Research Article Oxovanadium(IV) Complexes with Nitrogen...

Hindawi Publishing CorporationJournal of Inorganic ChemistryVolume 2013 Article ID 982965 11 pageshttpdxdoiorg1011552013982965

Research ArticleOxovanadium(IV) Complexes with Nitrogen DonorsSynthesis Characterisation and Biological Activities

Gauri D Bajju1 Puja Sharma1 Ashu Kapahi1 Madhulika Bhagat2

Sujata Kundan1 and Deepmala Gupta1

1 Department of Chemistry University of Jammu Jammu and Kashmir 180006 India2 School of Biotechnology University of Jammu Jammu and Kashmir 180006 India

Correspondence should be addressed to Gauri D Bajju gauribajjugmailcom

Received 25 April 2013 Accepted 18 July 2013

Academic Editor Radhey Srivastava

Copyright copy 2013 Gauri D Bajju et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Some oxovanadium(IV) complexes of SASSA and 5 10 15 and 20-meso-tetraphenylporphyrin (H2tpp) with unidentate and

bidentate nitrogen donors have been synthesized and characterized by elemental analysis conductivity measurements magneticsusceptibility UV-Vis IR mass spectroscopy TGADTA and 1H 13C and 51VNMR studies to investigate the steric and electroniceffects of axial ligands on the properties of porphyrins On the basis of these studies it has been investigated that the axial ligandsbind to the sixth coordination site of the vanadium ion to form a relatively stable six-coordinate-porphyrin complex where as inthe case of SASSA complexes the nitrogen donors bind to the equatorial position giving square pyramidal geometry The in vitrocytotoxicity against human cancer cell lines and antimicrobial activities of the synthesized compounds have been done againstvarious fungal and bacterial pathogens The [VO(SASSA)LL-L] complexes were found to possess higher antibacterial antifungalactivity and in vitro cytotoxicity against human cancer cell lines than VO(tpp)L complexes

1 Introduction

Macrocyclic nitrogen donor ligands [1] have received specialattention because of their versatile coordination modes [2]and for their biological activities that is toxicity againstbacterial [3] and fungal growth anticancerous [4] andother biochemical properties [5] Such ligands for exampleporphyrins salicylates and sulphosalicylates are known toplay a very important and vital role in the stability of themetal complexes with the factor of having specific cavity sizestereochemical rigidity flexibility and ability to coordinatewith metal atom [6] SASSA ligands and their complexesare widespread in nature and of considerable relevance inmedicinal chemistry [7] and also in industries [8 9] (eg inthe preparation of heterometallic precursors to oxide mate-rials) VO2+ complexes have extensive clinical applicationsHowever there have been no reports on the correspondingorgano oxovanadium(IV) salicylates sulphosalicylates andporphyrins though these compounds are expected to bebiomedically relevant [10 11]

We report herein the synthesis of some mixed ligandcomplexes (containing different donor atoms) and character-isation by means of spectral and magnetic studies as well asin vitro biological assays of some of the complexes Structuralcorrelation of these complexes has also been made and asquare pyramidal geometry around [VO(SASSA)LL-L] andan octahedral geometry around [VO(tpp)L] complexes areproposed on the basis of electronic spectroscopic studies

2 Materials and Methods

All reagent grade solvents were purified by the standardprocedure Vanadyl sulphate and vanadium pentaoxide werepurchased fromLobaChemie and salicylic acid (SA) and sul-fosalicylic acid (SSA) were purchased fromQualigens Chem-icals and were used as received Gravimetrically vanadiumwas estimated as silver orthovanadate Carbon hydrogennitrogen and sulphur were analysed microanalytically usingCHNSAnalyser CHNS-932 IR spectra of the complexes overthe region 4000ndash400 cmminus1 were recorded on Perkin Elmer

