In 81.57 % of the samples, fluoride values exceeded the limit of 1.5 mg/L


30

recommended by WHO for human consumption. Out of total 331 groundwater samples collected from 316 representative villages, 18.43% (n=61) were found in the range of 0-1.5 mg/L, 29.61% (n=98) in 1.5-3.0 mg/L, 26.89% (n=89) in 3.0-5.0 mg/L and 25.08% (n=83) above 5.0 mg/L respectively. Fluoride concentrations ranged between 0.12-40.70 mg/L with over all mean and median values of 4.96 and 3.09 mg/L, respectively. Considerable positive correlation of F- with pH and bicarbonate, and negative correlation with Ca2+, Mg2+ and the depth of well were observed and found significant for the occurrence and distribution of fluoride in the groundwater. Results obtained from aqueous speciation modeling using PHREEQC reveal that the groundwater is undersaturated with respect to fluorite and oversaturated with respect to calcite, this strongly supports that the plausible geochemical reactions in the study area are precipitation of calcite and dissolution of fluorite minerals.

Global Warming and Food Security - the Impact of Enhanced Atmospheric Carbon Dioxide on Nutritional Balance of Spinach, Cauliflower and Pea

1A. Azam,

1I.Khan,

2B.Lomax and

3A.Mahmood

1Institute of Chemical Sciences, University of Peshawar, Pakistan

2Agriculture and Environmental Science, University of Nottingham, Sutton Bonington Campus,

Sutton Bonington Leicestershire, UK 3Barani Agriculture Research Institution, Chakwal, Pakistan

Abstract: Impact of future atmospheric carbon dioxide concentration on the quality of agricultural products is very important, however comprehensive reports of its effect on the nutritional quality of vegetables arestill rare. In the present study, nutritional quality of spinach (Spinaciaoleraceacv Local), cauliflower (Brassica oleraceacv Snow Grace) and pea (Pisumsativumcv 10691) grown under elevated CO2 was evaluated. Proteins, vitamin C and fat contents of all the three vegetables reduced while sugars and fiber contents increased under CO2 enriched atmosphere. Among the elements, C and H increased while most of the elements analyzed(N, S, Ca, Mg, K, Zn, Mn, Fe, Pb, Ni, Cu, Cr and Cd) decreased for vegetables except Ca for spinach and Mn for pea which increased under elevated CO2. Fatty acid composition of the vegetables was disturbed by elevated CO2; most of the fatty acids were reduced with a major decrease in essential fatty acids, i.e. linoleic and linolenic acids. Elevated CO2 also altered amino acid composition of the vegetables. It was observed that although the yield of vegetables is increased by increased concentration of CO2 in the atmosphere, the quality is adversely affected with decrease in many important nutritional parameters.


31

Estimation of Trace and Toxic Elements in the Samples of Different Cigarette and Wine Brands and their Impact on Human Health of Irish

Arthritis and Diabetic Consumers

Hassan Imran Afridi, Tasneem Gul Kazi, Dermot Brabazon

Mechanical and Manufacturing Engineering, Dublin City University, Dublin, Ireland / National

Center of Excellence in Analytical Chemistry, University of Sindh Jamshoro, Pakistan

Abstract:

The purpose of this study was to determine the levels of trace and toxic metals, chromium (Cr), cadmium (Cd), lead (Pb), manganese (Mn), nickel (Ni) and cobalt (Co), zinc (Zn) in commonly consumed cigarette and wine samples of different brands and arthritis and diabetic consumers biological samples (scalp hair and blood) (n= 135), age ranged (30–55), living in Dublin, Ireland. An age and socio-economics matched 108 nondrinkers and cigarette smokers, residing in the same locality, were selected as referents. These toxic metals were determined using inductively coupled plasma atomic emission spectrophotometry (ICPAES), prior to microwave-assisted acid digestion. The mean values of Cd, Pb, Mn, Ni and Co in the wine and cigarette samples of different brands and in the biological samples of their arthritis and diabetic consumers were significantly higher (p< 0.01). A long-term and/or excessive consumption of cigarette and wines containing heavy metals above the tolerance levels has a hazardous impact on human health. Because different types of cigarette and wines are widely consumed, they contribute a large fraction of the heavy metals intake and, therefore, strict control of these metals is advisable.

Speciation and Evaluation of Arsenic, Species in Underground Water with Fluoride and other Physicochemical Parameters Determination in two

Subdistricts of Tharparkar, Pakistan. A Multivariate Case Study

Kapil Dev Brahman٭, Tasneem G. Kazi, Hassan Imaran afridi

National Center of Excellence in Analytical Chemistry, University of Sindh Jamshoro, Pakistan.

Abstract:

In present study total arsenic, inorganic arsenic species and fluoride ion contamination in underground water of Diplo and Chachro subdistricts of Tharparkar, Pakistan were investigated. The concentration of total As and inorganic As species, F- and others physicochemical parameters were reported in terms of basic statistical parameters, principal component analysis, cluster analysis, sodium absorption ratio and saturation indices. The As3+ was determined by cloud point extraction; where as total inorganic arsenic (iAs) was determined by solid phase extraction. The extracted As species were determined by electrothermal atomic absorption spectrometry. The concentration of As5+ in the water samples was calculated by the difference of the total inorganic arsenic and As3+. F- ion and other anions were determined by ion chromatography. The positive correlation of F- and As species with Na+ and HCO3

- showed that the water with high salinity and alkalinity stabilizes the As species and F- in the groundwater. The positive correlation (r= 0.640 =0.671, p) was observed between total As and it species with F-, Results showed that underground water samples of these two areas of Tharparkar were severely contaminated with arsenic and fluoride ion, which are exceeded the World Health Organization provisional guideline value, and United States Environmental Protection Agency, maximum contaminant level of 0.01mg/L and 1.5 mg/L, respectively.


32

Current Status of Food Irradiation as an Environment Friendly Sanitary and Phytosanitary Technique in Asia and Pacific Countries

Ihsanullah

Nuclear Institute for Food & Agriculture (NIFA),

Tarnab, Peshawar, Pakistan

Abstract:

In order to utilize irradiation as a sanitary and phytosanitary treatment for food and agricultural commodities in the country, food irradiation activities were initiated in Pakistan by Pakistan Atomic Energy Commission (PAEC) in Lahore in 1967. In 1972, the program was shifted to Nuclear Institute for Agriculture and Biology (NIAB), Faisalabad and finally to Nuclear Institute for Food and Agriculture (NIFA), Peshawar in 1982. NIFA is the only institute in Pakistan research and development in the discipline of food irradiation. A Co-60 gamma irradiator was installed at NIFA by IAEA in 1983.The main focus was to develop techniques for conservation of food resources to minimize post-harvest losses and enhance food safety/security and trade. Extensive research work on food irradiation was conducted. The studies included diversified approaches involving laboratory, pilot and commercial scale experiments. A number of IAEA projects on food irradiation were carried out at NIFA. Government of Pakistan has issued legislation in 1996 which covers a variety of foods to be irradiated to diffident doses of radiation for different purposes. Any food (fresh, frozen) fresh fruits and vegetables can be irradiated for disinfestation, shelf life extension and decontamination. Pakistan Nuclear Regulatory Authority awards license to the irradiation facility on the basis of radiation safety At the moment we follow the guidelines as described in Codex Alimentarius. To sterilize medical appliances using Co-60, PAEC established a commercial facility in Lahore, PARAS in 1967. This facility was also providing limited services to food industries in the country. PAEC and Pakistan Horticultural Export Board agreed to build 4 more Commercial Food Irradiators in Karachi, Peshawar, Multan and Quetta. During 2010, the irradiated items (in tones) by PARAS FOODS (pvt) Ltd included mangoes (50), dates (10), potatoes (30), spices (200), pulses (500), rice (50) and meals ready to eat (100). In 2009, around 136 tons of mangoes were irradiated. Status of food irradiation of Pakistan is compared with other countries of Asia and Pacific countries

Arsenic Contents in Groundwater of District Rahimyar Khan, Punjab, Pakistan

Muhammad Tariq Mahar1, Muhammad Yar Khuhawar

2, Mushtaque Ahmed Baloch

1, and Taj

Muhammad Jahangir2

1Center for Environmental Sciences, University of Sindh, Jamshoro, Pakistan

2Institute of Advanced Research Studies in Chemical Sciences, University of Sindh,

Jamshoro, Pakistan

Abstract:

This is a preliminary study based on the analysis of arsenic in groundwater of district Rahimyar Khan, Panjab, Pakistan. 121 samples of the district were analyzed for arsenic. The arsenic contents of the water samples found in the range BDL (below detection limit) - 100 ppb. In the light of results of analysis, it is observed that only 40% water samples were found as unsuitable for drinking purpose on the basis of their arsenic contents.


33

Synthesis and Characterization of CdS-P(NIPAM-co-MAA) Hybrid Microgels

Mohammad Saleem Khan*, Gul Tiaz Khan,

1National Centre of excellence in physical Chemistry university of Peshawar,

Peshawar-25120, Pakistan

Abstract: N-isopropylacrylamide (NIPAM) and Methacrylic acid (MAA) copolymer microspheres with various compositions were prepared by emulsion polymerization technique and characterized by Fourier transform infrared spectroscopy (FTIR) and their hydrodynamic radius were determined using Dynamic Laser Light Scattering. The effects that the pH, temperature and salt concentration have on the microgel particles were investigated. The microspheres thus prepared were employed as micro-reactors for the deposition of semiconductor cadmium sulfide (CdS) nanoparticles. The obtained composite was characterized using optical, structural and thermal techniques. The results indicated that the microgels were stable under thermal conditions up to 200 ºC. The crystal structure and grain size of Cadmium sulfide-poly (isopropylacrylamide-co-methacrylic acid) [CdS-P(NIPAM-co-MAA)] hybrid microgels was studied by using X - ray Diffraction. The optical properties of the samples were examined by UV – Visible spectroscopy and photoluminescence spectroscopy. It was also found that the synthesized nanoparticles have a blue shift at about 360 nm to a higher energy which is due to the typical quantum confinement effects.

Monitoring of Gamma Radiolytic Degradation Products of Aqueous Methoxychlor: Preconcentration study by Solid Phase Micro-extraction

Amina Zafar1,*, Shahid bilal Butt1, Muhammad Riaz2

1Central Analytical facility Division, PINSTECH, Islamabad, Pakistan

2Chemistry Division, PINSTECH, Islamabad, Pakistan

Abstract:

The study of toxic chemicals is an essential area regarding their monitoring, removal and management for sustainable development. To eliminate these toxic contaminants from water and waste water different approaches are adopted. Among them gamma radiolysis is an emerging tool. This ionization radiation generates highly reactive radicals that react with pollutants and hence eliminate them. Since trace and ultra trace products and parent compound are to be monitored. Therefore, solid-phase micro-extraction (SPME) procedures were developed for the successful pre-concentration of degraded organic pollutants. In this research work, degradation of priority organic pollutant methoxychlor in water by gamma irradiation under varied experimental conditions was investigated. A SPME fused-silica fiber coated with Polyacrylate was used as a probe to extract the organic pollutant after irradiation. Post-research reactor operation with a dose rate of 200 Gyh-1 was used as a source for gamma irradiation with a varied accumulated dose of 1-5 kGy. The degree of gamma radiolytic degradation was monitored by HPLC-UV and GC-MS. The degradation products were identified by GC-MS after comparing their mass spectra with the NIST mass spectral library. Substituted chlorophenols were identified as major degraded products. However at higher dose of 5 kGy the degradation products were completely eliminated. The attained degradation of methoxychlor was ~ 95 %.


34

Potential use of Peat in Brunei Darussalam: Application of Peat as Low Cost Biosorbent for Removal of Cu(II) and other Metal Ions from Industrial

Waste Water Effluents

Tasneem Zehra*1, Linda B. Lim

1, DTB Tennakoon

1, Namal Priyantha

2, M. Tahir Soomro

3

1 Faculty of Science, Department of Chemistry, Universiti Brunei Darussalam, Jalan Tungku

Link, Gadong, BE 1410, Negara Brunei Darussalam 2Department of Chemistry, University of Peradeniya, Peradeniya, Sri Lanka

3National Centre of Excellence in Analytical Chemistry Jamshoro, Pakistan

Abstract: Peat has been used as a fuel in many countries such as Ireland, England, the Netherlands, Germany, Sweden, Poland, Finland and the USSR. Brunei is blessed with a large supply of peat. About 18% of the land area in Brunei consists of peat lands. Hence peat is a possible future source of energy for Brunei. Energy contents of peat could be expressed as its calorific value. Peat samples were collected from 3 different locations in Brunei Darussalam. Calorific values of the peat samples were determined using bomb calorimeter. Results indicate that the peat in Brunei Darussalam is of good quality and could be used as a resource for energy purposes. Other than that, peat could be used as an adsorbent for the removal of toxic materials such as heavy metals and dyes from waste water. The following study aimed to remove Cu(II) and other metal ions from real industrial effluents using low cost biosorbent i.e., peat. There are several effects that we have investigated for increasing the efficiency of peat in removing metal ions such as pH of the solution can play very important role beside that we can also modified peat with some other material like graphite, nanocarbon etc. The results showed that peat in Brunei Darusaalam could be used as an efficient and low cost biosorbent for removing metal ions from industrial or waste water effluents.

Simultaneous Preconcentration and Determination of Nickel and Cobalt using Functionalized Nanosized Silica Particles by ICP-OES

*Maria Sadia, *M. Rasul Jan, *Jasmin Shah and �Gillian M. Greenway

*Institute of Chemical Sciences, University of Peshawar, K.P.K., Pakistan

� Department of Physical Sciences, University of Hull, United Kingdom

Abstract: In this work functionalized nanosized silica particles have been utilized for the simultaneous preconcentration of nickel and cobalt. The silica nanoparticles (SiNPs) prepared by the sol-gel method were functionalized with sodium diethyldithiocarbamate (DDTC-SiNPs). They were characterized by SEM, TEM, XRD and FTIR. The adsorption efficiency of DDTC-SiNPs was examined by batch equilibrium technique. The DDTC-SiNPs showed 100 % adsorption for Ni (II) and Co (II). The effect of changing variables such as pH, shaking time, sample volume, preconcentration factor, eluent type and volume were investigated so as to obtain maximum recovery with high selectivity over interfering ions. The maximum adsorption capacity was found to be 15.15 mgg-1 and 11.80 mgg-1 for Ni (II) and Co (II) respectively using DDTC-SiNPs. 100 % recovery was achieved with 5 mL of 2 M HNO3. The maximum precocentration factor was 400 and the 3σ limits of detection were 0.201 µgL-1 and 0.198 µgL-1 for Ni (II) and Co (II)


35

respectively. Thermodynamic studies showed that adsorption of Ni (II) and Co (II) on DDTC-SiNPs is exothermic with enthalpy changes of -0.514 KJ mol-1 and -0.854 KJ mol-1 for Ni (II) and Co (II) respectively. The method was applied to the preconcentration and determination of Ni (II) and Co (II) from tap, river and sea water.

Synthesis, Characterization, X-ray Structure, Biological Screenings and Interaction with Salomon Sperm DNA of Potential Bioactive

Schiff Base Compounds

Muhammad Sirajuddin, Saqib Ali*

Department of Chemistry, Quaid-i-Azam University, Islamabad

Abstract: The Schiff base compounds, 4-tert-butyl-N'-(2-hydroxy-3-methoxybenzylidene)benzohydrazide (1), N'-(5-bromo-2-hydroxybenzylidene)-4-tert-butylbenzohydrazide(2) and N'-(2-hydroxy-3-methoxybenzylidene)-4-methylbenzenesulfonohydrazide (3) were synthesized and characterized by elemental analysis, FT-IR, 1H, 13C NMR spectroscopy and single crystal analysis. The title compounds have been screened for their biological activities including enzymatic study, antibacterial, antifungal, cytotoxicity, antioxidant and interaction with SS-DNA, and showed remarkable activities in each area of research. The DNA binding of the compounds 1-3with SS‐DNA has been carried out with absorption spectroscopy, which reveals that all the compounds show binding propensity towards SS‐DNA via intercalation mode of interaction. In intercalation, the compound inserts itself into the base pairs of DNA and the compound-DNA complex is stabilized by π-π stacking.DNA viscosity experimental results further suggested that all the compounds intercalate into the base pairs of DNA.The synthesized compound were also found to be effective antioxidant of 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) and show almost comparable antioxidant activity to that of the standard and known antioxidant, ascorbic acid.

Fabrication of Molecularly Imprinted-based Fiber for Solid-phase Microextraction and Gas Chromatographic Determination of Endosulfan

Huma I. Shaikh, Najma Memon*, M. Iqbal Bhanger and S. M. Nizamani

National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro,

Sindh-Pakistan

Abstract: A molecularly imprinted polymer with endosulfan as the template molecule was synthesized and used as the coating for solid-phase microextraction of endosulfan I and II for their selective determination. A method based on solid-phase micro extraction (SPME) and gas chromatography with micro-electron capture detection (GC-µECD) has been optimized for the analysis of endosulfan I and II in water samples. The influence of parameters such as temperature, fiber coating, salting out effect, pH, extraction and desorption time on the extraction efficiency has been studied by means of a multivariate factorial design, which allowed the study of main

effects as well as two factor interactions. Finally, a method based on direct SPME at 50 °C, at pH

1 is proposed. The method showed good linearity (r2 = 0.997) and repeatability (RSD < 6 %) for endosulfan I and II, with detection limits ranging from 0.011 to 0.018 µg ml-1. Reliability was


36

demonstrated through the evaluation of the recoveries in different water samples, such as river water and waste water. These studies demonstrated the validity of external standard calibration to quantify the target compound in real samples. The fiber was also characterized in terms of morphology and a uniform distribution of the coating was obtained.

Treatment of Cattle Slaughterhouse Wastewater by Electrocoagulation Method using Aluminium Electrodes

Muhammad Kaleem Khosa, Mohsin Raza, Khalid Mahmood Zia, Hafiz Muhammad Shoaib

Department of Chemistry, Government College University Faisalabad, Pakistan.

Abstract: Cattle slaughterhouse wastewater is treated by electrocoagulation method with aluminium electrodes in batch reactor. The effect of different parameters, pH, electrolyte concentration, and current density was studied. The evaluation of treatment efficiency was determined by measuring both the reduction of chemical oxygen demand (COD) and residual turbidity. It showed that the optimum removal efficiency was achieved when the wastewater initial pH, coagulant dosage and current density was 7.8, 0.05M and 2.16A/m2 respectively. Under optimum conditions, the removal efficiency was 88% and 99.3% for COD and turbidity. The COD of wastewater was analyzed by closed reflux method, using UV-spectrophotometer.

Rapid Determination of Free Fatty Acid Content in Waste Deodorizer Distillates Using SB-ATR-FTIR

STH Sherazi

National Center of Excellence in Analytical Chemistry, University of Sindh Jamshoro, Pakistan

Abstract: A simple, rapid, economical and environmental friendly analytical method was developed for the quantitative assessment of free fatty acids (FFA) present in deodorizer distillates and crude oils by single bounce attenuated total reflectance (SB-ATR) FTIR method. Partial least squares (PLS) was applied for the calibration model which based on the peak region of carbonyl group (C=O) from 1,726–1,664cm-1 associated with the free fatty acids. The proposed method totally avoided the use of organic solvents or costly standards and could be applied easily in the oil processing industries. The accuracy of the method was checked by comparing conventional standard AOCS titrimetric procedure which provided good correlation R= 0.99995 with the standard deviation (SD) of ±0.05%. Therefore, proposed method could be used as an alternate to AOCS titrimetric method for the quantitative determination of FFA especially in the deodorizer distillates


37

Adsorptive Removal of Congo Red and Sunset Yellow Dyes from Water Systems by Lady Finger Stem

1*Aadil Abbas,

2Rabia Rehman*,

1Shahzad Murtaza,

2Tariq Mahmud,

1Rabia Ayub

1Department of Chemistry, University of Gujrat, 50700 Gujrat. Pakistan,

2Institute of Organic Chemistry, University of Innsbruck, 6020 Innsbruck, Austria

Abstract: In this research work two anionic dyes, i.e. Congo Red and Sunset Yellow were removed successfully from aqueous media by Lady Finger stem in batch mode. Operational conditions optimization showed that agitation speed and particle size did not affect much in adsorption of these dyes; but contact time, pH, adsorbent dose and temperature of system effects the adsorption rate. Optimized conditions of adsorption for Congo Red dye were: 40 minute contact time, 8.0 pH, 0.5 g adsorbent dose, 40-60 microns mesh sized particles, 150 rpm agitation speed and 50 ºC temperature. Whereas for Sunset Yellow optimized conditions were: 30 minute contact time, 2.0 pH, 2.5 g adsorbent dose, 20-40 microns mesh sized particles, 50 rpm agitation speed and 30 ºC temperature. Suitability of equilibrium data was modulated with Langmuir, Freundlich and Temkin models and found that both physiosorption and chemisorption processes play important role in adsorption of these dyes by Lady Finger stem. The results demonstrated that Lady Finger stem can be efficiently employed on larger scale wastewater treatment.