2 Journal of Inorganic Chemistry

grating spectrophotometer using KBr discs Electronic spec-tra of [VO(SASSA)LL-L] complexes were run in DMSOand those of porphyrins in different solvents on a PerkinElmer spectrophotometer in the 200ndash600 nm range using10minus3M solution of the complexes The MALDI mass spectraof [VO(SASSA)LL-L] complexes were recorded on BrukerDaltonics spectrophotometer whereas those of [VO(tpp)L]complexes were recorded on Bruker Daltonics spectropho-tometer using positive linear high power of detection atan accelerating voltage of 20KV and laser power tuneddepending on the sample The 1H and 13C NMR spectrawere recorded on a Bruker Avans 400MHz spectrophotome-ter Molar conductivity of [VO(SASSA)LL-L] complexesin DMSO at room temperature was measured by DigitalConductivity Meter Century CC 601 having conductivity cellwith a cell constant of 11 using 10minus3M solution of complexesand also magnetic measurements at room temperature werecarried out by VSM method The thermogravimetric anal-yses (TGA) and differential thermal analyses (DTA) wereperformed on a Linseis STA PT-1000 in air atmosphere at aheating rate of 10∘Cmin

3 Procedure for Synthesis of[VO(SASSA)LL-L] Complexes

The VO(SASSA) precursors were prepared by the reactionof vanadyl sulphate (040 g 25mM) with salicylic acid (SA)(034 g 25mM)sulphosalicylic acid (SSA) (054 g 25mM)and granular zinc (mesh size 20 010 g 15mM) in 30mLmethanol The reaction mixture was refluxed for one hourThe refluxing led to the formation of [VO(SASSA)] precur-sor The complexes of [VO(SASSA)L] with pyridines hadbeen prepared by adding the appropriate ligand directly tothe solution of this [VO(SASSA)] precursor as

VOSO4+ SA + 2L Znmethanol

997888997888997888997888997888997888997888997888997888rarr [VO(SA)(L)2] (1)

where L = o-aminopyridine and o and m-methyl pyridinesThe complexes were also synthesized by using bidentate

nitrogen donors such as ethylene diamine 221015840-bipyridyland 110-phenanthrolineThe saturated solution of ligand wasadded dropwise to the hot reactionmixture of [VO(SASSA)]precursor The addition of ligand resulted in the precipita-tion of complex This reaction mixture obtained was againrefluxed for fifteen minutes The complex was filtered anddried The colour of complexes was muddy brown andphysical state was dry powder

Consider the following

VOSO4+ SA + L-L Znmethanol

997888997888997888997888997888997888997888997888997888rarr [VO(SA)(L-L)] (2)

where L-L = ethylene diamine and 110-phenanthrolineSpectroscopic characterisation has been given in Tables

1ndash5

4 Procedure for Synthesis of [VO(tpp)L]Complexes

41 Step I Synthesis of 5 10 15 and 20-Tetraphenylporphyrin[H2tpp] The metal-free-base H

2tpp was synthesized by the

conventional method of aldehyde condensation with pyrroleand was characterized by UV-Vis and 1H NMR spectro-scopies using Adler and longo method [12] and and thegeneral scheme was outlined by Menotti et al [13] for thesynthesis of H

2tpp (Scheme 1)

42 Physical Analytical and Spectral Data of 5 10 15 and20-Tetraphenylporphyrin [H

2tpp] Yield (purple crystalline

60) m p 453∘C IR (KBr cmminus1) 2963 (CH) 3450 (NH)1637 (C=C) 1095 (CndashN) and 1350 (C=N pyrrole) 1H NMR(CDCl

3) 120575 884 (s 8H 120573-pyrrole protons) 279 (s 2H imino

protons) 817 (s 8H Ho) and 76 (s 12H Hmp) for meso-arylprotons anal calcd for C

44H30N4(61475) C 8592 H 489

N 910 found C 8582 H 463 N 901

43 Step II Synthesis of Oxovanadium(IV)Porphyrin [VO(tpp)] Precursor 0114 gm of H

2tpp and 030 g of VO(acac)

2

over salt bath were stirred at 290∘C for ten minutes in along neck round bottom flask covered with a funnel Aftercompletion as indicated by TLC the reaction mixture wascooled at room temperature extracted with distilled waterand filtered through anhydrous sodium sulphateThe solventwas evaporated under vacuum to afford crude product whichwas purified by column chromatography recrystallized andcharacterized (Scheme 2)

Yield (greenish) UV-Vis(CHCl3) 120582max (in nm) (log 120576)

420(0846) for B-band and 550(0215) for Q-band IR (KBrcmminus1) 2961 (CH) 1634 (C=C) 1088 (CndashN) 1348 (C=N) 1015(V=O) 1H NMR (CDCl