Impact of Arsenic Level in Livestock Drinking Water on Cow’s Raw Milk using Graphite Furnace and Hydride Generation Atomic Absorption

Spectrometry

Sadia Ata*, Tanzeelagulabshahzady ‡ Institute of Chemistry, University of the Punjab, New Campus Lahore 54590, Pakistan

Abstract: Cow milk is an essential component for growth and maintenance of human; it should be free from all types of toxic substances. It is therefore, important to control heavy metal and other carcinogenic and hazardous materials like arsenic, in milk. The ultra-tracer level of arsenic usually found in water lead to the use of sensitive, reliable, and accessible method. In this research, Hydride generation coupled with atomic spectrometry and graphite furnace atomic absorption technique was optimized, validated and compared in terms of recovery and limit of detection for the estimation of As(III) in drinking water and cow’milk. Comparatively, GF-AAS technique was evaluated better than HG-AAS having minimized analyte losses and less matrix interferences in water and milk matrix for As (III) evaluation. The level of total arsenic in cow’ milk and in the drinking water were measured and compared, in order to build up impact of arsenic concentration in livestock drinking water relay on final presence of arsenic in raw milk from kasur’dairy forms. Mineralization of milk’sample was evaluated using potassium dihydrogen phosphate under graphite furnace atomic absorption technique (GF-AAS) and magnesium nitrate under hydride generation atomic absorption technique (HG-AAS). The recovery data of spiked level 2.5ug/l,5.0ug/l and 7.5ug/l of arsenic in milk were 88±2.2%,98±1.5% and 104±2.0% using GF-AAS. The accuracy values with same spiking level of arsenic in milk were 96± 2.1%, 96±1.8%, 92±1.8% using HG-AAS. Detection and quantification


38

limits of GF-AAS and HG-AAS were 1.23 µgL-1 and 3.69 µgL-1, 0.8ug/l and 2.4 ug/l respectively. The results exhibited a biological devolution level of arsenic to the cow milk from the drinking water intake.The arsenic amount found in all dairy farmswas higher than the limits adopted by the World Health Organization (WHO) that is 10 µgL-1.

Potential use of Desert Plant, for the Removal of Textile Dye

Warda Hassan1, Umar Farooq

2, Karamt Mahmood

1, Misbahul Ain Khan

1

1The Islamia University of Bahawalpur.

2 Institte of Chemistry, Punjab University, Lahore

Abstract: Conventional technologies for the removal of dyes from the waste water are proving expensive due to non–regenerable materials used and their high costs. The use of dried biomass of Haloxilon recurvum plant stems (HRS) was studied for the removal of textile dye from its aqueous solutions. The biosorbent material was characterized by different techniques such as: scanning electron microscopy (SEM) and elemental analysis. FTIR studies, revealed a variety of functional groups on the plant surface including carboxyl and amino groups. The pH at the point of zero charge (pHpzc) was found to be 6.3. The dye uptake by the plant increased with increasing pH, time of contact and dye concentration. The extent of dye removal decreased with increase in the temperature as well as the particle size of the biomass. Lagergren’s Pseudo first order and the pseudo second order models were used to study the kinetics. The Langmuir and Freundlich equilibrium models were studied and the qmax was found to be 22.93mg/g. The changes in the values of free energy (∆Go) and enthalpy (∆Ho) indicated the spontaneous, feasible and exothermic nature of sorption process. Haloxilon recurvum plant is locally available in large quantities, so the powdered stems can act as cost-effective and ecofriendly biosorbent for the removal of the dye from its aqueous solutions. The results in this study indicated that HRS biomass was very attractive material, for removing dye from textile effluents, than many of those reported in the literature.

Harvesting the Solar Light Employing Food Dyes as Sensitizers for Dye-Sensitized Solar Cells

Iqbal Ahmada *

, Safeer Ahmeda , Shahzad Murtaza

b

aDepartment of Chemistry, Quaid-i-Azam University Islamabad

bDepartment of Chemistry, University of Gujrat Gujrat

Abstract: Two commercial food dyes namely sunset yellow (SY) and tartrazine (TZ) have been used as photosensitizers to fabricate dye-sensitized solar cells (DSSCs). These dyes have been characterized by voltammetric techniques (cyclic voltammetry, differential-pulse voltammetry and square-wave voltammetry) , UV/Visible spectroscopy and density functional theory and the obtained parameters revealed that these dyes are suitable for DSSCs. ZnO has been synthesized potentiostatically on fluorine doped tin oxide (FTO) conducting glss as a photoanode and characterized by XRD and SEM. XRD results revealed the formation of single phase of ZnO with average crystallite size ~29 nm. SEM analysis showed the uniform, homogeneous and porous


39

morphology of ZnO thin film fabricated on FTO glass. Electrochemical impedance spectroscopy has been used to investigate the charge transfer and charge recombination processes occurring within the DSSCs and the impedance data showed that the overall charge recombination process is slow as compared to charge transfer processes. Further performance of DSSCs has been assessed by current-voltage measurements and the solar energy to electric current conversion

efficiency (η) is found to be 0.27% and 0.28% for SY and TZ, respectively.

A Direct Approach Towards the Preparation of Intermediates to the Synthesis of Amaryllidaceae Alkaloids from Morita-Baylis-Hillman Adducts

Hamid Ullah, Kristerson Reinaldo Luna-Freire and Fernando Coelho*

Laboratory of Synthesis of Natural Products and Drugs, Institute of Chemistry, University of

Campinas, UNICAMP, 13084-971, Campinas, SP, Brazil.

Abstract: Plants from the Amaryllidaceae family are famous due to its pharmacological relevance. Due to having potent biological activities and highly sophisticated substitution pattern of the carbon skeleton, many of these alkaloids, induced the interest of the organic synthesis community. The goal of this work is the total synthesis of plicamine skeleton and Narciclasin skeleton from Morita-Baylis-Hillman (MBH) adducts.

Our approach begins with MBH adduct 2 which was obtained from aldehyde 1 in 82% of ionic liquid ([bmim]Br). The secondary hydroxyl group was protected and the ester group was reduced with DIBAL-H to give3 in 92%, which in turn was protected and then ozonolysed to afford 5 in 85%. The carbonyl group of 5 is used as substrate for oximation and successive reduction to the corresponding amine 6 in 77% yield, which in turn will be used toward the synthesis of 7 (Scheme 1).

Scheme 1

O

O Br

O

1

1) Methyl acrilate,DABCO, r.t. 82% O

O Br

OH

MBH adduct (2)

O

O 1) Cl3NHOPMB,

CH2Cl2, CSA,

r.t., 18h, 95%

2) DIBAL-H,

CH2Cl2, -78 0C,

2h, 89%

O

O Br

O OHPMB

3

1) Imidazole, TBSClDMF r.t., 4h, 92%

O

O Br

O OTBSPMB

4

1) O3, MeOH,

- 72 0C, then

S(CH3)2, 85%

1) i. NH4OCl, pyr,

MeOH;

ii. NaBH4, MoCl5NaHSO4.H2O, 77%

O

O Br

O

R

OTBSPMB

5, R= C=O

6, R= NH2

O

O

O

NR

OTBSPMB

O

R= p-hydroxy-phenethyl

ADVANCED

INTERMEDIATE

7

The synthesis of 6 is described in 6 steps from MBH adduct 2. This intermediate should allow the access to an advanced intermediate 7, that could be used in the synthesis of Amaryllidaceae alkaloids.


40

Synthesis and Characterization of Processible Soluble Polyaniline Salts

Salma Gula, Anwar-ul-Haq Ali Shah

b, Salma Bilal

a *

aNational Centre of Excellence in Physical Chemistry, University of Peshawar

bInstitue of Chemical Sciences, University of Peshawar

Abstract:

Polyaniline (PANI) is one of the most promising candidates for possible technological applications. PANI has potential applications in batteries, anion exchanger, tissue engineering, inhibition of steel corrosion, fuel cell, sensors and so on. However, its insolubility in common organic solvents limits its range of applications. In the present study an attempt has been made to synthesize soluble polyaniline salt via inverse polymerization pathway using benzoyl peroxide as oxidant and dodecylbenzenesulfonic acid (DBSA) as dopant as well as a surfactant. A mixture of chloroform and 2-butanol was used as dispersion medium for the first time. The influence of synthesis parameters such as concentration of aniline, benzoyl peroxide and DBSA on the yield and other properties of the resulting PANI salt was studied. The synthesized PANI salt was found to be completely soluble in DMSO, DMF, chloroform and in a mixture of toluene and 2-propanol. The synthesized polymer salt was also characterized with cyclic voltammetry, SEM, XRD, UV-Vis spectroscopy and viscosity measurements. TGA was used to analyze the thermal properties of synthesized polymer. The extent of doping of the PANI salt was determined from UV-Vis spectra and TGA analysis. The activation energy for the degradation of the polymer was calculated with the help of TGA

Physical Properties, Chemical Composition and Antimicrobial Activity of Essential Oil Extracted from Cupressus Sempervirens

Zahed Mahmood1, Muhammad Usman Qamar Saeed1, Shaukst Ali Shahid 2 and Farooq Anwar3

1Department of Chemistry & Biochemistry, University of Agriculture,

Faisalabad-38040, Pakistan

2Department of Physics, University of Agriculture, Faisalabad-38040, Pakistan

3Department of Chemistry, University of Sargodha, Sargodha -40100, Pakistan

Abstract: The widening trade gaps necessitate the search for new sources for essential oil and to develop their potential, pharmaceutical and commercial spectrum. Cupressus Sempervirens plant which despite its exotic legendary attributes has been almost ignored up to now was selected for this purpose. The essential oil from needles and twigs of plant was extracted by steam distillation technique and various physical and chemical parameters were determined, i.e., specific gravity, refractive index, acid and ester values and composition profile by gas liquid chromatography. The antimicrobial properties of oil were investigated by flask culture and diffusion method. In flask culture method two fungal strains viz. A. niger and A. flavous demonstrated positive antifungal results while in diffusion method five strains of fungus viz. A. niger, A. flavous, A. Penecillium

digitatum and Candida uterus and three strains of bacteria viz. E. coli, M. leutius, B. lacto illustrated 100% results.


41

Novel Bis-Pyrrolidinium Compounds as Multi-Site Phase-Transfer Catalysts: Application in Williamson Etherification

Muhammad Jawwad Saif

Department of Applied Chemistry, Government College University Faisalabad – Pakistan

Abstract: This work describes the synthesis of some novel bis-pyrrolidinium compounds and its application in Williamson etherification reaction in aqueous/organic two-phase medium. A rational mechanism of the etherification is proposed based on the experimental results and a kinetic model is proposed. The novel multi-site phase-transfer catalysts demonstrated higher catalytic activity than the conventional cetyltrimethylammonium bromide & tetrabutylammonium bromide “single-site” quaternary ammonium salts.

Geochemistry and Origin of Petroleum from Cretaceous Reservoirs, Lower Indus Basin, Pakistan

Arif Nazir* and Tahira Fazeelat

Chemistry Department, University of Engineering & Technology, Lahore

Abstract: The study focused on the petroleum geochemistry of crude oils produced from Cretaceous reservoirs and to ascertain genetic liaison among them. Geochemical portrayal of crude oils has been carried out by means of bulk properties and diagnostic biomarker parameters. Full suite of n-alkanes, low isoprenoid/n-alkane ratios, elevated saturates/aromatics ratios and absence of unresolved complex mixture (UCM) indicate typical non-biodegraded light crude oils. Low sulfur (<1 %) and high Pristane/Phytane ratio (2.14-5.27) suggest abundant non-marine source organic matter (OM) deposited in highly toxic depositional environments. Compositional distribution of hydrocarbons clearly indicates paraffinic natures of these crude oils. Biomarker parameters like relative distribution of steranes (C27-C28-C29 ααα-20R steranes), C19 and C23 tricyclic terpanes (TT), C24 tetracyclic terpanes (TeT) and hopanes (steranes/hopanes ratio, oleanane index) suggest that the crude oils contain terrigenous OM mixed with small input of marine OM. The crude oil samples are mature for carbon preference index (CPI), odd even predominance (OEP), Pr/n-C17 and Ph/n-C18 ratios, C32 22S/(22S + 22R) homohopanes while for the C29 sterane isomerization ratios [20S/(20S + 20R), αββ/(αββ+ ααα)] the crude oil samples are produced from the source rocks at early mature stage to mature stage. Bulk analyses and biomarker parameters indicate these crude oils contain mixed source OM, deposited in oxic depositional environments and have reached to the early to peak thermal maturity. The study also indicates more than one source origin of these hydrocarbons and is an initiative to understand petroleum source, formation, migration and accumulation in Cretaceous reservoirs of the Lower Indus Basin.


42

Application of Rapidly Generated Bidentate Ligand Libraries to Rhodium Catalyzed Reductions

1Tariq Zaman*,

1Habib Nasir,

2Robin Frauenlob, and

2Enda Bergin

1School of Chemical & Materials Engineering, NUST, H-12, Islamabad, Pakistan, 44000

2School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland

Abstract:

A study for the combinatorial catalysis of bidentate ligands – allowing direct screening of the products without the need for isolation or purification – has been employed in a rhodium catalyzed hydrosilylation. Four different ligand families have been examined: oxazolines, imines, aminals and bis-imines, with a small library of each type produced and directly screened in the reaction. In each class a ligand providing an ee of 70% in this very demanding reaction was identified, and ees and conversions were equivalent whether the ligand was obtained in purified form or as a crude mixture.

Ph Me

O

PMHS, toluene

OH

MePh*

R1

OR2NH2+

[RhCp*Cl2]2R1

NR2

A New Facile One-Pot, Three-Component Method for the Synthesis of N-(4-Acetyl-5-methyl-1,3-oxathiol-2-ylidine)benzamides

Aamer Saeed Bhatti, Asma Khurshid

Quaid-I-Azam University Islamabad

Abstract: 1,3-Oxathiol-2-ylidenes have got importance as an important heterocylic nucleus in view of its synthetic strategies. The present research paper reports one- pot, three-component synthesis of 1, 3-oxathiol-2-ylidene benzamides as a result of reflux between aroyl isothiocyanates, ethyl-2-chloro acetoacetate and N-methyl imidazole using acetonitrile as a solvent.

C

R

O

NO

S

Me

C

O

OEt

1,3-oxathiolan-2-ylidenes have an exocyclic imine group that can be used in the organic synthesis for the preparation of biological active compounds. 1,3-oxathioles are not common and their properties remain unexplored. One- pot, three-component reactions have attracted considerable attention in organic synthesis as they can produce the target products in a single operation without isolating the intermediates and thus reducing the reaction times and energy and hence increasing the chemical yield.


43

New Thermophilic Cellulases Enzymes Production by Humicola gyrsia

M. Javaid Asad *†, Nazia Mehboob *, M. Asghar** and M. Gulfraz*

Department of Biochemistry,

*PMAS Arid Agriculture University Rawalpindi, Rawalpindi,

**Department of Chemistry and Biochemistry, University of Agriculture, Faisalabad.

Abstract:

In this study extremozymes were produced by a thermophillic Aspergillus sydowii. The extremozymes (Endoglucanase, Endoglucanase and β-glucosidase) production was optimized by studying the effect of incubation period, pH, temperature, moisture level, addition of carbon and nitrogen sources, inoculum size, effect of surfactants like tween-20, tween --80 and SDS, effect of mediators like urea, peptone, cane molasses, yeast extract, ammonium sulphate and effect of different metal ions. Maximum Endoglucanase activity (4.12 IU/mL/min) was observed at 55 0C temperaure, 5.0 pH, 2 mL inoculum, 70 % moisture and maximum Exooglucanase activity (3.98 IU/ml/min) was observed at 55 0C, 5.0 pH, 3 ml inoculum and 60 % moisture level. β-glucosidase showed maximum activity (4.29 IU/ml/min) at 55 0C, 5.5 pH, 2 ml inoculums size, 80% moisture level. The optimum cultural conditions for endoglucanse were glucose (0.3 %), peptone (0.3 %), tween-80 (0.2 %), and cane molasses (0.4 %). While, fructose (0.3 %), urea (0.4 %), tween-80 (0.3 %) and ammonium sulphate (0.2%) were most suitable conditions for exoglucanase. β-glucosidase gave maximum activity at (0.2 %) glucose, (0.2 %) peptone, (0.2 %) tween-20 and (0.3 %) ammonium sulphte. The enzymes produced were subjected to purification by ammonium sulphate precipitation and gel filtration chromatography. Maximum precipitation was observed at 60 %, 40 % and 40 % of ammonium sulphate for endoglucanase, exoglucanase and β-glucosidase respectively. The purified enzymes were characterized with regard to pH, temperature, substrate specificity and kinetic parameters such as Km and Vmax. All three extremozymes showed maximum activity at 55 0C temperature and 5.0 pH. Metal ions like Ca2+, Mg2+ and Zn2+ enhanced the activity of the three extremozymes. The Km and Vmax was found to be 5.19 µM/min and 9.53 mM, 5.56 µM/min and 8.45 mM, 2.51 µM/min and 4.21 mM for endoglucanase, exoglucanase and β-glucosidase, respectively.

Gemmotherapy: A New Way to Treat Cardiac Diseases

Nazish Jahan, Khalil-ur-Rahman

Department of Chemistry and Biochemistry,

University of Agriculture Faisalabad

Abstract: In this study we investigate a newly emerging way of therapy, the gemmotherapy to treat the myocardial infarction induced by isoproterenol in rabbits. Gemmotherapy is super active form of medicine with powerful medicinal potential, made from embryonic tissues and fresh germinating parts of plants. To assess the cardioprotective potential of gemmomodified and seed extract of Trigonella foenum in rabbits, both curative and preventive mode of treatment were selected. In curative cardioprotective activity ischemia/myocardial infarction was induced in rabbits and then plant doses fed orally to ischemic/ myocardial infarcted rabbits once daily for


44

four days. In preventive cardioprotective activity experimental animals were pretreated with three different doses of both extracts of Trigonella foenum for 21 days and then myocardial infarction was induced with isoproterenol. The level of cardiac marker enzymes (CK-MB, AST, ALT, LDH), lipids (cholesterol, triglyceride, LDL, HDL), and antioxidants enzymes (SOD, CAT) were analyzed in serum and heart tissues of rabbits. Isoproterenol significantly (p<0.001) increases the secretion of cardiac enzymes in the serum of different experimental rabbits. The three week pretreatment and curative treatment of rabbits with gemmomodified extract of T. foenum

decreased the elevated cardiac enzymes and lipids level. Gemmomodified plant extract also restored the antioxidants level equal to normal. HPLC analysis of the extracts confirmed the presence of important flavonol and phenolic acids in both gemmomodified and seed extracts. Results of this study revealed the better cardioprotective potential of gemmomodified extract than seed extract of Trigonella foenum.

Synthesis and Characterization of Chiral 2,5-disubstituted 1,3,4-thiadiazoles and their Derivatives

Maria Shafique and Shahid Hameed

Departmaent of Chemistry, Quaid-i-Azam University, Islamabad-45320, Pakistan

Abstract: The synthesis of N-(1-(5-amino-1,3,4-thiadiazol-2-yl)alkyl)-4-arylsulfonamides (7-12) was carried out by the condensation of N-(4-chloro/methylbenzenesulfonyl)amino acids (1-6) with thiosemicarbazide in the presence of phosphorous oxychloride. N-(4-Chloro/methylbenzenesulfonyl)amino acids (1-6) were in turn synthesized by the reaction of three different amino acids (alanine, valine and leucine) with 4-chloro/methylbenzenesulfonyl chloride. The synthesized N-(1-(5-amino-1,3,4-thiadiazol-2-yl)alkyl)-4-arylsulfonamides (7-12) were further derivatized to N-(1-(5-(N-arylsulfonyl)amino-1,3,4-thiadiazol-2-yl)alkyl)-4-arylsulfonamides (13-36) and N-(5-(1-(4-methylphenylsulfonamido)ethyl)-1,3,4-thiadiazol-2-yl)benzamide (37) using different arylsulfonyl chlorides and benzoyl chloride, respectively. Reaction conditions were optimized to get the desired products in good yields. Structures of the target products were confirmed by available spectroscopic techniques.

HN

NN

S NH2

R

SOO

X

HN

NN

S NH

R

SOO

X O

HN

NN

S NH

R

SOO

X

S

Y

OO

ArCOCl ArSO2Cl

(7-12)

(13-36)(37)


45

Microwave Treated Saccharum Bengalense as an Eco Friendly Biosorbent for the Removal of Toxic Congo Red Dye from Aqueous Solution-A Green

approach

Muhammad Imran Din*1, Muhammad Latif Mirza

2, Muhammad Makshoof Athar

1,

Asma Tufail Shah1 1Institute of Chemistry, University of Punjab, Lahore-54590, Pakistan

2Department of Chemistry, The Islamia University of Bahawalpur, Pakistan

Abstract:

In the present study microwave treated Saccharum bengalense (MW-SB) was investigated a potential biosorbent for the removal toxic Congo Red (CR) dye. The effect of various operating variables, viz., adsorbent dosage, pH, contact time and temperature on the removal of dye has been studied. Nearly 99.99% removal of dye is possible at about 30 minutes; at a pH 2.0 under the batch test conditions. It was found that the pseudo-second-order mechanism is predominant and the overall rate of the dye adsorption process appears to be controlled by the more than one-step. The intra- particle diffusion model was applied to investigate the rate determining step. Langmuir, Freundlich and Dubinin–Radushkevich (D–R) adsorption isotherms models were applied to describe the biosorption isotherm. The biosorption data was better represented by Langmuir model. The biosorption efficiency of MW-SB biosorbent has also been compared with unmodified material Saccharum bengalense (SB). It was found that the sorption capacity (qmax) increased from 7.4 mg/g to 114.9 mg/g on MW treatment. Thermodynamic parameters such as free energy change (∆G°), enthalpy change (∆H°) and entropy change (∆S°) have been calculated respectively, revealed the spontaneous, endothermic and feasible nature of adsorption process. The preparation of MW-SB did not require any additional chemical treatment and less time is required to possess high adsorption of CR dye. Thus, it is in agreement with the principles of green chemistry. The results of the present research suggested that MW-SB can be used an environmentally and economically feasible alternative biosorbent for the removal Congo Red dye from aqueous solutions.

Characterization of Crude oils of Southern Indus Basin, Pakistan on the basis of Physiochemical properties and GCMS analysis of saturated

fractions

Shagufta Nasir, Fazeelat Tahira

University of Engineering and Technology Lahore

Abstract:

A suit of twenty crude oils from various oil fields of Southern Indus Basin have been analysed for characterization in this study. Bulk properties like API, Pour point and sulfur contents were used for the grouping of the crude oils. Four of the twenty crude oils show API values between 33-39, seven crude oils have API ranging from 41-45 and rest nine oils have API value between 46-60 indicating three groups of the Southern Indus Basin oils, i.e. medium light and condensates. Pour points show a wide range -14˚C – 24˚C and sulfur contents are negligible. Total ion gas chromatograms of the saturated fractions of the Crude oils revealed that these oils contain abundance of n-C20+ n-akanes indicating waxy nature and input of terrigeneous organic

matter in Southern Indus Basin oils.


46

Redox Behaviour of 4-[(E)-(thiophene-2-ylmethylidene)amino]benzenesulfonamide and Kinetics of its Interaction

with Deoxyribonucleic Acid

Muhammad Aslam Malana, Ayesha Batool, Zahid Hussain Chohan and Iqbal Ahmad


Abstract: Electrochemical behaviour of 4-[(E)-(thiophene-2-ylmethylidene)amino]benzenesulfonamide was investigated using voltammetric techniques (cyclic voltammetry, differential pulse voltammetry and square wave voltammetry). Cyclic voltammetric studies of this compound showed a well defined reduction peak ascribed for copper (II) / copper (I) whereas quasi reversible nature of 4 -[(E)-(thiophene-2-ylmethylidene)amino]benzenesulfonamide was confirmed by square wave voltammetry. Differential pulse voltammetric studies of this compound revealed involvement of one electron in its redox process. The interaction of 4-[(E)-(thiophene-2-ylmethylidene)amino]benzenesulfonamide with DNA was also undertaken using cyclic voltammetric and uv / visible spectrophotometric methods. It was found that mode of binding of the 4-[(E)-(thiophene-2-ylmethylidene)amino]benzenesulfonamide with DNA was of intercalation type. Binding of 4-[(E)-(thiophene-2-ylmethylidene)amino]benzenesulfonamide with DNA followed Ist order kinetics and value of the rate constant for this reaction was calculated to be 1.43x10-3 sec-1

WAXD Characterization of Rice Husk Cellulose

Noor Rehman, Simone M. L. Rosa, Maria Inez G. de Miranda, Sônia M.B. Nachtigall,

Clara I. D. Bica

Institute of Chemistry, Federal University of Rio Grande do Sul (UFRGS), Brazil

Abstract:

In the last few decades, all over the world, there has been a growing interest in the development of “green” technologies which make possible the use of products not harmful to the environment and implies the development of chemical processes and products that lead to a cleaner, healthier and more sustainable environment. With the aim of reaching sustainability, many studies have been done on extracting cellulose micro fibrils and on isolation of whiskers from various sources using them as reinforcement in composite manufacturing. In present work we report the cellulose extraction and bleaching from rice husks by means of an environmental friendly process. X-ray diffraction (WAXD) was used a main technique to calculate the crystallinity index (around 70 %) showed that the overall process was adequate to obtain cellulose with high crystallinity when it was compared with corn straw and commercial microcrystalline cellulose. Moreover, supplementary techniques as infrared absorption spectroscopy (ATR-FTIR), of extracted cellulose showed that, after bleaching, lignin and hemicellulose were efficiently removed from the pulp, as well as scanning electron microscopy (SEM) was used to observe the surface morphology.


47

Effect of Drug Concentration and the Cross Linker on the Release Behavior and Kinetic Evaluation of Tramadol HCl from Chemically Cross Linked

Copolymeric Hydrogels

M. Aslam Malana and Rubab Zohra

Department of Chemistry, Bahauddin Zakariya University, Multan.

Abstract: The use of chemically crosslinked copolymeric hydrogels for drug release was investigated. Copolymers of methacrylate, vinyl acetate and acrylic acid cross linked with ethylene glycol dimethacrylate (EGDMA) were prepared by free radical polymerization. The drug release rates, dynamic swelling behavior and pH sensitivity of hydrogels ranging in composition from 1-10 mol % EGDMA were studied. Tramadol HCl was used as model drug substance. The release behavior was investigated at pH 8 where all formulations exhibited non-Fickian diffusion mechanism. Absorbency was found to be more than 99% indicating good drug loading capability of these hydrogels towards the selected drug substance. Formulations designed with increasing amounts of EGDMA had a decreased equilibrium media content and thus exhibited a slower drug release rate. Fitting of release data to different kinetic models indicates shift of kinetic order from first to zero order as the concentration of drug was increased in the medium. Formulations with low drug content showed best fit with Higuchi model whereas, those with higher concentration of drug, followed Hixone-Clowell model with better correlation values. Release exponent (n) derived from Korse-Meyer Peppas equation implied that the release of Tramadol HCl from these formulations was generally non-Fickian (0.5< n<1) showing that the drug release was more swelling controlled than that diffusion controlled. These copolymeric hydrogels have potential to be used as colon drug delivery device through oral administration.

Synthesis and Characterization of Ag-Cu Alloy Nanoparticles Prepared in Various Ratios

Latif ur Rahman, Afzal Shah and Rumana Qureshi

Department of Chemistry, Quaid-i-Azam University Islamabad, Pakistan

Abstract:

Ag-Cu alloy nanoparticles with various compositions of Ag and Cu i.e., 4:1, 3:1, 2:1, 1:1, 1:2, 1:3 and 1:4 were synthesized by polyol process. The alloy nanoparticles formed were characterized by XRD techniques, UV-Visible and fluorescence spectroscopy. XRD spectra of the samples evidenced the formation of alloys. Debye Scherrer’s equation was used for the calculation of particle size. The particle size was found to decrease from 28-18 nm with the increase in mole fraction of Cu in Ag-Cu alloy nanoparticles. The dissolution of Cu in Ag matrix caused crystal lattice contraction. The appearance of the spectral peaks of the alloy nanoparticles between the peaks of Ag (λmax = 412 nm) and Cu (λmax = 541 nm) also revealed the formation of alloy nanoparticles. The spectral peak Ag-Cu alloy nanoparticles underwent bathochromic shift with the increase in composition of Cu as expected. The extinction coefficient was found to have maximum value for Ag-Cu alloy of 1:1 composition.


48

The results of fluorescence spectroscopy indicated Cu as a quencher which caused hypochromic effect to Ag-Cu alloy nanoparticles. From the fluorescence spectroscopic data total number of atoms in alloy nanoparticle of all samples, number of binding sites, binding constant and free energy of binding were calculated.

Temperature Responsive Poly(N-isopropylacrylamide-acrylamide-phenylboronic acid) Microgels for Stabilization of Silver Nanoparticles

Zahoor H. Farooqi, †,‡

Abbas Khan, † Mohammad Siddiq,

†,

† Department of Chemistry,

Quaid-I-Azam University, Islamabad 45320, Pakistan

‡

Institute of Chemistry, University of the Punjab, New Campus Lahore 54590, Pakistan

Abstract: Poly(N-isopropylacrylamide-acrylamide-phenylboronic acid) [P(NIPAM-AAm-PBA)] microgels of uniform size were prepared by the chemical reaction of 3-aminophenylboronic acid with poly(N-isopropylacrylamide-acrylamide-acrylic acid) [p(NIPAM-AAm-AA)] microgels in aqueous medium in the presence of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride catalyst via carbodiimide coupling. Ag nanoparticles were prepared using seed mediated growth method and were stabilized in P(NIPAM-AAm-PBA)] microgels. Ag nanoparticles and hybrid microgels were characterized by TEM, UV-visible and DLS techniques. The temperature responsive behavior of hybrid microgels was found to be similar to that of the pure microgels. The value of volume transition temperature of hybrid microgels was found to be slightly higher than that of pure microgels due to shielding effect of Ag nanoparticles present on the surface of microgel particle. The decrease in the size of hybrid microgels as compared to that of pure microgels in swollen state is due to physical cross-linking by Ag nanoparticles inside the network of microgels. The stable hybrid polymer microgel system has a potential to be used for optical sensors.

Synthesis and Rheological Studies of Acrylamide–Methacrylate-Acrylicacid Hydro gels.

M. Aslam Malana, Saima Asghar* and M. Saleem Khan


Abstract: Physically cross linked acryl amide– methacrylate- acrylic acid hydro gels containing varying amount of acryl amide were synthesized through radical polymerization. Flow curves, frequency sweep test, adhesion tack test were carried out at five different temperatures. Viscosity profiles of all the hydro gels at all the temperatures showed pseudo plastic nature of the hydrogels. The values of consistency co-efficient obtained from Ostwald de Wale model increased with temperature showing thermo sensitive nature of these hydro gels. However, a random trend of entanglement was observed with change in acryl amide content in the gels. Complex viscosities of the gels as a function of angular velocity were also measured at different temperatures. Rate of change of complex viscosity with angular velocity declined with temperature and became constant after 50°C. The storage moduli (G’) and loss moduli (G”) of each hydro gel at different temperatures were also determined.


49

Evaluation of Cr(VI) and Pb(II) in Drinking Water and Industrial Effluents before and after Treatment by Dispersive Liquid-Liquid Microextraction

Jameel Ahmed Baig1, 2, 3

, Latif Elci1, Tasneem Gul Kazi

3

1Chemistry Department, Pamukkale University, 20017 Denizli, Turkey

2Environmental Sciences, International Islamic University, Islamabad, Pakistan

3National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro Pakistan

Abstract:

Simple, robust and novel analytical procedures were developed for hexavalent chromium [Cr(VI)] and lead [Pb(II)] by dispersive liquid-liquid microextraction (DLLME) using microsample injection system coupled with flame atomic absorption spectrophotometry (MIS-FAAS). Ammonium pyrrolidinedithiocarbamate (APDC), carbon tetrachloride and ethanol were used as chelating agent, extraction solvent and disperser solvent, respectively for the determination of Cr(VI) by DLLME. The effective parameters of developed methods have been optimized and studied in detail. The limits of detection factor of Cr(VI) and Pb(II) were 0.037 and 0.054 µg L-1, respectively. The enrichment factor in both cases was 400 with 40 mL of initial volumes. The relative standard deviations (RSD, n = 6) were < 4%. The applicability and the accuracy of DLLME was estimated the analysis of Cr(VI) and Pb(II) in industrial effluent wastewater by standard addition method (recoveries > 96%). The proposed method was successfully applied to the Cr(VI) and Pb(II) at ultra-trace levels in natural drinking water, industrial effluents waste water of Denizli. Moreover, proposed method was compared with literature reported method.

Nanofiltration Membrane: Preparation Characterization and Application

Fozia T. Minhas1, Shahabuddin Memon

1, Nadeem Iqbal

2, M. Mujahid

2, and M. I. Bhanger

1

1National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro

2School of Chemical and Materials Engineering, NUST, 44000, Islamabad

Abstract:

Nanofiltration (NF) is distinctive membrane separation technology whose characteristics combine both ultrafiltration (UF) and reverse osmosis (RO) features. It can operate at comparatively lower pressure than RO and with similar solute retention. Pores exhibited by NF are very tiny in ranges from 0.1~10 nm, normally 1~2 nm. This makes NF an amazing separation technology as it works in low operating pressure with high permeate flux and economical process. NF have molecular weight cut-offs for organic molecules in range of 200-1000 Da. It offers solution for number of challenging problems like water softening, removal of pesticides and heavy metals/color removal, recovery of many products of pharmaceutical importance, separation of amino acids and antibiotics, treatment of waste of chemical industries. In this study, polypropylene (PP) Celgard 2400 microfiltration membrane was taken as support to prepare thin film composite NF membranes. Flat sheet PP Celgard 2400 membranes were coated by the interfacial polymerization (IP) procedure standardized by Korikov et al. After that membrane was treated with ethylene diamine (EDA) and hexane solution of Trimesoyl Chloride (TMC). The surface morphology of prepared membranes were examined by Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and atomic force microscopy (AFM). For confirmation of pores below 2nm water and solvents permeation through membranes were analyzed using homemade NF cell. Solute rejection was also checked simultaneously.


50

Voltammetric Studies of Irreversible Reductive/Oxidative Quenchers Involve in Photoinduced Electron Transfer Reactions

M. Tahir Soomro1, Günter Grampp

2, Truong X. Nguyen

2

1National Centre of Excellence in Analytical Chemistry

University of Sindh, Jamshoro Pakistan 2Institute of Physical and Theoretical Chemistry

Graz University of Technology, Austria

Abstract:

The electrooxidation of DNA bases, amino acids and electroreduction of dyes are reported elsewhere. However, the interest is focused particularly on the determination of voltammetric oxidation/reduction peak potentials. The following paper repots on the determination of the oxidation/reduction potential for irreversible systems measured by cyclic voltammetry. The determination founded on the Rehm-Weller free energy relationship for the electrochemical electron transfer reaction. Furthermore, to understand the nature of the photoinduced electron transfer reaction the dependence of redox potential on pH of the solution also established.

Absorption and Emission Charateristics of p-phenylenediamine (PPD) and N,N,N/,N/-tetramethyl-p-phenylenediamine

Muhammad Zahid*

1,2, Guenter Grampp

2, Saida Asim

1,2 , Asim Mansha

1,3, Ijaz Ahmad Bhatti

1

1Department of Chemistry & Biochemistry, Universty of Agriculture Faisalabad

2Institute of Physical and Theoretical Chemistry, Graz University of Technology, Austria

3Department of Chemistry, G. C. University Faisalabad, Pakistan

Abstract: It has been shown that cyano-substituted aromatic amines (p-phenylenediamine derivatives) have very interesting photophysical and electrochemical properties, and the solvatochromic properties of cyano-substituted p-phenylenediamines have been investigated [1-3]. In order to get insight into the mechanism, the absorption, emission and solvatochromism properties of p-Phenylenediamine (PPD) and its methylated derivative, N,N,N/,N/-tetramethyl-p-phenylenediamine, have been studied. Two empirical scales for solvent paramters, Kamlet-Taft (, and *) and Javier Catalan (SA, SB, SP and Sdp), have been applied to study the effect of solvent on the absorption and the fluorescence spectra. These approaches account for both specific, such as hydrogen bond donating and accepting ability, and non-specific solvent-solute interactions (solute-solvent polarizability and dipolarity). Linear dependence of these solvent parameters has been analyzed by multi-parameter approach (Linear Solavtion Energy Relation, LSER) given as

oXYZ XYZ aA bB cC dD= + + + +

A, B, C and D are parameters of solvent and a, b, c and d are the respective contributions of solute. XYZ is the solvent dependent value of physicochemical property and XYZo is corresponding statistically calculated value for gas phase.


51

The results of the two similar solvent parameter scales are presented and compared to each other. Additionally, the observed trends in the response of solutes towards different solvent properties with the substitution of methyl groups on p-phenylenediamine will be discussed.

Bio-Treatment of Cotton Fabric: A Green Strategy for Textile Surface Modification

Aisha Rehman, Zulfiqar Ali Raza*, Muhammad Tahir Hussain and Rashid Masood

Chemistry Research Laboratory, National Textile University, Faisabad-37610, Pakistan

Abstract: Pakistan is going through the worst delima of energy crisis which mostly affects the major revenue generating industry of textiles. Traditional textile processes throughout require high amount of water, chemical reagents and energy causing pollution burden on the environment. The present study proposes the bio pre-treatment of cotton fabric using eco-friendly textile enzymes including amylase, pectinase, catalase, laccase and cellulase. The process time, temperature, enzyme concentrations were investigated at various pre-treatment stages to optimize the process. The results were assessed by using Tegawa rating test, weight loss, drop test, whiteness index (°CIE) and color strength (K/S), and the fabric surfaces were investigated under stereo and scanning electron microscopes (SEM). A comprehensive comparison of bio-treated fabrics was done with the conventional chemical treated fabrics. Minimum reduction in fabric weight and the best Tegawa rating to be 6-7 were achieved by using enzymatic treatment. The absorbency, °CIE and K/S values were comparable for the both chemical and biological treated fabrics. The results of stereo microscopy and SEM showed an adequate modification in the surface of cotton fabric. So the enzyme treatment could be more promising alternative of chemical treatment making the textile processes cost effective, energy efficient and environmental sustainable.

Wastewater Treatment using Immobilized Natural Coagulants

Muhammad Asif Hanif, Haq Nawaz Bhatti, Raziya Nadeem and Tariq Mahmood Ansari

Department of Chemistry and Biochemistry, University of Agriculture, Faiasalabad

Abstract: In certain areas of the developing world natural coagulantshave been used for centuries within traditionalwater treatment practices. The most common natural coagulants were immobilized into granular form using calcium alginate. The laboratory scale trials have been demonstrated the effectiveness of natural coagulants for the clarification of highly turbid water. The performance of microfiltration coupled with coagulation using optimum dosage of natural coagulant was investigated. Results showed that the values of COD, BOD, alkalinity, TS, VSS, turbidity and pH in the filtrate were influenced significantly by natural coagulants. The results of the present study clearly demonstrate that immobilization of natural materials can be a very useful way to deal with increasing water pollution problems.


52

Detection of Arsenic and Nitrate in Drinking Water and their Removal by Some Newly Synthesized Adsorbents

Hafiz Badaruddin Ahmad1*

, Yasir Abbas1, Mazhar Hussain

1,

Ijaz Ahmad Bhatti2 And Shafiq Ahmad Arain

3

1Institute of Chemical Sciences, Bahauddin Zakariya University Multan, Pakistan 2 Department of Chemistry & Biochemistry University of Agriculture, Faisalabad, Pakistan

3Department of Chemistry, Shah Abdul Latif University Khairpur, Pakistan

Abstract: The contamination of groundwater with nitrate and arsenic is a serious health issue in many parts of the world and its removal is very challenging task for the chemists. High concentration of nitrate in drinking water causes many health problems like blue body syndrome (methaemoglobinemia) and potential formation of carcinogenic nitrosamine while that of arsenic causes cancer in skin, lungs, urinary bladder, and kidneys. It also causes skin thickening (hyperkeratosis), neurological disorders, muscular weakness, loss of appetite and nausea. WHO standard values of nitrate and arsenic in drinking water is 10 ppm and 10 ppb respectively. The most common methods for the removal of nitrate and arsenic from drinking water are ion exchange, reverse osmosis, electro dialysis, membrane filtration, froth flotation, catalytic and biological denitrification. However none of them is widely accepted because of cost or maintenance of the process. In this study, samples of drinking water have been collected from different areas, i.e. flood affected zone of Pakistan (Muzzafar Garh and Layyah), agricultural zone, power plant surroundings and some rural and urban areas. Arsenic and nitrate in the samples have been determined spectrophotometrically. It is found that nitrate and arsenic concentration in many samples is higher than WHO standards. For the removal of arsenic and nitrate, some novel adsorbents have been synthesized. Zerovalent iron and zinc nanoparticles have been coated on alumina by stabilizing with polyvinyl alcohol (PVA). A mixture of silver-zinc and silver-iron nanoparticles has also been coated on alumina which shows much better efficiency as compared to separate iron and zinc nanoparticles. Because of the presence of silver, the adsorbent also shows antimicrobial activity. The synthesized adsorbents have been characterized by FTIR, XRD and SEM, which show the presence of nanoparticles on the adsorbents. Incorporation of ZnCl2 increases the adsorption capacity of adsorbent. Langmuir, Freundlich and DR isotherms were plotted and their parameters have been calculated. Kinetic parameters were also evaluated to determine the order of reaction. It is concluded that the adsorption follows second order mechanism.


53

Determination of Sulpiride in Pharmaceutical Preparations and Biological Fluids Using a Cr (III) Enhanced Chemiluminescence Method

Muhammad Naeem Khan1,2

, Muhammad Rasul Jan1, Jasmin Shah

1, Sang Hak Lee

2, 4*,

Young Ho Kim3*

1Institute of Chemical Sciences, University of Peshawar, Peshawar, Pakistan. 2Department of Chemistry, Kyungpook National University, Daegu, 702-701, South Korea

3Research Institutes of Advanced Energy Technology, Kyungpook National University, Daegu

702-701, South Korea 4Korea Basic Science Institute Daegu Center, Daegu 702-701, South Korea

Abstract: A highly sensitive and simple method for identifying sulpiride in pharmaceutical formulations and biological fluids is presented. The method is based on increased chemiluminescence (CL) intensity of a luminol-H2O2 system in response to the addition of Cr (III) under alkaline conditions. The CL intensity of the luminol-H2O2-Cr (III) system was greatly enhanced by the addition of sulpiride and the obtained CL intensity was proportional to the concentration of sulpiride in a sample solution. Various parameters affecting the CL intensity were systematically investigated and optimized for determination of the sulpiride in a sample. Under the optimum conditions, the CL intensity was proportional to the concentration of sulpiride in the range of 0.068–4.0 µg mL-1, with a good correlation coefficient of 0.9965. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 8.50 × 10-6 µg mL-1 and 2.83 × 10-5 µg mL-1 respectively. The method present here produced good reproducibility with a relative standard deviation (RSD) value of 2.70 % (n=7). The effects of common excipients and metal ions were studied for their interference effect. The developed method was validated statistically through recovery studies and successfully applied for the determination of sulpiride in pure form, pharmaceutical preparations and spiked human plasma samples. The percentage recoveries were found to range from 99.10-100.05 % for pure form, 98.12-100.18 % for pharmaceutical preparations and 97.89-101.41 % for spiked human plasma.

The Application of Neutron Induced Fission Technique for the estimation of uranium concentration in drinking water sources of Tehsil Takht-e-Nasrati,

district Karak, Khyber Pakhtukhwa, Pakistan

Hussain Ullah1, Nimat Ullah Khattak

2, Nawab Ali

3, Muhammad Akram

3, Ali Rehman

1,

Muhammad Safdar1, Rizwan Ullah

1, Muhammad Suleman Khan

1, Shahid Ullah

1, Ijaz Ahmad

1*

1Department of Chemistry, Kohat University of Science & Technology, Kohat, Pakistan 2National Center of Excellence in Geology, University of Peshawar, Pakistan

3Physics Division, PINSTICS, P.O. Nilore, Islamabad, Pakistan

Abstract: The Neutron Induced Fission Technique has been applied for the estimation of uranium in 30 drinking water sources of Tehsil Takht-e-Nasrati and district Karak, Pakistan. These samples have mean, minimum and maximum concentration of uranium of 13.45 ± 3.207, 1.07 ± 0.6, 84.23 ± 15.63 µg L1-, respectively. The significant finding was the observation of very high level of uranium in drinking water sources obtained from uranium rich bedrocks than the safe


54

limit of WHO (15 µg L1- ) for human consumption. On the basis of this study, it was concluded that the origin of uranium may be potentially due to one of the Asia richest mineral deposit of uranium in Union council (UC) Shanawa Gudi Khel (Karak, Pakistan). The result could be of vital concern in the diagnosis and prognosis of uranium induced disease in the local population under investigation.

Impact of Traditional Processing on Pesticide Residues in Okra

Asif Ali Jamali, S.M. Nizamani, Amber R. Solangi, Najma Memon

National Centre of Excellence in Analytical Chemistry, University of Sindh Jamshoro

Abstract:

Demand for vegetables in Pakistan is constantly increasing to feed growing population. Okra crop is attacked by variety of insect/pests and commercial okra production relies heavily on the pesticides belonging to organochlorine, organophosphate, carbamate, pyrethroid and nicotinoid groups for pest control. Moreover, growers do not observe safety interval for okra harvest. Hence the okra sold in Pakistani markets is highly contaminated with pesticide residues. Okra crop was sprayed with commonly used pesticides bifenthrin and endosulfan, and then different traditional processing were applied on Okra such as washing, detergent washing, sun-drying and cooking, etc. Pesticides were extracted and cleaned up. Cleaned up residues were analyzed through Agilent 7890A Gas Chromatograph coupled with micro-ECD. The results revealed that the residues were reduced by the traditional processing, plain water and detergent water washing and more were reduced by the frying and detergent water wash may be due to the fat solubility of these pesticides and volatility factor because in frying the temperatures may be higher than 1200C. From the research it is recommended that the vegetables may be washed thoroughly with water specially detergent-water (washing) to effectively remove pesticide residues. Moreover, this process may also remove dirt particles.

Flow Injection Spectrophotometric Determination of Glyphosate Herbicide in wheat grains via Condensation Reaction with p-

dimethylaminobenzaldehyde

Mian Muhammad*, M. Rasul Jan1, Jasmin Shah

2

*Department of Chemistry, University of Malakand 1Vice Chancellor, University of Malakand

2Institute of Chemical Sciences, University of Peshawar, Pakistan

Abstract: In this paper a sensitive and faster method for the determination of glyphosate herbicide, using flow Injection (FI) system coupled with a spectrophotometer, has been described. Glyphosate molecule undergoes an addition reaction with alkaline p-dimethylaminobenzaldehyde (DMAB) that leads to a yellow colored product after acidification and the subsequent condensation. The absorbance of the product was measured at 405 nm. The Beer’s law range for the proposed method was found to be 2-15 µg mL-1 for batch analysis and 0.6-20 µg mL-1 for flow injection analysis (FIA) with molar absorptivity values of 2.7 x 103 and 4.3 x 103 L mol-1cm-1 for batch and FI analysis respectively. The limit of detection (LOD) and quantification (LOQ) were


55

calculated and found to be 0.2 ± 0.06 and 0.7 ± 0.1 µg mL-1 respectively for batch analysis and 0.2 ± 0.07 and 0.6 ± 0.02 µg mL-1 for FI analysis. The proposed method was successfully applied with a reasonable sample throughput of 60 samples h-1 for the analysis of wheat grains sample.

Rapid Detection of Melamine Adulteration in Dairy Milk by SB-ATR-Fourier Transform Infrared Spectroscopy

Sana Jawaid*, Farah N. Talpur, S.T. H Sherazi, Shafique M. Nizamani

National Center of Excellence in Analytical Chemistry, University of Sindh, 76080,

Jamshoro, Pakistan

Abstract: Melamine (2, 4, 6-triamino-1, 3, 5-triazine), is an inexpensive synthetic molecule commonly used as an industrial chemical in the synthesis of melamine formaldehyde resins for manufacturing laminates, plastics, coatings, commercial filters and other products. It is not approved as an ingredient in food, but some manufacturers illegally used it as an adulterant to increase the apparent protein content. In present study we have used single bounce attenuated total reflectance (SB-ATR) fourier transform infrared spectroscopy (FTIR) method is an effective tool for the detection and quantification of melamine in milk (liquid and powder). Linear calibration curves were obtained over the calibration range of 25 to 0.0625 %. Partial least-squares (PLS) models were established for correlating spectral data to melamine concentration with R2 > 0.99, and RMSEC 0.291. The mid- FTIR spectroscopy facilitate rapid sensitive, robust, and low-cost for the detection of 1 ppm melamine in milk (liquid and powder). FTIR method requires little or no sample preparation. The Mid-IR method has an assay time of 1 min, and a 2 min total time to detection.

Investigation of Groundwater of Taluka Sakrand, District Shaheed Benazirabad, Sindh, Pakistan

Subhan Ali Majidano and Muhammad Yar Khuhawar

Institute of Advanced Research Studies in Chemical Sciences, University of Sindh, Jamshoro,

Pakistan

Abstract: Eighteen water samples were collected from taluka Sakrand district Shaheed Benazirabad, and analyzed for different parameters. The Electrical conductivity and Total dissolved salts of the water samples found in the range 886 - 2850 µS/cm and 567 – 1824 mg / L respectively. In the light of results of analysis, it is observed that only one water sample was found as suitable for drinking purpose and fifteen samples may be used for irrigation. However the samples containing TDS 200mg/L or above may be used with caution.


56

On Demand Electrochemical Production of Hydrogen for Mobile Applications: Development of Alkaline Electrolyser

Syed Khrram Raza, Jack Silver and Poopathy Kathirgamanathan

Wolfson Centre, Brunel University, Uxbridge, Middlesex, UB8 3PH, UK

Absract:

Global warming and the energy crisis are two of the greatest challenges on which mankind is currently focused. This has forced governments and other organisations to think how to protect the environment and how to reduce fuel costs. A variety of new and exciting technologies is being investigated to address the energy problem. Alternative energy sources such as solar power, fuel cells, wind power and tidal waves are active areas of commercial and scientific pursuit. Current research is moving towards the hydrogen economy and hydrogen based energy systems. Hydrogen can be produced in many ways, most commonly by steam reforming of hydrocarbon (70% to 85% thermal efficiency) but the downside is that it releases carbon dioxide (CO2)), compared with commercial PEM electrolysers where performance has been reported to be 56 -73% at normal temperature pressure(NTP) with zero carbon emission. Electrochemical production of hydrogen has several advantages: (i). It gives pure hydrogen. (ii). Allows portability (eg. Solar energy can be used to power the electrochemical cell). (iii). It can be produced on demand. The paper presents our recent work on the fabrication of low cost continuous flow alkaline (KOH, up to 30%) electrolysers using low cost electrodes (stainless steel 316) and membranes based on ultrahigh molecular weight polyethylene (UHMW PE) and production of hydrogen. A high coulombic efficiency of up to 90% has been achieved. Typical cell voltage is 2.5 ± 0.5 V at a current densities ranging from 30 to 120 mAcm-2.

Order Disorder Transition of PS-b-P4VP and its Interaction with Disperse Red1

Nauman Ali, Khalid Saeed, Sajjad Hadier, Soo Young Park

Institute of Chemical Sciences University of Peshawar

Abstract:

The order disorder structure of poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) with temperature variation effects of Disperse Red 1 (DR1) were studied using small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR), transmission electron microscopy (TEM) and differential scanning calorimeteric (DSC) analysis. PS-b-P2VP was coupled with DR1 in 10 mg/mL THF solutions. Hydrogen bonds were formed between the –OH group of DR1 with the pyridine ring in PS(14K)-b-P2VP(6K). The free pyridine ring stretching in PS(14K)-b-P2VP(6K)/DR1 peaks at 1010, 1350, and 1500 cm-1 appeared due to the breaking of hydrogen bonds at higher temperature. Similarly, the –OH peak of DR1 was not observed at 30oC but with increase in temperature the peak at 3200-3500 cm-1 appeared as the hydrogen bond breaks. The disorder to order transition was observed with no clear structure formation for net PS(14K)-b-P2VP(6K) with increase in temperature till 163oC and started defuse thereafter. However, with incorporation of DR1 in the PS(14K)-b-P2VP(6K) led to the gyroid structure. These structures were freeze dried in liquid nitrogen confirmed by TEM.


57

Evaluation of Sintering, Microstructural and Electrical Properties of SiO2 Added LiNbO3 Ceramics

Tahira Mahmooda, Sadaf Tasneem

a*, Yaseen Iqbal

b, Abdul Naeem

a

a NCE in Physical Chemistry, University of Peshawar

b Materials Research Laboratory, University of Peshawar

Abstract: The effect of SiO2 addition on the sintering parameters, microstructure and conductivity of LiNbO3 ceramics were investigated. X-ray studies identified crystalline phases of Li4SiO4, LiNb3O8 and quartz in all of the silica added samples along the presence of major phase of LiNbO3. Scanning electron microscopy of the samples revealed enhanced densification of LiNbO3

ceramics due to an increase in grain size of LiNbO3 with elevation in silica concentration probably due to liquid phase sintering of Li4SiO4. Dielectric constant was found to decrease with the addition of silica whereas, opposite results were obtained for AC conductivity measurements.

Equilibrium and Kinetic Modeling for the Biosorption of Cu (II) by Pretreated Corncob Powder

Hazafa Zafar, Raziya Nadeem

Department of Chemistry and Biochemistry, University of Agriculture,

Faisalabad (38040), Pakistan

Abstract: The potential to remove Cu (II) ions from aqueous solutions through biosorption using corncob powder were investigated as a function of initial metal concentration, pH and contact time. The corncob powder was chemically modified with inorganic acids and bases. The order of maximum sorption efficiency qmax (mgg-1) exhibited by the native and resultant novel biomaterial was Ba(OH)2 (103.1)> H3PO4 (101.4) > NaOH (100.1) > H2SO4 (94) > Al(OH)3 > HCl (84.4) > Native (79.4) at initial Cu(II) concentration of 400mgL-1. A significant increase in Cu(II) uptake per weight of biomass was obtained as the pH increased from 2-6. Maximum biosorption was observed at pH 5, above this precipitation was occurred. The kinetic studies revealed that the Cu(II) ion sorption was rapid within first 30 minutes followed by slow sorption till equilibrium was reached. The equilibrium and kinetic data was satisfactorily fitted to Langmuir Isotherm and Pseudo second order model with correlation coefficient 0.997 and 1 respectively. It was concluded that corncob was a plentiful, inexpensive and effective medium for capture of dissolved Cu (II) from aqueous solutions. The findings open up new avenues in the modern Green Technology of water treatment using biosorbent possessing potential for commercialization.


58

Oxidative Removal of Phenol from Water Catalyzed by Nickel Hydroxide

Muhammad Saeed, Mohammad Ilyas

National Cntre of Excellence in Physical Chemistry, University of Peshawar,

Peshawar 25120, KPK, Pakistan

Abstract:

This work explores the preparation and characterization of nickel hydroxide catalyst and investigation of its catalytic activities for oxidative degradation of phenol in aqueous medium using batch reactor. The catalyst was prepared by reaction of sodium hypochlorite, sodium hydroxide and nickel sulfatehexahydrate in distilled water. The prepared catalyst was characterized by surface area, particle size, FTIR, XRD, SEM,and determination of oxygen content measurements. The prepared nickel hydroxide was used as catalyst for oxidative degradation of phenol in aqueous medium by taking 15 mL of 0.71 M phenol solution. The catalytic performance of nickel hydroxide was explored in terms of effect of time, temperature, partial pressure of oxygen, initial concentration of phenol, catalyst loading and effect of stirring speed on degradation of phenol. The catalyst was separated from the reaction mixture by filtration. Langmuir-Hinshelwood type of mechanism was followed in the reaction where adsorption of phenol and oxygen at the surface of catalyst was taking place according to competitive Langmuir and Temkin adsorption isotherm respectively.

Flow Injection Online Determination of Uranium (VI) after Preconcentration on Solid Sorbent

Shabnam Shahida*1, Akbar Ali

2

1Department of Chemistry, University of Azad Jammu and Kashmir,

Muzaffarabad, AJK, Pakistan 2Chemistry Division, Pakistan Institute of Nuclear Science and Technology,

P.O. Nilore, Islamabad, Pakistan

Abstract:

An economical, fast, sensitive and selective method from aqueous media based on the flow injection on-line preconcentration of uranium (VI) on dual columns having amberlite XAD-4 resin impregnated with nalidixic acid (HNA) is described. The objective of this work was to check the efficiency of dual column in the enhancement of sensitivity. For this purpose nalidixic acid was impregnated on XAD-4 resin and uranium (VI) was selectively adsorbed on the resin as uranium-nalidixic acid complex from aqueous solution of pH 6.0 on the two mini-columns of the same size (5mm i.d. and 5cm in length) at a flow rate of 15.2 ml min-1. The uranium complex was eluted from the resin by using HClO4 (0.2 mol L-1, 4.9 ml min-1) and mixed with chromogenic reagent (CR), arsenazo-III (0.05%, 4.9 ml min-1), and passed through the flow through cell of spectrophotometer where its absorbance was measured at 651 nm. Various parameters responsible for the adsorption and elution of the uranium complex were optimized. For data analysis peak height was used for convenience. For 60s and 300s preconcentration time, preconcentration factor

54 and 270, sampling frequency 40 h-1 and 11 h-1; and detection limit (3σ) 0.6 µg L-1 and 0.12 µg L-1 were obtained respectively. The effect of various anions and cations was studied. High selectivity of this method was observed. The proposed method was applied on different spiked water samples, sea water, biological sample and good recovery was obtained. The method was also applied on synthetic ore sample for the determination of uranium (VI) and the results were in good agreement with the reported value.


59

The Analysis of Different Fish and Human Milk for their Food Value and Presence of Toxic Values

Murad Ali Khan

1 M. Kashif Gul

1, Mohammad Adil

1, Zawar Hussain

1 and Inayat Ur Rahman

2

1Department of Chemistry, Kohat University of Science and Technology

Kohat, Pakistan. 2Medicinal Botanic Center, PCSIR Labs Complex Peshawar

Abstract: Fish samples were collected from the river Kabul and the trout fish from Swat and the human milk was collected from volunteers of different localities. These samples were analyzed for their protein content and various fatty acids. The samples were also analyzed for the presence of various metals and correlate the presence of these heavy metals with their habitat. The results show interesting effects of the environment on the food values and the presence of toxic metals.

Antioxidant, Antimicrobial Activities and Cytotoxicity Studies of Various Parts of Achillea Wilhelmsii

Muhammad Asghara, Nasir Rasool

a, Rasool Bakhsh Tareen

e, Muhammad Zubair

a, Muhammad

Riaza, Komal Rizwan

a, Muhammad Farman

b, Muhammad Athar Abbasi

c, Afsar Khan

d

aDepartment of Chemistry, Government College University, Faisalabad bDepartment of Chemistry, Quaid-I-Azam University, Islamabad

cDepartment of Chemistry, Government College University, Lahore

dDepartment of Chemistry, COMSATS Institute of Information Technology, Abbottabad

eDepartment of Botany University of Baluchistan Quetta, Pakistan

Abstract: Nature has been a source of medicinal agents for thousands of years and a substantial number of modern drugs have been isolated from natural sources, many based on their use in traditional medicines. The various parts of Achillea wilhelmsii were extracted with absolute methanol and further fractionated by solvent-solvent extraction method with increasing polarity based absolute solvents i.e. chloroform, ethyl acetate and n-butanol, n-hexane. The methanol extract of various parts of Achillea wilhelmsii and their fractions were analyzed for their antioxidant and antimicrobial activities. The methanol extract and different fractions of various parts of Achillea wilhelmsii contained appreciable levels of total flavonoid contents and total phenolic contents. The DPPH radical scavenging activity, reducing power activity, ascorbic acid activity and inhibition linoleic acid peroxidation were also analyzed. Qualitative and quantitative analysis of secondary metabolites was carried out. The GC-MS analysis of Achillea wilhelmsii essential oil and n-hexane extract revealed the presence of several chemical constituents. LCMS analysis of plant also carried out to evaluate the presence of phenolics. HPLC analysis of chloroform, ethyl acetate and n-butanol fraction of various parts for total phenolics and flavonoids also carried out. The plant extract and fractions were assessed against human blood erythrocytes for cytotoxic studies by haemolytic activity. The results of the present study have shown significant variations in the antioxidant activities of various parts of Achillea wilhelmsii and their fractions.


60

Volumetric and Ultrasonic Studies of Some Amino Acids in Aqueous Glucose Solution at Different Temperatures

Muhammad Asghar Jamal*, Tosif Hanif and Khurram Shahzad

Department of Chemistry, Government College University Faisalabad, 38000, Pakistan

Abstract: Densities and sound velocities of glycine, and methionine in aqueous glucose solutions have been measured at T=298.15, 303.15, 308.15 and 313.15 K by an Anton Paar density sound

analyzer (DSA 5000). This data have been used to calculate apparent molar volumes, Vφ, partial

molar volume, V0, and partial molar compressibility, φk. The negative values of partial molar compressibility with rise in temperature were observed which indicating that the water molecules around ionic charged groups of amino acids are less compressible than the water molecules in the bulk solution and hence indicate smaller solute-solvent interactions caused by electrostriction of water molecules. All partial molar volume, ∆Φo

v tr, transfer values are found to be negative which

have been discussed in terms of the interactions between ions (charged centers), hydrophilic groups (OH and CONH) and hydrophobic groups. The results are interpreted in terms of structure-making or structure-breaking effects of these amino acids in the mixture.

Preparation, Characterization and Antimicrobial Activities of Chitosan/ZnO Complexes

1Shabir Ahmad,

1Shaukat Mehmood,

2Tariq Yasin,

1Saima Gul

1Kohat University of Science and Technology (KUST), Kohat, 2600 Khyber Pakhtunkwa

2Pakistan Institute of Engineering and Applied Sciences (PIEAS)

Abstract: Chitosan–ZnO complexes were prepared from deaccetylated and irradiated chitin with Zinc Oxide by direct precipitation method. Five different irradiated chitosan with ZnO complexes were prepared in a sheet form. The chitosan–ZnO complex formations were then characterized by FTIR spectroscopic analysis, UV–vis absorption spectroscopy, X-ray diffraction, Scanning electron microscopy. The complexes were then checked for their antimicrobial activities. All the complexes showed promising results against the test bacterial strains. Chitosan/ZnO Complexes can be good candidates against the diseases caused by the test bacterial strains.


61

Extraction, Identification and Antioxidant Activity of the Flavonoid-Rich Fractions of Cassia angustifolia

Abdul Qayoom Laghari*, Shahabuddin Memon

National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro-76080,

Pakistan

Abstract:

Since ancient times, plants have formed the basis of traditional medical systems, such as the Ayurvedic, Chinese and African ones. Plants produce very complicated mixtures of chemical substances, some of them are medicinally important. In order to study the active constituents, it is necessary to extract them from the plant material. Cassia angustifolia Vahl. (Caesalpiniaceae) commonly known as Sanna makkai, a reputed drug in traditional medicine and frequently used in folk medicine as a purgative for a long time. Present study describes extraction, identification, total flavonoid contents and antioxidant potential of extracts obtained from leaves and flowers of Cassia angustifolia. Five different extraction techniques were used for the extraction of flavonoids from leaves and flowers. Total flavonoid contents (TFC) in the extracts were determined by UV-visible spectrophotometry. Individual flavonoids were identified and quantified by High-performance liquid chromatography coupled with photodiode array detection and electrospray ionization tandem mass spectrometry (HPLC-PDA–ESI-MS/MS). It has been examined that aqueous ethanol (70%) fractions of C. angustifolia flowers and leaves are highly rich in flavonoids and microwave extraction is the best method for the extraction of individual flavanoid constituents (1-9) as well as total flavonoid contents. 2,2-Diphenyl-1-picrylhydrazyl (DPPH) antioxidant activity of the extracts was also determined and it has been noticed that microwave extract has highest antioxidant activity as compared to other extracts obtained by sonication, reflux, marination and soxhlet extraction methods.

Effect of Drying Method and Extraction Solvent on the Total Phenolics and Antioxidant Activity of Cauliflower (Brassica oleracea L.) Extracts

Farooq Anwar1* Bushra Sultana

2, Muhammad Mushtaq

2

1Department of Chemistry, University of Sargodha, Sargodha

2Department of Chemistry and Biochemistry, University of Agriculture Faisalabad

Abstract: Plants, being a rich source of medicinally important compounds such as antioxidants, have chemo-preventive role against the risk of oxidative stress-related diseases. There has been much interest in fruits and vegetable rich diets as a natural source of antioxidants and functional ingredients. As well as targeting plants high in antioxidant activity it is also important to optimise extraction parameters. Four extracting solvents, methanol, ethanol, aqueous methanol (80 % v/v) and aqueous ethanol (80 % v/v) were evaluated for their efficacy to extract antioxidants from cauliflower that had undergone different drying processes namely air-drying, sun-drying and oven-drying. There was a significant difference (P < 0.05) in the extracting ability of each of the solvents. The aqueous solvents were superior in their ability to extract the antioxidants and aqueous methanol was significantly more efficient than aqueous ethanol. This result was consistent across a number of parameters including extraction yield, total phenolic content and


62

antioxidant activity. Furthermore, the samples drying process prior to extraction, also significantly influenced (P < 0.05) the extraction yield. Oven dried (40 oC) cauliflower had the highest yield of extractable antioxidants while air dried (ambient, approx 25 oC) had the lowest. Again, there was excellent correlation between extraction yield, antioxidant activity and total phenolic content.

Breakthourgh Analysis of Continuous Biosorption of Cd(II) Ions by Eco-Friendly Wheat Straw Biomass

Umar Farooq1, Misbahul Ain Khan

1,2, Makshoof Athar

1, Janusz A. Kozinski

3

1Instt. Of Chemistry, University of the Punjab, Lahore

2Department of Chemistry, The Islamia University of Bahawalpur

3Faculty of Science and Engineering, York University, Toronto, Canada

Absract: Straw from common wheat (Triticum aestivum) is found as waste/by-product all over Pakistan. The present work is aimed to explore the efficiency of powdered wheat straw for removal of toxic Cd(II) ions from aqueous solutions under flow conditions. The data obtained from the experiments have been used to draw the breakthrough curves. S-shaped curve were obtained with 131min as breakthrough time for a 10 cm long column at 3.03cm/min flow rate of 50mg/L Cd(II) solution. The bed height was changed from 10 cm to 30 cm and the data obtained were used to study the column performance. Bohart-Adams’ bed depth service time model (BDST) was successfully applied to study various column properties.

Synthesis and Thermomechanical Studies of Polyurethane Elastomers Incorporated with Disperse Red-5 Dye as a Chain Extender

Fazal-ur-Rehman1, Ijaz Ahmed Bhatti

2, Mohammad Zuber

1,

Khalid Mahmud Zia1 and Shahid Adeel

3

1Department of Applied Chemistry, Government College University, Faisalabad.

2Department of Chemistry and Biochemistry, University of Agriculture, Faisalabad.

3Department of Chemistry, Government College University, Faisalabad.

Abstract: Coloured polyurethane elastomers (CPUEs) were formulated by prepolymer methodology using hydroxyl-terminated polybutadiene (HTPB), tolylene diisocyanate and chain extender (1,4-butane diol & disperse red-5). Different compositions of chain extenders and the dye were used in order to optimize the process of polymerization. Chemical constitution of these polymer samples were executed by Fourier transform infrared (FTIR) spectroscopy. Thermal characteristics were analysed using thermogravimetric analysis (TGA) and differential thermal analysis (DTA), which presented that the synthesized CPUs were thermally stable up to 320°C. Universal tensile tester was used to determine the mechanical behaviour of the CPUs in terms of tensile strength, modulus and elongation at break. The results showed that the elongation at break increased, while modulus was decreased with the concentration of dye (disperse red-5) in the polymeric chains.


63

New Reactive Azo Dyes with Sulfatoethylsulfone Reactive Groups: Synthesis and Applications on Cotton

Bazgha Ahmad, Ijaz Ahmad Bhatti, Muhammad Abbas*, Muhammad Shahid

Department of Chemistry & Biochemistry, University of Agriculture, Faisalabad

*Haaris Dyes and Chemicals, Pvt. Ltd. Faisalabad

Abstract:

Three sulfatoethylsulfone reactive dyes have been synthesized by following subsequent condensations, diazotization with vinylsulfonepara-ester (VSPE) and coupling reactions by using H- acid, J- acid and γ- acid respectively.Structure revelation of these synthesized reactive dyes is carried out by spectral techniques i.e. FTIR, H1NMR and ESI-MS. Mill desized, bleached and mercerized cotton was used for pad- thermosol dyeing with 3% dye (stock) solution.The effect of different dyeing parameters such as dye concentration, pH of the dye solution, dyeing temperature, dyeing time etc. on dying process are studied. The dyeing is performed at optimum conditionsand the colour strength of the dyed fabrics has beeninspected for the fastness tests according to ISO standard method using Spectraflash- 600 at Noor Fatima Textile Pvt. Limited, Faisalabad. The results show moderate to goodfastness properties compared by the grey scale for washing, crocking, chlorinated water, perspiration, dry cleaning and light. Printing is also practiced using the same dyes by printing paste formulation using sodium alginate as thickening agent which also exhibit good colour strength and fastness values.

HPLC Determination of Guanidino Compounds in Serum of Uremic Patients using Methylglyoxal as Derivatizing Reagent

A. J. Kandhro and M. Y. Khuhawar

Institute of Advanced Research Studies in Chemical Sciences,

University of Sindh, Jamshoro, Pakistan

Abstract: Guanidino compounds: guanidine (GD), methylguanidine (MG), guanidinoacetic acid (GAA), guanidinopropionic acid (GPA), guanidinobutyric acid (GBA), arginine (Arg), guanidinosuccinic acid (GSA), and creatinine (CRN) as derivatives ofmethylglyoxal were separated on a Kromasil C-18, 5 µm (150×4.6 mm id) column, when eluted with methanol-water-sodium tetraborate buffer (0.1M, pH 7.5)-acetonitrile (57:25:15:3 v/v/v/v) with a flow rate of 1ml/min. The UV detection was at 275 nm, linear calibrations were observed with 1.22-113.6 µmol/L and limits of detection (LOD) within 0.041-0.12 µmol/L. The derivatization and separation was repeatable (n=4) with relative standard deviation (RSD) within 4.3 %. The method was used for the determination of guanidino compounds from the serum of uremic patients and healthy volunteers and higher concentrations were observed for uremic patients than healthy volunteers. The serum was also analyzed by standard addition for guanidino compounds and recoveries calculated were GPA 94.89 %, GBA 96.61 %, GD 97.21 % and MG 97.58 % with RSD 1.7 -2.8 % respectively.


64

Peroxidase Mediated Efficient Degradation of Trypan Blue, a Diazo Dye: Optimization and Mechanistic Study

Umme Kalsoom

1, Haq Nawaz Bhatti

1*, S. Salman Ashraf

2

1Department of Chemistry & Biochemistry, University of Agriculture,

Faisalabad, Pakistan 2Department of Chemistry, P. O. Box 17551, UAE University, Al-Ain, UAE

Abstract: Enzyme mediated remediation of wastewater is emerging as a novel, efficient and environmentally-friendlier approach. The present study describes the use of Soybean Peroxidase to efficiently degrade an azo dye, Trypan Blue. Various parameters that can affect the dye degradation ability of the enzyme, including H2O2 concentration, enzyme concentration, dye concentration, pH and immobilization state of the enzyme was investigated. It was shown that under proper conditions, low concentration of hydrogen peroxide (64 µM) was able to efficiently degrade Trypan Blue. Furthermore, surprisingly, pH studies showed that the enzyme was most active at low pH values as opposed to pH 8, e.g. ~ 50−60% degradation at pH 3-5 vs only 10-15% degradation at pH 8/9. It was also seen that Soybean Peroxidase could be successfully immobilized in Polyacrylamide gel and used up to 6 times without significant loss of activity. Lastly HPLC-DAD and LC/MS studies were carried out to confirm dye degradation and analyze the intermediate metabolites. The results showed that Soybean peroxidase causes Trypan Blue degradation via symmetrical azo cleavage and subsequent radical-initiated ring opening of the metabolites.

Photo-catalytic Degradation of Drimarene Red CL-6BN: Optimization through Response Surface Methodology

Munawar Iqbal1, Ijaz Ahmad Bhatti

1*, Muhammad Zahid

1, Majid Muneer

2 and Ehsan Ullah Abid

1

1Department of Chemistry and Biochemistry, University of Agriculture Faisalabad, Pakistan

2Department of Chemistry, GC University Faisalabad, Pakistan

Abstract: Drimarene, an anthraquinone dye, belongs to the second largest class of textile reactive dyes and is used extensively due to their wide range of color shades and ease of application. The traditional technologies for degradation of these dyes have proven to be markedly ineffective due to their chemical stability and complex aromatic structures. Among the wide range of methods that has been developed for the removal of these dyes to mimic their environmental impact, some treatment methods have secondary pollution problem and are also cost effective. The advance oxidation process has been applied successfully for the degradation of non-biodegradable dyes. In present study, the UV irradiations in the presence of TiO2 and H2O2 were employed for photo-catalytic degradation of Drimarene Red CL-6BN (DRCL-6BN). Aqueous solutions of DRCL-6BN in the presence of TiO2 and H2O2 were treated with UV (254 nm) and the factors such as dye concentration, TiO2 and H2O2 percentage, UV exposure time, pH and stirring speed were optimized through response surface methodology for maximum dye degradation. Factorial 2n


65

design (Rotatable Center Composite Design) was employed for optimization of variables. It is found that the degradation of DRCL-6BN was enhanced significantly (P<0.05) in the presence of TiO2 and H2O2. For maximum dye degradation the optimized values were found for H2O2

(3%), TiO2 (0.06%), dye concentration (100 ppm), UV exposure time (90 min.), pH (3) and shaking speed (150 rpm).

Study of Radon Emanation Rate from the Soil of Okara District by Solid State Nuclear Track Detector CR-39

Abdul Hamid*, Amjad Ali, Ch. Azam Mukhtar, Junaid Anwar, Atif ur Rehman

University of Education, Lahore, Okara Campus

Abstract: Radium is known to be present naturally in soil, building materials, water etc., and decays to its daughter chain up to lead-260. One of its progeny is radon (Rn), which is the only decay product in gaseous state and can be inhaled by living organisms-where it may cause cancer. Many active and passive techniques had been developed to measure the indoor and outdoor Rn concentration. Solid-sate nuclear track detectors (SSNTD) are successfully used as a passive technique for detecting ambient Rn due to their many advantages. One of such detector is CR-39 which is a polymer of diethylene glycol bis-(allyl carbonate). Rn emanation rate was measured by close CAN technique using CR-39 detector to monitor the emission of alpha particles. The emanation rate of radon was measured from the soil of different towns of Okara district. Twelve towns, Okara city, Jaboka, Bama Kohla, Satgahrah, Hujra Shah Moqeem, Fort Dedar singh, Mana wala, Depalpur city, Renala city, Akhter abad, Shair garh and Chuchaq were selected. 1 Kg soil sample from each region was collected in polythene bags. The samples were finely ground and passed through 200 mesh sieve. The samples were dried at 400C for 24 hours in oven to remove moisture content. The soil sample of 5cm thickness was taken in plastic CANS of

12cm height and 7cm diameter for 40 days. Track density ( ( )tρ ) and radon emanation rate (E)

were calculated by following equations ( )

−−−= λte1λ

1t

λV

ηEAρ t

and ( )( )

−−=

−λt

(t)

e11/λt

λ

η

hρE

respectively.

The radon emanation rate was maximal from the soil of Dedar Singh Fort and Bama Kohla, and was minimal from the soil of Okara city and Chuchaq.

Endemic Fluorosis in a Village in the Thar Desert, Pakistan and Fluoride Levels in Plasma, Serum and Urine

Tahir Rafique,1 Iftekhar Ahmed,2 Faisal Soomro3*, Khoula Shirin1 1Applied Chemistry Research Centre, PCSIR Laboratories Complex, Karachi

2Department of Medicine, Dow University of Health Sciences, Karachi

3Department of Chemistry, University of Karachi, Karachi

Abstract: Fluoride toxicity has been a severe problem all around the world. It appears in variant forms but skeletal and dental fluorosis are the most dominant types. In Pakistan, areas of Thar Desert in Sindh Province are endemic in fluorosis. Fluoride levels in the blood plasma, serum and


66

urine samples of 121 people living in a village in Thar Desert were analysed where fluorosis is endemic and groundwater contains fluoride as high as 9.09 mg/L. The fluoride levels in serum, plasma and urine were found to be much higher than the normal expected values. The values were much higher than the values in some of the other fluorosis endemic areas of the world. A strong correlation (r = 0.884) was found between plasma & serum fluoride levels whereas moderate correlations were found between the urine & plasma (r= 0.576) and urine & serum (r= 0.621) fluoride levels, respectively. Urinary fluoride levels had been found to increase with age but with an insignificant correlation (0.119). Serum and plasma fluoride do not vary drastically age wise. After the age of 50 the urinary fluoride was found to decrease with a concomitant increase in serum level. The groundwater is the sole source of water which has higher fluoride than WHO limit and is the main cause of fluorosis in the area.

Effects of Selenium and Zinc Status in Biological Samples of Hepatitis C Patient after Herbal and Pharmaceutical Supplements

Nida Fatima Kolachi*, Tasneem Gul Kazi, Hassan Imran Afridi

National Center of Excellence in Analytical Chemistry, University of Sindh Jamshoro, Pakistan

Abstract: The aim of the present study was to compare the level of Selenium (Se) and zinc (Zn) in biological samples (serum and whole blood) of female hepatitis C patients (n = 143), age ranged 30–45 years before and after thirty days treatment with herbal/ pharmaceutical supplements. For comparative study, 137 age-matched control subjects, residing in the same city were selected as referents. The biological Samples were oxidized by 65% HNO3: 30% H2O2 (2:1) in microwave oven. The digests of all biological samples were analysed for selenium and zinc by electrothermal atomic absorption spectrometry. It was observed that Zn and Se in blood and serum samples of HCV patients were reduced in the range of 28.6 -39 % and 24-36%, respectively, as compared to those of referents. After herbal/ pharmaceutical supplementations 20.6 – 25.0 and 9.15- 13.2 % Zn, where as Se 10.6 -12.1 and 19.6- 21.4% were enhanced in sera and blood samples of HCV patients respectively. It was observed that the status of Se and Zn was improved in biological samples of HCV patients after thirty days treatment with herbal/pharmaceutical mineral supplementation. The effects of both supplements were not significantly different (p>0.05).

In-vitro Phytochemical Analysis of Some Ethnomedicinal Plants of Balochistan, Pakistan

Afrasiab Khan Tareen, Imrana Niaz Sultan, Muhammad Azam Kakar, Muhammad Waseem

Department of Environmental Management & Policy,

Department of Biotechnology & Informatics

Balochistan University of information Technology, Engineering & Management Sciences

(BUITEMS) Quetta

Abstract: Balochistan is tremendously rich in medicinal plants that are used against various diseases since ages. A study was carried out to find the bioactive agents of these ethnobotanical plants which are responsible for healing and curing from numerous diseases and infections. The


67

crude ethanolic extracts of medicinal plants, collected from different districts of Balochistan, used in the present study included the leaves of Azadirachta indica (Bolan district) , whole plants of Foeniculum vulgare (Quetta district) and Fumaria indica (Harboi,Kalat district) and flowers of Cichorium intybus (pishin district) . The plants were screened to determine the bioactive compounds. The phytochemical tests that were used in the analysis included alkaloids, anthraquinones, Carbohydrate, cardiac glycoside, flavonoids, protein, saponins, tannins and terpenoids. Phytochemical screening of the plants showed that Azadirachta indica contains alkaloids, anthraquinones, cardiac glycoside, fatty acids, flavonoids, tannins and terpenoids. Foeniculum vulgare showed the presence of alkaloids, anthraquinones, cardiac glycoside, fatty acids, flavonoids, and tannins. Whereas Fumaria indica showed positive results for alkaloids, anthraquinone, fatty acids, flavonids, tannins, anthraquinone (Harboi district). There were only two positive results of Cichorium intybus i.e saponins and fatty acids. The chemical constituents found probably are the active compounds that lower the effect of microorganisms and diseases.

Design and Characterization of 2D and 3D Novel Metal-Organic Frameworks by using Carboxylates Based Ligands through

Hydro/Solvothermal Treatment

M. Athar and Muhammad Adnan Asghar

Institute of Chemical Sciences, Bahauddin Zakariya University, Multan

Abstract:

The young family of hybrid inorganic-organic porous materials named metal-organic frameworks (MOFs) or porous coordination polymers features highly interesting properties, which are potentially attractive for various applications in gas storage, separation, catalysis, sensing, ion exchange, luminescent, biomedicence and drug delivery. The huge advantage of MOFs compared to conventional porous materials is its robustness and the ability to tune the individual building blocks and therefore the properties of the related porous hybrid materials on the molecular level. Our study has involved the synthesis and characterisation of functionalized porous metal organic framework materials based on carboxylate based ligands by using transition and lanthanide metals through hydrothermal processes. Single crystal X-ray crystallographic determination revealed that the designed MOF’s are falls in the of two dimensional and three dimensional supramolecule structural category.The overall objective was to increase pore size by using specified functional groups and framework flexibility in determining the adsorption characteristics of gases and vapours and assess the possible applications of these materials for gas storage and separation.

Synthesis and Characterization of Spirosilanes

Ezzat Khan

Department of Chemistry, University of Malakand, Chakdara, Khyber Pakhtunkhwa, Pakistan

Abstract:

Since last few years the process of organoboration and hydroboration proved to be a facile route for the synthesis of silicon heterocycles. The silicon heterocycles such as siloles obtained via 1,2-ethylboration of silanes have been reported and the reaction has been fully explored. Similarly 1,2-hydroboration has led to a group of silanes bearing both silyl and boryl groups linked to the gemenal carbon atom. The combination of 1,2-hydroboration and 1,1-organoboration is in practice in our group. This combination has successfuly produced 1-


68

silacyclobutene, 1-silasyclopent-2-ene and 1-silacyclohex-2-ene derivatives. Various organic (alkyl and aryls) as well as inorganic groups (Cl, H, SiMe3) have been included. Besides simple silicon heterocycles the processes have been proved to be applicable for the synthesis of spirosilanes such as 4-silaspiro[3.3]hepta-1,5-dienes and 5-silaspiro[4.4]nona-1,6-dienes. The structure of all new silanes were determined by using modren analytical techniques. Analytical data (NMR and X-ray diffraction) regarding these compounds and complete reaction mechanism will be discussed.

SiB

R

B

RR

R

Si

B

B

R

R

A B

Scheme 1. Representation of spirosilanes in general

Antioxidant and Antimicrobial Activities of Different Parts of Plant Ranunculus glacialis

Hafiz Muhammad Adeel

a, Matloob Ahmad

a, Nasir Rasool

a, Muhammad Zubair

a, Muhammad

Riaza, Lubna Tahir

b, Shafqat Ali

c

aDepartment of Chemistry, Government College University, Faisalabad-38000, Pakistan bApplied Chemistry Research Center, PCSIR Laboratories Complex, Lahore, Pakistan

cDepartment of Chemistry, Quaid-I-Azam University, Islamabad 45320, Pakistan

Abstract:

Modern drugs have been isolated from natural source and use in traditional medicines. Plants generally produce many secondary metabolites which constitute an important source of microbicides, pesticides and many pharmaceutical drugs. Present research work is a part of such investigations on Ranunculus glacialis. It belongs to the family Renunculaceae. There is a very little work on this plant so far and limited information published on the biological activities of this plant. So there is a need to analyze antimicrobial activity of this plant. The various parts of Ranunculus glacialis were extracted with absolute methanol and further fractionated by solvent-solvent extraction method with increasing polarity based absolute solvents i.e. chloroform, ethyl acetate and n-butanol, n-hexane. The methanolic extract of various parts of Ranunculus glacialis and their fractions were analyzed for their antioxidant and antimicrobial activities. It contained appreciable levels of total phenolic and flavonoid contents. HPLC analysis of n-hexane, Chloroform, ethyle acetate and n-butanol fraction of various parts for total phenolic and flavoniods also carried out. The GC-MS analysis of Ranunculus glacialis essential oil and n-hexane extract revealed the presence of several compounds. LCMS analysis of dry plant also carried out. The plant extract and fraction were assessed against human blood erythrocytes (RBCs) for cytotoxic studies by haemolytic activity


69

Biochemical Modification in Canola Exposed to Water Deficit Stress after Exogenous Supplementation of Calcium

Rizwan alam1, Ikhtiar Khan

1, Aqib Iqbal

2

1Institute of Chemical Sciences, University of Peshawar, Peshawar, Pakistan

2Institute of Biotechnology & Genetic Engineering, KPK, Agricultural University, Peshawar,

Peshawar, Pakistan

Abstract: An experiment was conducted to investigate the biochemical modifications triggered in canola (Brassica napus) seedlings after exogenous calcium supplementation followed by imposition of water deficit stress by withholding the irrigation water supply for 10 days. It was observed that drought stress increased the accumulation of proline, hydrogen peroxide,catalase and ascorbate peroxidase activity. Exogenous calcium supplementation further increased the accumulation of proline and catalase and ascorbate peroxidase activity but decreased the hydrogen peroxide content under water stress condition.

Isolation and Characterization of 1,3,7-Trihydroxy Xanthone from Hypericum oblongifolium

Mumtaz Ali and Mohammad Arfan

Department of Chemistry, University of Malakand

Abstract: The phytochemical investigation on Hypericum oblongifolium has led to the isolation 1,3,7-Trihydroxy xanthone along with other compounds. The structure of copound was established on the basis of 1 D and 2 D NMR spectroscopic techniques.

O

C

O OH

OH

H

HO

H

H

H

H


70

Effeciency of Fenton and Fenton like Processes for Removal of Reactive Red 195 from Synthtic Wastewater

Sofia Nosheen2, Iffat Batool, Sadaf Ghaffar, Khalil-U-Rehman4

Department of chemistry and biochemistry, University of Agriculture, Faisalabad

Abstract: Waste matter released from the textile manufacturing confines numerous contaminant involving a large amount of organic materials and colour. Relying on nature of the dyes present inside this water causes a number of serious health and environmental problems. The existence of very small concentration of dyes in effluent is clearly seen and their possible degradation products causing cancer. The present research exertion involved removal of reactive azo dye red 195based on fenton and fenton like oxidizing agents using ultraviolet-Visible spectroscopy as measure of color removal. Various operational parameters like pH, concentration of oxidizing agents, effect of shaking vs. static and effect of ratio of oxidizing components was checked in order to get highest degree of decolorization. Maximum decolorization was found to be at pH 4.5, in fenton like reaction. Shaking condition showed more proficient results than static. Decolorization rate went on increasing with increasing contact time from 60-120 min progressively.COD and TOC values also confirmed that fenton and fenton like processes being employed are active in not only reducing color but also degrading the dye into smaller components which are less toxic.

Exhaust Dyeing and Printing Properties of Mono Azo Reactive Dyes on Cotton Fabric

Qurat-ul-ain Saeed, Ijaz Ahmad Bhatti,Muhammad Zahid and Muhammad Abbas*

Department of Chemistry & Biochemistry, University of Agriculture, Faisalabad

Harrris Dyes and Chemicals (PVT) Limited, Faisalabad

Abstract: This study explores the printing properties and exhaust dyeing of four newly synthesized reactive dyes. Dyes was applied atdifferent conditions of dyeing parameters such as pH, electrolyte concentration, time and temperature in order to get maximum fixation. After printing on fabric, color strength was determined with Spectraflash SF 600 spectrophotometer and fastness properties such as washing, crocking, light; perspiration, chlorinated water and dry cleaning were investigated by ISO standard methods. Exhaustion and fixation values were evaluated by UV/VISSpectrophotometer. All dyes showed remarkable color strength in the range of 70 to 80% for printing. Percentage dye bath exhaustion and fixation has been found to be in the range of 65 to 85%, which is reasonably good and acceptable. Fastness properties were good to excellent.


71

Adsorptive Removal of Novacron Orange P-2R by Agricultural Wastes in the Aqueous Solution

Saima Noreen and Haq Nawaz Bhatti 1Department of Chemistry & Biochemistry, University of Agriculture, Faisalabad

Abstract: Synthetic dyes are commonly used in textile industries. The release of unused dyes poses a serious threat to aqueous environment. In this context agricultural wastes were utilized as a replacement for the current expensive chemical and biological methods of removing reactive dyes from synthetic aqueous solutions. The study was carried out in batch mode by using Novacron Orange P-2R reactive dye. The effect of process parameters such as pH, biosorbent dose, initial dye concentration, contact time, and temperature was evaluated. The best adsorptions conditions were optimized during the study. The optimum pH and dose for the maximum removal was found to be 2 and 0.05. The equilibrium time of raw biosorbent used for the removal of Novacron Orange P-2R was 2 h. The equilibrium time of pretreated biosorbent used for the elimination of Novacron Orange P-2R was 90 minutes. The equilibrium time of immobilized biosorbent for the removal of Novacron Orange P-2R it was found to be 90 minutes. The optimum initial concentration of Novacron Orange P-2R for raw, pretreated and immobilized bagasse was found to be 200, 400 and 400 ppm. The optimum temperature for all biosorbents was 30oC but for pretreated bagasse was found to be 600C. The effect of salt, heavy metal ions and surfactants was also analyzed because industrial waste water mostly contains these auxiliaries. The equilibrium data for all used reactive dye was analyzed by using linear form of different isotherm models like Langmuir, Freundlich, D-R, Harkins-Jurra and Temkin. The kinetic data was also analyzed by using pseudo-first-order, second-order and intra- particle diffusion kinetic models. The best fit equilibrium model for Novacron Orange P-2R was found to be Langmuir isotherm and best fitted kinetic model was found to be pseudo-second-order. Different thermodynamic parameters like ∆Go, ∆So and ∆Ho was also calculated by using thermal data. The results were analyzed statistically using regression analysis

Synthesis of SBA-16 Supported Copper Nanoparticles and their use for Fabrication of Carbon Nanotubes by Chemical Vapour Deposition Method

Asma Tufail Shah, †

M. Makshoof Athar, Tajamal Hussain ‡ Institute of Chemistry, University of the Punjab, New Campus Lahore 54590, Pakistan

Abstract: A novel catalyst ‘SBA-16 supported copper nanoparticles’ has been synthesized by reduction method using SBA-16 as a support. SBA-16 plays a vital role in maintaining the particle size of the metal and prevents particle agglomeration at high temperature. SEM image reveals that nano-size particles of spherical morphology have been uniformly dispersed on SBA-16 spheres. TGA results indicate that the synthesized material is thermally stable. The material has been used as a nanocatalyst for the fabrication of carbon nanotubes by thermal chemical vapour deposition (CVD) method using benzene as a precursor. The fabricated carbon material was characterized by XRD and SEM techniques. Their results showed that carbon nanotubes (CNTs) of average diameter 100 nm and length 10 um along with micro-sized carbon beads were produced.


72

Highly Sensitive, Selective and Stable Multi-metal Ions Sensor Based on Ibuprofen Capped Mercury Nanoparticles

Sirajuddin


Abstract: We report a one pot synthesis of mercury nanoparticles (HgNps) from mercuric chloride using hydrazine as a reducing agent and ibuprofen to coat the particles. The particles were synthesized under various conditions of pH and varying mercuric chloride, hydrazine, ibuprofen and sodium hydroxide concentrations. Ibuprofen capped HgNps (Ibu-HgNps) were characterized by UV–visible spectroscopy, scanning transmission electron microscopy (STEM) and Fourier transform infrared (FT-IR) spectroscopy. The as prepared Ibu-HgNps were applied onto glassy carbon electrode (GCE) and used as voltammetric sensor for simultaneous determination of Zn(II), Cd(II), Pb(II) and Cu(II) ions. Response was linear in the range of 0.1–600 ppb with regression coefficients around 0.999 for all metals. The lowest detection limit (LDL) for Zn(II), Cd(II), Pb(II) and Cu(II) was 0.05 ppb, 0.042 ppb, 0.03 ppb and 0.035 ppb showing high reproducibility with relative standard deviation (RSD) of 3.8%, 1.35%, 1.62% and 3.55% respectively for 15 repetitive scans. The sensor was successfully used for monitoring Zn(II), Cd(II), Pb(II) and Cu(II) in various types of water samples.

Detoxification of Chillies by Reducing the Fungal Load and Aflatoxins using Ionizing Radiation

Shahzad Zafar Iqbal

a, Ijaz Ahmad Bhatti

b, Muhammad Rafique Asi

c, Muhammad Shahid

b

aDepartment of Applied Chemistry, Government College University Faisalabad, 38000, Pakistan

bDepartment of Chemistry & Biochemistry, University of Agriculture Faisalabad, 38040,

Pakistan cFood Toxicology Lab, Plant Protection Division, Nuclear Institute for Agriculture and Biology,

Faisalabad, Pakistan

Abstract: Chillies are very important cash crop of Pakistan and most of the time its export comes to the bottom line due to the fungal load. They are much vulnerable to fungal due to poor storage conditions and effective methods for their decontaminations which are acceptable worldwide are still unavailable. The aim of this study was to analyze the effect of gamma irradiation on the populations of Aspergillus section Flavi and aflatoxins in chillies samples collected from different districts of Punjab, Pakistan. It is found that among the Aspergillus species isolated, those belonging to section parasiticus were predominant. Gamma ray absorbed doses of 0, 2, 4 and 6 were employed on fungi and chilli samples using Cs-137 gamma irradiator at Nuclear Institute of Agriculture and Biology (NIAB), Faisalabad. The un-irradiated and irradiated samples were subjected to the isolation of aflatoxins followed by their detection using HPLC system equipped with the fluorescence detector. The fungal load and colonization of the chilli was assessed as colony forming unit per gram of chilli (cfu/g). The results demonstrate that the dose of 6 kGy has shown significant effect (α ˂ 0.05) on the fungal load reduction has predominantly reduced the level of AFB1 from 86 to 97% while 81 to 92% of total AFs in ground and whole chillies, respectively. The study reveals that the radiation treatment is safe and effective method to decontaminate the chillies from the aflatoxins load to make them wholesome.


73

Study on Different Rapid Corrosion Tests and its Passivation on Iron and Steel

Zahra Batool Butt, Salman Iqbal, I.H.Khan¹, Arshad Mahmood²

¹Ex.Member Science PCSIR

²Maki Calibration Lab

Abstract: The iron and steel materials used in the commercial hardware is not surface treated by passivation. This cause corrosion during the course of their use. Based on results of data analysed during research the following conclusions are drawn. All out of three cases of acids (CH3COOH,

NaCl, HNO3+HCl+NaCl) used for rapid corrosion, the experiment using HNO3+HCl+NaCl shows very rapid corrosion rate as compared with other. All conditions comprises of three samples were kept same in situations for 1, 2 and 4 hours treatment time. The maximum prevention/protection from corrosion is achieved by coating of epoxy on iron samples.

Adsorption Studies of Cobalt from Aqueous Media by using Rice Husk

Shagufta Zafara*, Nasir Khalid

b and Muhammad Latif Mirza

a

aDepartment of Chemistry, The Islamia University of Bahawalpur, Pakistan

bChemistry Division, Pakistan Institute of Nuclear Science and Technology, P.O. Nilore,

Islamabad, Pakistan

Abstract: The aim of this study was to find out the use of rice husk for the adsorption of cobalt from aqueous media. Various parameters were optimized like contact time, weight of adsorbent, pH, initial metal concentration and temperature. Maximum adsorption was observed at 10 minute

shaking time by 0.2g of adsorbent at 0.0001MHNO3 using 10 mL of 2.43 x 10-−5 mol / L of cobalt solution. Batch method was used and the quantification of Co was made by AAS technique. Kinetic data reveled that the adsorption of Co on rice husk followed pseudo 2nd order model R2 = 0.9974.The adsorption data obeyed the Langmuir, Freundlich, D-R and Temkin isotherm. The determined adsorption capacity of Co on rice husk through Langmuir and Freundlich isotherm was 0.960 and 43.27 mg/g respectively. The sorption free energy calculated from D-R isotherm was found to be 10.31 k j/mol indicating chemisorption nature of Co adsorption on rice husk. The effect of temperature was also studied which showed that adsorption increased with increase in temperature. Thermodynamic parameters like ∆G, ∆H & ∆S were evaluated from Vont,Hoff plot. Negative values of ∆G confirmed favorable and spontaneous nature of cobalt adsorption on rice husk. Positive value of ∆H showed endothermic nature of adsorption whereas positive value of ∆S suggested increase in the randomness at the inter-phase of solid and liquid. Effect of various cations and anions were also studied. The developed procedure was successfully applied to the spiked sample of tap water for the removal of Co from aqueous media.


74

Methanolysis of Eruca Sativa Oil for Optimized Production of Biodiesel

Muhammad Waseem Mumtaz a, b

, Muhammad Danish a

, Muhammad Zubair a, Muhammad

Nadeem Zafer a

, Mehrban Ashiq a

a Department of Chemistry, University of Gujrat, Pakistan

b Department of Chemistry, GC University Lahore, Pakistan

Abstract: Present work describes the optimized methanolysis of Eruca sativa oil for the production of biodiesel. The reaction parameters for biodiesel production using chemical and enzymatic methanolysis of Eruca sativa oil were optimized using RSM. Different reaction parameters viz catalyst/enzyme type, catalyst/enzyme concentration, reaction temperature, reaction time and methanol to oil molar ratio were optimized and comprehensive study was conducted to achieve highest biodiesel yields using both chemical and enzymatic methanolysis. NaOCH3 catalyzed methanolysis was depicted to give highest biodiesel yields comparative to KOH, NaOH catalyzed methanolysis whereas, during enzymatic methanolysis, NOVOZYME-435 catalyzed methanolysis resulted into higher biodiesel yields comparative to A.n.Lipase catalyzed methanolysis reactions. For optimized chemical methanolysis, 0.5 to 0.75% catalyst concentrations, 6:1 to 7.5:1 methanol to oil molar ratio, 45 to 52.5oC and 60 min reaction time, whereas, for enzymatic methanolysis 1.0 to 1.25% enzyme concentrations, 6:1 to 9:1 methanol to oil molar ratio, 30 to 32.5oC reaction temperature and 60 to 96 hrs were found to be optimized reaction parameters to obtain highest product yields. Monitoring of methanolysis of Eruca sativa oil was carried out using FTIR spectroscopy and High Performance Liquid Chromatography (HPLC), while compositional analysis of synthesized biodiesels was performed with Gas Chromatography equipped with Mass Spectrometric detector (GC-MS).

Hydrothermal Synthesis of Hydroxyapatite Nanoparticles using Different Organic Surfactants

*Sumaira Naz, Shahid Khan Durrani, Qanita Tayyaba, Khalid Saeed and Nazar Hussain

Materials Division, Directorate of Technology, PINSTECH, P. O. Nilore, Islamabad, Pakistan

Abstract: Hydroxyapatite, Ca10(PO4)6(OH)2 is the emerging most bioceramic, which is widely used in various biochemical applications, mainly in orthopedics and dentistry due to its close similarities with organic mineral component of bone and teeth. Synthetic hydroxyapatite is known to be similar to naturally occurring hydroxyapatite on the basis of crystallographic and chemical studies. Nanoparticles of hydroxyapatite (Ca10(PO4)6(OH)2) were prepared synthetically by hydrothermal method using surfactants such as CTAB, Twin 80, SDS, PVA, TEAOH and TPABr as organic templates. Mixtures of precursors and surfactants were placed in autoclave for 3 h at 150ºC, which produces fine powder of hydroxyapatite. The products were characterized for phase analysis, thermal properties, structure composition, and structure morphology by using XRD, TGA-DTA, FTIR and SEM. The XRD patterns revealed the formation of similar hydroxyapatite phase using different surfactants (CTAB, Twin 80, SDS, PVA, TEAOH and TPABr) at the same hydrothermal processing conditions. It is observed that organic templates (surfactants) affect the morphologies and nanosize of hydroxyapatite nanoparticles.


75

Treatment of Reactive Violet 1 Dye by Ultraviolet Radiation in Presence of Hydrogen Peroxide

Majid Muneer1, Ijaz A. Bhatti

2, Munawar Iqbal

1. Department of Chemistry Government College University Faisalabad, Pakistan.

2. Department of Chemistry University of Agriculture, Faisalabad, Pakistan

Abstract: The discharge of massive amount of coloured wastewater from dyes and textile industries cause environmental problem due to release of dyes and related compounds into water bodies. The conventional treatment methods are insufficient for the complete degradation and removal of these pollutants from wastewater, which require an effective method for the degradation as well as mineralization of organic compounds such as dyes. Advanced oxidation process, using UV radiations in combination with H2O2 (UV/H2O2) is an effective alternative for treatment of dyes. In the present work the degradation of synthetic dye (Reactive Violet 1) in aqueous media concentration ranges from 10-50 mg/L, has been carried out by advanced oxidation treatment using UV radiation in combination of H2O2. The effect of different operational parameters such as UV-radiation dose (time), H2O2 concentration and dye initial concentration on degradation has been evaluated. A feasible degradation scheme is proposed as well. The change in absorption of dye solutions were monitored by double beam UV/Vis spectrophotometer. The Radiolytic end products are analyzed by FTIR and GC-MS. The proposed scheme has been correlated with the experimental results which show good agreement. The advanced oxidation treatment is found to be an efficient treatment method for manipulating textile wastewater containing dyestuff.

Permanganate Oxidation of Ascorbic Acid in Acidic Medium: Kinetics and Mechanism

Raheela Naz

a, Rafia Azmat

a, Noshab Qamar

b, Anum Shafi

b

Department of Chemistry University of Karachi

Department of Chemistry, Jinnah University for Women, Karachi, Pakistan

Abstract: The kinetics of oxidation of ascorbic acid by permanganate ion in acidic medium at 30±10C, I=0.01mol dm-3(KNO3) and [H+] = 1mol dm-3 have been studied. The reaction follows first order kinetics with respect to [MnO4

-], [Ascorbic acid] and [H+]. Sulphuric acid was used to maintain an acidic medium. Direct relation of increasing ionic strength on reaction rate indicates the presence of ionic species in the rate determining step. The rate of oxidation was affected by the change in temperature. The energy of activation for the reaction (Ea) was 16.2kJ/mol. A reaction mechanism has been proposed.


76

Bioethanol Production from Potato Waste

Zaib Hussain and Syeda Shafaq Gilani

Institute of Chemistry, University of the Punjab, Lahore 54590

Abstract: The potato is considered as a tuberous crop capable of growing in almost all conditions in diverse climate. Owing to the large quantity of vitamins, minerals and thickener contained within, potato and potato peel waste contains sufficient quantity of starch, cellulose, hemicellulose and fermentable sugars. These constituents are important in the production of bioethanol and studies were performed to optimize the conditions for bioethanol production viz effect of pH (4-9), temperature (30 - 90°C), heat treatment and enzyme specificity with 0.5 ml amylase / diastase bacterial solution with the addition of yeast. Effect of pH had considerable impact on bioethanol production with maximum yield of product obtained in a slightly acidic medium. The optimum temperature for combined microbial growth and ethanol tolerance was 60°C. Saccharification at 77°C and fermentation of the potatoes under anaerobic conditions by enzyme treatment enhanced production of the biofuel. The biofuel yield per kilogram tubers was 49.52 ml/kg, compared to the theoretical value of 83.72 ml/kg. Agricultural products and waste materials can be used for production of bioethanol fuel as the optimum alternative fuel for gasoline. Bioethanol produced from potato waste has a large potential market and is an environmentally friendly fuel which has the potential to provide comparable engine performance results.

Heavy Metal Content of Mangoes (Mangifera Indica L.) Cultivated in Different Regions of Pakistan

Nusrat Jalbani,*

Pakistan Council Scientific and Industrial Research Laboratories Complex, Karachi, Pakistan

Abstract: The objective of present study is to determine the essential/non essential elements in mango (Mangifera indica L.) the fifty samples of three varities such as Dusahri, Langra and

Chaunsa grown in were analysed. These samnples were collected from different region of Pakistan i.e. Multan, Sadiqabad, Rahim yar khan and Mirpurkhas. The understudy elements were determined by flame atomic absorption technique and Graphite Furnace using wet acid digestion method. These samples were provided by cultivators of above mentioned areas. The concentrations of toxic elements (TEs) were determined in 50 samples of mango. The under study elements were determined by flame atomic absorption technique and Graphite Furnace using wet acid digestion method. The concentrations of Cd and Pb were found to vary from 1.86- 5.80 µg/Kg and 8.14-13.0 µg/Kg, respectively, whereas lower levl of Cd and Pb were found in. The Limit of detections (LODs) of the method were found to be; 0.113, 2.0, 22.7, 3.85, and 3.05 µg/L for Pb, Cd, Cu, Fe, and Zn, respectively. The proposed method provides quantitative recoveries of target metal ions ranging from 96.0 to 99.3%. Accuracy was checked by performing addition-recovery experiments as well as by using reference materials (wheat Flour). All results obtained for reference materials were in agreement with certified values at a 95% confidence level.


77

Synthesis and Antimicrobial Activity of some Novel β-lactam Derivatives.

S.Shah N.N *, M.A.Baseer

P.G. Department of Chemistry, Yeshwant College Nanded, Maharashtra (India)

Abstract:

The β-lactams are well-known heterocyclic compounds among the organic and medicinal chemists1 The activity of the famous antibiotics such as penicillins , cephalosporins and carbapenems are attributed to the presence of 2-azetidinone ring in them. Recently, some other types of biological activity besides the antibacterial activity have been reported in compounds containing 2-azetidinone ring2-3. Such biological activities includes antifungal, antitubercular, antitumar, cholesterol absorption inhibition and enzyme inhibition activity. The β-lactams also serve as synthons for many biologically important classes of organic compounds4. Due to this, the investigation of chemistry and biology of these compounds continue to appeal the synthetic and medicinal organic chemists. 1-4

In present work we have synthesized the some novel derivatives of β-lactams . The newly synthesized derivatives are characterized by spectral analysis and are screened for antimicrobial studies and showed moderate to good activity.

R-CH=N-R'

NO

R'

R

R''

Reagent ( ----R'')

Serum Concentration of Thyroid Related Hormones in Children Presenting with and without Goiter

Shan Elahi, Muhammad Khalid, Ghulam Rasool and Mansoor Khan

Centre for Nuclear Medicine (CENUM), P.O. Box 53, Mayo Hospital, Lahore

Abstract: During January 2010 to December 2011, among 1571 children attending CENUM 945 were selected for this study. Their mean (+ SD) age was 10.0 + 2.2 years with age range between 1 to 12 years. Among selected children 334 (35.3%; 241 female, 93 male) presented with goiter. The rest of children (n=611; 421 female, 190 male) were without goiter. Serum FT4 was estimated by radioimmunoassay (RIA) and TSH by immunoradiometric assay (IRMA) techniques using commercial kits of Immunotech Inc. (Beckman, Czech Republic). Results showed that more children without goiter (n=508; 83.1%) as compared to children with goiter (n=250; 74.8%) had normal values of FT4 (11-22 pmol/L) and TSH (0.3-4.0 IU/L). The difference was statistically significant (P<0.05). Hypothyroidism (low FT4 and high TSH) was detected in 76(8.0%) children. The children presented with goiter had significantly more incidence of hypothyroidism as compared to controls (12.9% vs 5.4%; p<0.05). Hyperthyroidism (high FT4 and low TSH) was detected in 19(2.0%) children and its incidence was comparatively more in goitrous children


78

(4.8% vs 0.5%; p<0.05). Overall thyroid dysfunctions (hyperthyroidism and hypothyroidism) were detected in 59(17.7%) children presented with goiter and 36(5.9%) without goiter. It is concluded that among children referred to CENUM those presenting with goiter had three times more incidence of thyroid dysfunctions as compared to those presenting without goiter.

Synthesis and Characterization of Methyl [4-oxo-2-(Substituted Benzoylimino)-3 (Substituted Phenyl) Thiazolidin-5-ylidene]acetates:

Aamer Saeed,* Naeem Abbas**

*Quaid-i-Azam University Islamabad

** University of Gujrat

Abstract: The cyclic condensation of 1-aroyl-3-aryl thioureas with dimethyl acetylene dicarboxylate (DMAD) in methanolic solution at room temperature resulted in the formation of methyl [4-oxo-2-(substituted benzoylimino)-3-(substituted phenyl) thiazolidin-5-ylidene] acetates in good to excellent yield.

Synthesis and Biological Evaluation of Benzothiazine-based Schiff-Bases

Farhana Aman, Waseeq Ahmad Siddiqui, Adnan Ashraf

Department of Chemistry, University of Sargodha, Sargodha-40100, Pakistan

O

NH

SO

O

SN

O

OOH

OO

R SN

O

OO

R SN

N

OO

R

N

R'

1 4-6 7-9 10-12 13-46

SN

N

OO

R

NH2

Scheme

Abstract: The 1,2-benzothiazine 1,1-dioxide nuclei find their application for the synthesis of the most recent class of Non-steroidal Anti-inflammaotry Drugs (NSAIDs), Oxicams1. Piroxicam2 and Meloxicam3 are the representative drug molecules of this class currently in use in Pakistan. The Schiff-base molecules are historically important with respect to their biodeiversity4. As part of our ongoing research programme5-6, we have synthesized thirtythree (33)novel Schiff-base ligand molecules for the first time using 1,2 –benzothiazine 1,1 dioxide as the basicfunctional entity. Commercial readily available saccharin (1) was employed as starting material. Condensation of this molecule with methyl chloroacetate to form N-methylacetate derivative, followed by Gabriel Colman rearrangement resulted into the precursor 4-hydroxy-3-carbomethoxy-2H-1,2-benzothiazine 1,1-dioxide nuclei (4-6).These benzothiazineswere decarboxylatedto yield corresponding ketones (7-9) which upon reaction with hydrazine and subsequently with a variety of un/substituted aromatic aldehydes yielded respective mono- and di-imine group containing Schiff-base ligands (13-46).


79

All the spectroscopic and spectrometric analyses, including Singly Beam X-ray crystallography has confirmed the formation of these new potent biologically important molecules. The Bioassay studies such as antibacterial, antifungal have revealed promising results. Biological screening for other activities is continued.

ββββ-Carotene: A Green, Inexpensive, and Convenient Solvatochromic Probe for the Determination of Solvent Polarizabilities

Muhammad Imran, Omar A. El Seoud

Institute of Chemistry, University of São Paulo Brazil,

Higher Education Department, Govt. of Punjab Pakistan

Abstract:

Solvent polarizability, SP, has been previously determined by using the solvatochromic probe 3,20-di-tert-butyl-2,2,21,21-tetramethyl-3,5,7,9,11,13,15,17,19-docosanonaene, ttbP9,

whose synthesis involves 15 steps. We show here that the natural dye β-carotene, 1,1'-(3,7,12,16-tetramethyl-1,3,5,7,9,11,13,15,17-octadecanonaene-1,18-diyl)bis[2,6,6-trimethylcyclohexene], can be conveniently employed for the accurate determination of the same solvent property. This conclusion is based on both theoretical calculations and experimental data. The former includes free energies of solvation, and the wavenumber of the longest wavelength (i.e., the

solvatochromic) transition. Both quantities for β-carotene correlate linearly with the corresponding values of ttbP9, with slopes and correlation coefficients of practically unity. The

plot of experimentally calculated SPββββ-carotene versus SPttbP9 was found to be linear for 68 solvents. Previously unknown SP values are reported for eight ROCH2CH2OH (R = C1 to C10) and four 1-allyl-3-R-imidazolium chloride ionic liquids.

Antioxidant Activity and Phenolics Contents Different Parts of Citrus Limon and Citrus

Pseudolimon

Bushra Sultana1*, Farooq Anwar

2, Muhammad Mushtaq

1, Mahboob Alim

1

1Department of Chemistry and Biochemistry, University of Agriculture, Faisalabad

2Department of Chemistry, University of Sargodha, Sargodha

Abstract:

The present research work was designed to investigate phenolicl contents and antioxidant activity of different parts (leaves, peels and seeds) of Lemon (Citrus limon) and Galgal (Citrus pseudolimon) indigenous to Pakistan. Methanolic extracts of from different parts of these two Citrus species were tested for total phenolic contents (TPC), total flavonoid contents (TFC), DPPH radical scavenging activity, % inhibition of linoleic acid peroxidation and reducing power by using respective in vitro antioxidant model assays. The percentage yield of extracts, total phenolic and flavonoid contents among parts tested varied from 6.13 – 24.20 g/100g, 98.20 – 199.18 (mg gallic acid equivalent/ g of extract) and 19.95 – 39.60 (mg catechin equivalent/ g of extract), respectively. Percent inhibition of linoleic acid peroxidation and DPPH radical scavenging capacity for the tested extracts ranged between 31-60 and 40-62, respectively. The overall order of antioxidant potential among parts of Citrus species was established to be: C.

pseudolimon leave > C. limon leave > C. pseudolimon peel > C. limon peel > C. pseudolimon

seed > C. limon. It could be concluded that extracts from the tested parts of Citrus species, especially, from the leaves can be explored as an economically viable source of natural antioxidants.


80

Phytochemical and Biological Analysis of Adonis aestivalis

Asim Anwara, Muhammad Zubair*

a, Komal Rizwan

a, Muhammad Zia-Ul-Haq

b, Nasir Rasool

a,

Muhammad Farmanc, Muhammad Riaz

a,

aDepartment of Chemistry, Government College University, Faisalabad-38000, Pakistan

bResearch Institute of Pharmaceutical Sciences, Department of Pharmacognosy, University of

Karachi, Karachi 75270, Pakistan cDepartment of Chemistry, Quaid-I-Azam University, Islamabad 45320, Pakistan

Abstract: Nature has been a source of medicinal agents for thousands of years and a substantial number of modern drugs have been isolated from natural sources, many based on their use in traditional medicines. Present research work is a part of such investigations on Adonis aestivalis. Different fractions were taken by solvent extraction method and their phytochemicals and biological analyses (antimicrobial and antioxidant) were carried out. Essential oil of the plant was extracted and subjected to GC-MS analysis. During the course of this work, n-butanol, Chloroform, Ethyl acetate and Methanol fractions were studied by HPLC and LC-MS. The cytotoxicity was analyzed by haemolytic assay.

High Performance Liquid Chromatographic Determination of Dopamine by Derivatization Method using 2-hydroxynaphthaldehyde as a Derivatizing

Reagent

Asghar Ali Majidano, Subhan Ali Majidano, Mohammad Tariq Mahar, Muhmmad Yar Khuhawar

Institute of Advanced Research Studies in Chemical Sciences, University of Sindh, Jamshoro

Abstract: Determination of Dopamine (DA) methyl dopa (MD) L-dopa (LD) and Tyrosine (TY) by High Performance Liquid Chromatography using 2-hydroxynaphthaldehyde as a Derivatizing Reagent, Borax buffer of pH 8.5 has been carried out using column Phenomenex C – 18, 5 µm (150×4.6mm id) followed by heating time 15 min at 75 0C, Flow rate of mobile phase 1ml/min. The linear calibration graphs were obtained within the range of 2.5-25µg/ml with relative standard deviation (RSD) 1.5-2% and recovery 98% with RSD 1.2%.


81

Investigate of CIE (L*,a*,b*) and the Total Colour Difference "∆∆∆∆E*" Value of Different Banknote Papers (Egyptian 5 pounds "EGP", Egyptian 10

pounds "EGP", 1 Riyal "SAR", 5 Dirham "AED", 1 Dolar "U$", 5 Euro "€") upon CMC Modification and Accelerated ageing

G.N. Simonian

1*, R.F. Basalah

2, F. T. Abd El Halim

3, F.F. Abd El Latif

4, A. M. Adel

5,

A. M. El Shafey6*

1Professor of Printing, Faculty of Applied Arts, Helwan University, Egypt

2General Director, Forgery and Counterfeiting Department, Ministry of Justice,

Egypt (Previously) 3Professor of physical chemistry, Faculty of Science, Minia University, Egypt

4Professor of Organic Chemistry, Faculty of Science, Minia University, Egypt

5Assistant professor of Cellulose Chemistry, National Resreach Center, Dokki, Egypt

6Forgery and Counterfeiting Expert, Ministry of Justice, Egypt

Abstract:

Banknote papers include an extensive range of security features that involve secure complex process such as watermark, security thread, micro printing etc. Security features are very important elements integrated into paper banknotes for facing counterfeiting as without the presence of security features within banknote papers how we can face the counterfeiting crime!

In the present paper, different banknote papers (Egyptian 5 pounds "EGP", Egyptian 10 pounds "EGP", 1 Riyal "SAR", 5 Dirham "AED", 1 Dolar "U$", 5 Euro "€") are coated by different concentrations and different layers of carboxymethyl cellulose (CMC). Accelerated ageing speeds the natural ageing process of paper by subjecting it to extreme conditions. We performed accelerated ageing; thermal ageing at 140 °C for 2 hours and UV-radiation ageing with

two different wavelengths (λ1= 256 nm, λ2 = 336 nm). Change CIE (L*, a*, b*) and the total colour difference (colour tolerance); AE* values were investigated before and after CMC coating. Change CIE (L*, a*, b*) and the total colour difference (colour tolerance); AE* values were measured and calculated before and after accelerated ageing. The security features of banknote papers were examined through transmitted light, UV light and IR. It can be concluded that the effectiveness of security features integrated into banknote papers are marvellous as the accelerated ageing have no effect even small on the security features after CMC modification which reflects in increasing banknote papers durability.

Facile Synthesis of Zinc Oxide Nanoparticles with Urea: Characterization and Optical Properties

1Samira Bagheri,

2Sharifah Bee Abd Hamid

1,2 Centre of Research in Nanotechnology & Catalysis

(COMBICAT), IPS Building, University of Malaya,

50603, Kuala Lumpur, Malaysia

Abstract: Nanosized zinc oxide (ZnO) in the size of 20 to 30nm, synthesized by precipitation method by using urea as a precipitation agent. The ZnO nanoparticles were characterized by a number of techniques, such as X-ray diffraction analysis (XRD), Fourier transform infrared


82

spectroscopy (FTIR), Transmission electron microscopy (TEM) and UV-Vis. The ZnO nanoparticles exhibited a hexagonal structure. The results showed that urea is an intresting material that can be used as a precipitation agent in this method for preparing zinc oxide nanoparticles.

Reduction of Hexavalent Chromium Using L-Cysteine Capped Nickel Nanocatalysts Supported by UV-Visible Irradiation

Nazar Hussain Kalwar, Sirajuddin*, Syed Tufail Hussain Sherazi


Abstract: The aim of present study is to reduce hexavalent chromium i.e. Cr(VI) species from aqueous environments. This study was conducted for reduction/remediation of Cr(VI) ions by strong reducing agent (namely sodium borohydride) that showed very low reduction of Cr(VI) ions in absence of catalyst and promoted to 99% reduction by the addition of l-cysteine capped nickel nanoparticles (Ni NPs) as catalysts. Microwave irradiation method was employed to synthesize l-cysteine capped Ni NPs in ethylene glycol, where the use of NaOH was essential to obtain nanoparticles with small size in an organic solvent. The Ni NPs obtained by microwave assisted method were used to achieve complete remediation/removal of Cr(VI) species from the aqueous solution. We demonstrate that as obtained Ni NPs are better catalysts for pollution control strategies because these lead to 99% reduction of Cr(VI) in a very short time (i.e. 5 minute) using only 0.5 mg quantity of nanocatalysts.

Surface Modification of Linear Low Density Polyethylene by Graft Copolymerization with Maleic Anhydride and its Blend with Polyamide 6

Mahmood Iqbal, Manzoor Iqbal, Kalsoom Mahmood, Ata ur Rahman

b, Chengzhi Chuai

a,

Abid Khan

PCSIR Labs Complex Karachi aSchool of Materials Science and Chemical Engineering Tianjin University of

Science and Technology, Tianjin, 3004571, China

Department of Chemistry University of Peshawar

Department of Chemistry University of Baluchistan Quetta Pakistan

Abstract: Linear low density polyethylene (LLDPE) surface properties can be modified by grafting maleic anhydride using counter-rotating twin screw extruder in the presence of benzoyl peroxide (BPO). The LLDPE/PA6 and LLDPE-g-MAH/PA6 blends were prepared by counter-rotating twin screw extruder.These blends were characterized by means of mechanical properties, differential scanning calorimeter (DSC), scanning electron microscopy (SEM), rheological properties and Fourier transform infrared spectroscopy (FTIR).Effects of the variation in temperature, initiator and maleic anhydride (MAH) concentration on the grafting degree and on the rheological behavior were evaluated. FT-IR spectroscopic results confirmed the presence of maleic anhydride onto (LLDPE) backbone. The results showed that with a proper selection of the reaction parameters, we obtained a grafting degree higher than 7.5%. Furthermore, the results


83

indicated that the tensile properties of the blends increased with increasing polyamide6 content. Scanning electron microcopy (SEM) results showed that LLDPE/PA6 blends have co-continuous structure which is reflected in the good interfacial adhesion and improved mechanical properties. Scope of the work was to use high density polyethylene as continuous phase while polyamide as dispersed phase. In Addition the home-synthesized maleated LLDPE offers the possibility to be used for the compatibilization of LLDPE / PA 6 blends.

Removal and Recovery of Zirconium from Aqueous Solution using White-Rot Fungus Coriolus versicolor

Misbah Amin* and Haq Nawaz Bhatti

University of Agriculture, Faisalabad

Abstract: Environmental engineers and scientists are facing the challenging task to develop appropriate low cost technologies for effluent treatment. Conventional methods for removing metals from aqueous solutions are either ineffective or extremely expensive. Biosorption is an emerging and innovative technology using economical biomasses to remove pollutants from wastewater. The present study reports on biosorption of zirconium by (Coriolus versicolor) white-rot fungus from aqueous solution at different experimental conditions. Optimum experimental parameters were determined to be: pH 3.5, contact time 120 min, biomass concentration 0.05 g/100 mL of solution, initial metal ion concentration 200 mg/L and temperature 30 °C. The maximum biosorption capacity of Coriolus versicolor was found to be 70.7 mg/g for zirconium. The qmax values evaluated by using the Langmuir and Freundlich models indicated that the biosorption of the metal ions onto Coriolus versicolor dead biomass was a simple non-interactive monolayer binding to the cell surface. The kinetic studies revealed that the biosorption process of the metal ions followed well pseudo-second-order model. The calculated thermodynamic parameters (∆G°, ∆H° and ∆S°) showed that the biosorption of zirconium onto Coriolus

versicolor dead biomass was feasible, exothermic in nature and spontaneous at room temperature. The recovery of the metal ions from Coriolus versicolor dead biomass was found as higher than 96 % using 0.1 M H2SO4.

Remediation of Textile Dyes Containing Wastewater using Agricultural Wastes: Kinetic and Equilibrium Modeling

Sana Sadaf and Haq Nawaz Bhatt*

Environmental Chemistry Laboratory, Department of Chemistry & Biochemistry, University of

Agriculture, Faisalabad-Pakistan

Abstract: This study involves the remediation of dyes containing synthetic wastewater using different agricultural wastes such as bagasse, peanut husk, sunflower biomass, corncobs and cotton sticks. The simulated wastewater was prepared using Indosol Black NF and Indosol Turquiose FBL commonly used dyes in the textile industry. The effect of different process parameters such as medium pH, biosorbent particle size, dose, contact time etc, was investigated in batch study. The effect of pretreatments on the dye adsorption capacity was also exploited. The


84

results indicated that equilibrium was established within 15-30 min. The equilibrium data was subjected to various kinetic and equilibrium modeling. The adsorption of both dyes followed pseudo-second order model and Langmuir isotherm model. Effect of surfactants, heavy metal ions and salt concentration was also explored. Desorption study was carried out using different eluents. Finally FTIR spectrum and Scanning electron microscopy images were also taken to investigate the functional groups involved and surface morphology of the agricultural wastes used in the present study. The results indicated that agricultural wastes could be used to treat dyes containing effluents and environmental pollution could be minimized.

Catalytic Efficiency of Cu/ZrO2 and Pt/ZrO2 at ≥200°C using 2-Propanol Conversion as Model reaction

Muhammad Ilyas and *Muhammad Abid Zia

National Center of Excellence in Physical Chemistry, University of Peshawar, Peshawar,

Pakistan

*Present Address: University of Education Attock Campus

Abstract: An environmental friendly support was used for loading of these metals (copper and platinum). The catalytic efficiency of the reduced 0.1 mol% Pt/Zro2 of the prepared catalyst for the conversion of 2- propanol in the deoxygenated environment was analyzed. Pure N2 gas was used for deoxygenate atmosphere while mixture of N2 + O2 was used for oxygenated environment. Acetone was the only product in the steady state. In order to compare the catalytic efficiency of copper loaded on Zirconia, a similar experiment was conducted at higher temperature. Again the acetone was the only product. The % conversion of isopropanol in deoxygenated atmosphere was 44% while in case of oxygenated atmosphere the conversion was up to 69%.

Kinetics and Thermodynamics Study of Arsenate Adsorption from Aqueous Solutions on Binary Mixed Oxide of Iron and Silicon

Salah ud Din*, Abdul Naeem, Tauqeer Ahmad, Afsar Khan, M. Hamayun

National centre of excellence in Physical Chemistry Unversity of Peshawar

Abstract: Detailed kinetic experiments of arsenate adsorption from aqueous solution on binary mixed oxide of iron and silicon were conducted with different concentrations of arsenic, time and temperature of the suspension. Kinetic data was found to follow pseudo second order model. Kinetic data was subjected to intra particle diffusion and Boyd models to probe the adsorption mechanism. The dual nature of intra particle diffusion plot indicated possibility of both the film and pore diffusion. Boyd model confirmed that main controlling mechanism for arsenate sorption on mixed oxide was film diffusion. The activation energy values revealed that chemical nature of adsorption was kinetically diffusion controlled process. Eyring model was used for the calculation

of activation parameters. Positive enthalpy of activation (∆H#) showed that the reaction required

energy while converting reactants to product. The negative values of entropy of activation (∆S#) indicated a decreased randomness at solid liquid interface and also suggested that the arsenate


85

adsorption by mixed oxide of iron and silicon is an associative mechanism. The entropic values

signified the existence of an entropy barrier in system. Similarly, the positive ∆G# values revealed the existence of energy barrier to be crossed over for the occurrence of a reaction.

The Study of Physicochemical properties and Mineral Contents of Olive Samples from Different Geographical Origin

M. Nasiruddin Khan1, Reda Soharwardi

2, Agha Arslan Wasim

3*

1 Department of Chemistry, University of Karachi, Karachi

2Riyadh Al Retaj Girls School, Jeddah

3Department of Chemistry, University of Karachi, Karachi

Abstract: In this study eight different cultivars of olives were analyzed for their physicochemical properties. Volatile matter, moisture, ash content, and calorific values were determined for each cultivar. Microwave digested samples were analyzed for the mineral content (Na, K, Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, Pb, Cd) using atomic absorption spectrophotometry. The respective range of moisture, volatile, ash content, and calorific values were 13.92-57.11%, 30.82-81.29%, 3.27-7.44%, and 3.87-7.32 Cal g-1. Potassium was the most abundant element (3.40 g kg-1) found in the samples while Cd had the lowest concentration (0.45 mg kg-1) in the tested samples. The data obtained in this study can be used to complement the available food composition data.

Screening of Antimicrobial Activities and Phytochemical Analysis of Datura

metal L Collected from Zhob, Balochistan, Pakistan

Afrasiab Khan Tareen, Imrana Niaz Sultan

Department of Environmental Management & Policy, Department of Biotechnology &

Informatics

Balochistan University of information Technology, Engineering & Management Sciences

(BUITEMS) Quetta

Abstract: Crude ethanolic extraxct of Datura metel L was screened for its antimicrobial activity against various ATCC strains of bacteria i.e. E.coli, Staphylococcus aureus , Streptococcus

pyogenes , Bacillus subtilis , Pseudomonas aeruginosa , Neisseria gonorrhoeae, and fungi i.e. Candida albicans and Trichophyton mentagrophyte by agar well diffusion and disk diffusion methods. Minimum inhibitory concentration (MIC) was obtained through broth dilution method. Streptomycin (against bacterial strains) and Nystatin (against fungal strains) were used as positive controls and Dimethyl sulphoxide was used as negative control. The results revealed that D.metel is more effective against B.subtilis and C.albicans. Whereas smaller zones of inhibition were found against P.auregonosa. Different Phytochemical tests were also performed and indicated that the antibiotic activities of Datura metel was due to the presence of phytochemical compounds like alkaloids, flavonoid, phenolic compounds, steroids, tannins and terpenoids. These results support the traditional medicinal usage of D.metel against various disease and infections.


86

Adsorption and Leaching Potential of Imidacloprid Pesticide through Alluvial Soil

Muhammad Ashraf Jiandani*, Syed Tufail Hussain Sherazi, Shafi Muhammad Nizamani and

Muhammad Iqbal Bhanger

Abstract:

This study was aimed to assess the adsorption and leaching potential of imidacloprid pesticide in column and field soil. To visibly understand these actions and factors affecting them, the experiments were carried out under laboratory and field conditions. Adsorption study was divided into kinetic and equilibrium sections. The evaluation of kinetic data was done through pseudo first and second order models. It was found that kinetic adsorption of imidacloprid on soil followed pseudo second order with rate constant value of 4.333 mg/g/h. Langmuir and Freundlich isotherms were used to explain equilibrium adsorption, from these isotherms it was evaluated that Freundlich isotherm was obeyed well with adsorption capacity of 2.190-4.573 mol/g. Leaching study was performed in laboratory using column made of polyvinyl chloride having 30 cm length. Known amount of imidacloprid pesticide was applied to column left for adsorption and then eluted with 500 mL water in five equal portions. These water portions and soil of column which was divided into three sections were analyzed by HPLC. The result revealed that the concentration of imidacloprid was decreased from 0.481 ppm in first portion of water to 0.327 ppm in last portion of water while 0.783 ppm in first section of column soil to 0.038 ppm in last section of column soil. In field the leaching power of imidacloprid was observed up to 60 cm depth, its concentration decreased with soil depth. It was 3.311 ppm in first portion of soil and 0.357 ppm in last portion of soil. The leaching potential of imidacloprid pesticide up to 60 cm soil depth was due to less organic matter, sandy texture, alkaline pH, and low cation exchange capacity.

Gas Chromatographic Determination of Guanidino Compounds Using β-diketones and Ethyl Chloroformate as Derivatizing Reagents

Rizwan Ali Zounr, M.Y Khuhawar, Taj Muhammad Jahangir

Institute of Advanced Research Studies in Chemical Sciences, University of Sindh, Jamshoro

Abstract:

Guanidino compounds play an important role in different biochemical processes, like, urea and guanidine cycle. They are present in biological fluids and are indicator of metabolic disorders in uremic patients. In present work, a GC method has been developed for the analysis of Six Guanidino compounds Gunidine (G), Methylguanidine (MG), Guanidinoacetic acid (GAA), Guanidinobutyric acid (GBA), Guanidinopropionic acid (GPA) and Guanidinosuccinic acid (GSA) by two stages derivatization with hexafluoroacetyl acetone and ethyl chloroformate from the column HP-5(30m × 0.32mm id) with film thickness of 0.25µm at an initial column temperature 90 0C for 2 minutes with ramping rate of 10 0C/min up to 220 0C with nitrogen flow rate of 1ml/min. The detection was performed by flame ionization detector. The total separation time was 17 minutes. The separation was repeatable for three times with relative standard deviation (RSD) less than 5% in terms of peak height/peak area. The linear calibration range for the guanidino compounds was obtained within 1-10µg/ml with coefficient of determination (R2) within 0.9974-0.9995. The limit of detection calculated as signal to noise (S/N) (3:1) within 0.054-0.25µg/ml. The method was applied for the determination of guanidino compounds from serum of uremic patients.


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Hydrothermal Synthesis of Four Noval Metal Organic Frameworks of P-coumaric Acid and Oxalic Acid with Cu(II) and Co(II) Transition Metals.

Athar Qureshi, Muhammad Asim Farid

Department of Chemistry, Bahauddin Zakariya University, Multan, Pakistan

Abstract: Four noval metal organic frameworks [Cu(ca)2(H2O)2](1), [Co(ca)2(H2O)2](2), [Cu(p-ca)(oxa)(H2O)2](3), [Co(p-ca)(oxa)2(H2O)2](4) where ca = p-coumaric acid and oxa = oxalic acid has been successfully synthesized in good yield under hydrothermal conditions using water and methanol (7:3) ratio by varying the temperature of the reaction mixture and adjusting the pH values. Compound 1 & 2 crystallize in cubic fashion while 3 & 4 crystallize in plate shaped round crystals. The synthesized metal organic frameworks were characterized by IR analysis, thermogravimetric analysis, melting points. These coordination polymers show topologies of dimensionality.

Synthesis and Characterization of Lanthanum Doped Zirconates Rod like Nanoparticals by Hydrothermal Process

M. Athar and Muhammad Saleem Qadri

Institute of Chemical Sciences, Bahauddin Zakariya University, Multan

Abstract: In our work, La-doped lanthanum-zirconates rodlike nanoparticles were synthesized by a hydrothermal method using LaCl3 and ZrOCl2 at 180 ◦C. The effects of treatment temperature and time on the crystallite structure, size and morphology were investigated. The lanthanum doped zirconates rodlike nanoparticles with a diameter of 20–30 nm and a mean length of 300 nm were prepared by hydrothermal method.The nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and fluorescence spectroscopy. This procedure provides an easy way for the synthesis of well-crystallized lanthanum-zirconates with uniform morphology at low temperature.

Evaluation of the Conducting Polymers as Anadsorbents for the Eradication of As (III) from Aqueous Solution using ICP-OES

Sadia Ata*, Andeelfarooq Institute of Chemistry, University of the Punjab, New Campus Lahore 54590, Pakistan

Abstract: There are many organic, inorganic and bio materials that had been synthesized and used for the removal of heavy metals .Polymers and resins also give good adsorbent properties. In this studies four conductive polymers (polypyrrole,polyaniline, polythiophene(FeCl3) and polythiophene(CuSO4) were synthesized chemically and characterized by FTIR and scanning electron microscope (SEM) analysis.The particle size of all synthesized polymers was ranged in nano scale. Removal efficiency of polymers was evaluated for arsenic from aqueous solution.


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Batch technique was carried out using Polypyrrole (PPY), polyanaline (PANI) and polythiophene (THOI). Different adsorbent parameters were applied and studied like dose, contact time, temperature, anpH. Langmuir and Freundich Isotherms were used to investigate the mechanism of arsenic removal from water .Polypyrrole has qmax19.41mg/g, polyanilne 4.60mg/g, polythiophene (FeCl3) 8.9mg/g and polythiophene (CuSO4) 78.12 mg/g. The values of R2 and n favored the Freundlich adsorption isotherm and were supported heterogeneity of adsorbentB.oth models Show satisfactory results for the removal of arsenic from water using conductive polymers. However, the effect of various adsorbents would be varying due to different type of surface area, particle size and morphology. As it can be seen in the scanning electron microscope (SEM) micrographs, THOI with different oxidants play a key role on the surface appearance of products because the total surface area increases as the particle size decreases. Hence, it can be concluded that all conducting polymers could be effectively used for removal of As (III) and other toxic metals from aqueous solution.

Significance of Chitosan as an Exhausting Agent for Reactive Dyes

Shahzad Ali ShahidChatha*a

, Abdullah IjazHussaina, ShaukatAli

b, ShabanaSabir

a and Ali Imran

Mallhia

aInstitute of Chemistry, Government College University, Faisalabad

bDepartment of Chemistry and Biochemistry, University of Agriculture, Faisalabad

Abstract: Chitosan (polysaccharide) is used for cat-ionization of cotton and to increase the uptake of reactive dye by cat-ionized cotton. Different properties of the dyed cotton (untreated and treated with chitosan) for example K/S values, washing fastness, light fastness and rubbing fastness were recorded and compared. The results of present study clearly demonstrated that the use of the chitosan as an exhausting agent significantly reduce the amount of dye for dyeing the cotton fabric and also improved the color properties of treated fabric except light fastness. From the results of present investigation it is reasonable to say that chitosan could be used in the textile industries to minimize the cost of dyeing process as well as to minimize the release of dyes in the effluents.

Effective Separation and Simultaneous Quantification of Permethrin Isomers in Household Products by Validated TLC-Densitometric Method

Muhammad Shoaib a, Syed Ghulam Musharraf b, *, Dileep Kumar b, Muhammad Najam-ul-Haq a

aDepartment of Chemistry, Bahauddin Zakariya University (B.Z.U.), Multan-60800, Pakistan

bH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological

Sciences, University of Karachi, Karachi-75270, Pakistan

Abstract: Permethrin is widely used in household pests and insects controlling products. A sensitive and robust TLC-densitometric method for the separation and quantification of an important pyrethroid, permethrin in household products was developed. TLC aluminum plates, precoated with 0.2 mm thick layer of silica gel 60F-254, were used for the analysis. Densitometric analysis of permethrin was carried out in the absorbance mode at λmax 227 nm for both cis and


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trans isomers. Mobile phase consisted of hexane-diethylether-ethylacetate (8.8:0.8:0.4 v/v/v) which gave sharp and symmetrical peaks of cis- and trans-permethrin at Rf = 0.72 and 0.62, respectively. Linear regression data for the calibration curves showed a good linearity r = 0.996 ± 0.0015 and r = 0.993 ± 0.0029 for cis- and trans-permethrin, respectively. The limits of detection (LODs) for cis- and trans-permethrin were found be 1.63 and 2.44 ng/spot, respectively and limits of quantitation (LOQs) were 4.94 and 7.4 ng/spot, respectively. The developed method was validated for various validation parameters that proved the method was reproducible, precise and highly accurate for the determination of permethrin isomers in household pesticide and insecticide products.

Quinuclidinone Catalysis for the Reactions of Dihydroxyacetone Sulfate

Rozina Khattak*1, 2

, Ann Marie C.O’Donoghue1 and David R. W. Hodgson

1

1Department of Chemistry, University of Durham, South Road, Durham, UK

2National Center of Excellence in Physical Chemistry, University of Peshawar,

Peshawar-25120, Pakistan

Abstract: Quinuclidinone (free base) catalysis was observed for the reactions (elimination and deuterium exchange) of dihydroxyacetone sulfate (DHAS) in quinuclidinone (Q'one) buffer (20% free base; fB in deuterium oxide; D2O, power of deutrons; pD 7.69 ± 0.03) at 1.0 M ionic strength and a temperature of 298.3 ± 0.05 K. The kinetic studies as well as the products analyses, pertaining to the subjected reactions, were carried out by high resolution (400 MHz) 1H NMR spectroscopy. The first order reaction kinetics with respect to each of DHAS and Q'one was observed for either of elimination, combined elimination + exchange and solo exchange reaction(s) of DHAS in Q'one buffer at pD of 7.69 ± 0.03. Consequently, values of the second

order rate constant(s); kB, for quinuclidinone catalyzed elimination (1.37 × 10‒3 M‒1 s‒1), mutual

elimination + exchange (5.92 × 10‒3 M‒1 s‒1) and exchange (4.26 × 10‒3 M‒1 s‒1) reaction(s) were

established.

Ion Exchange Removal of Chromium from Tannery Wastes using Hybrid Anion Exchange Resins of Amberlite IRA-400

(Equilibrium and Thermodynamic Studies)

Tauqeer Ahmad*, Syed Mustafa, Abdul Naeem

National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar-25120,

Pakistan

Abstract: The removal of chromium from tannery wastes is studies using Amberlite IRA-400 and its hybrids with Fe(OH)3, Mn(OH)2 and Cu(OH)2. In chrome tanning processes, basic chromium sulfate is used. Thus, in the present investigation chromium (III) is oxidized to chromium (VI) by hydrogen peroxide at pH > 9. The effect of temperature on the sorption of chromium is studied. The Langmuir adsorption isotherm model is found to be applicable to the experimental data with R2 > 0.992 at all the studied temperatures. The maximum sorption capacity of chromium by Amberlite IRA-400 is found to be 0.710, 0.762, 0.818 and 0.738 mmol g-1 at 293, 303, 313 and


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323 K respectively. The thermodynamic parameters entropy (∆So), enthalpy (∆Ho) and free energy changes (∆Go) are computed for the sorption mechanism which revealed that the process to be endothermic and spontaneous in nature. The results are compared with hybrid ion exchangers at 293 and 323 K temperatures show that the hybrid ion exchange (HIX) resins have better removal capacity as compared with parent exchangers.

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