3) 120575 98 (s 8H 120573-pyrrole protons)

849 (s 8H Ho) and 798 (m 12H Hmp) for meso-arylprotons anal calcd for (C

44H28N4)VO (679496) C 7776

H 415 N 824 V 749 found C 7773 H 414 N 820 V748

44 Step III Synthesis of [VO(tpp)L] Complexes Pyridine(3211 times 10minus2) (as axial ligand) and [VO(tpp)] in 1 1 molarratio were stirred without heating After completion ofreaction as again indicated by TLC the reaction mixture isextracted with distilled water The extracted portion con-taining compound was evaporated by vacuum pump andthe dried product was then dissolved in chloroform andfiltered through anhydrous sodium sulphate and evaporatedby vacuum pump Finally the purification of the productwas done by column chromatography through basic aluminausing chloroform as the eluent The dried product was crys-tallized with chloroform and recrystallized with petroleumether Finally the compound was characterized by UV-Visand 1H NMR spectra (Scheme 3)

UV-Vis(CHCl3) 120582max (in nm) (log 120576) 4276(4742) for B-

band and 5597(4284) and 6098(4109) forQ-bands IR (KBrcmminus1) 2965 (CH) 1652 (C=C) 1094 (CndashN) 1344 (C=N)1010 (V=O) 1H NMR (CDCl

3) 120575 93 (s 8H 120573-pyrrole

protons) 818 (d 10H J = 7 Ho) and 795 (m 14H Hmp) for

Journal of Inorganic Chemistry 3

Table 1 Molar conductance values of magnetic measurement UV-bands and119898119911 values of complexes

Codes Name of the complexMolar

conductance(Ωminus1 cmminus1 molminus1)

Magneticvalues(298K)

Bands observed120582max (nm)

119898119911 ratioObs (Calcd)

MB-1 Bis(o-methylpyridine)salicylatooxovanadium(IV)

[VO(C7H4O3)(C6H7N)2]9 173 27313 32686

42009 388811 (388942)

MB-2 Bis(m-methylpyridine)sulphosalicylatooxovanadium(IV)

[VO(C7H5O6S)(C6H7N)2]3 177 27213 32701

42001 468009 (469008)

MB-3 Bis(o-aminopyridine)sulphosalicylatooxovanadium(IV)

[VO(C7H5O6S)(C5H6N2)2]4 174 27412 32794

42021 471123 (471008)

MB-4 (110-Phenanthroline)sulphosalicylatooxovanadium(IV)

[VO(C7H5O6S)(C12H8N2)]7 173 27405 32732

42212 462999 (463008)

MB-5 (Ethylenediamine)sulphosalicylatooxovanadium(IV)

[VO(C7H5O6S)(C2H8N2)]7 173 27421 32682

41232 439000 (439008)

Table 2 Main infrared absorption frequencies (cmminus1) corresponding to various groups in the VO(SASSA) complexes with nitrogen donors

Codes Name of the complex 120592CndashO 120592C=O 120592C=N 120592C=C 120592VndashN 120592VndashO120592S=O

sym asym 120592V=O


[VO(C7H4O3)(C6H7N)2]13923 16624 16065 15833 4673 5402 mdash 9503


[VO(C7H4O6S)(C6H7N)2]13956 16638 16250 15627 4501 5512 11312

13254 9548


[VO(C7H4O6S)(C5H6N2)2]13905 16802 16050 15588 4702 6792 11286

13179 9155


[VO(C7H4O6S)(C12H8N2)]13963 16860 16027 15600 4533 5323 11263

13331 9459


[VO(C7H4O6S)(C2H8N2)]13802 16801 16019 15706 4700 6760 11240

13161 9476

meso-aryl protons 13C NMR (CDCl3) 1235 (Cmeso) 1284

(Cmm1015840) 1288 (Cp) 1315 (C120573) 1350 (Coo1015840) 1426 (Cp1015840) ppmand (1450 ppm) for C

120572carbons anal calcd for C

44H30N4

(61475) C 7605 H 442 N 1086 found C 7602 H 440N 1082

5 Biological Evaluation

51 Antifungal Studies In vitro antifungal activity of someof the selected complexes was tested against the pathogenldquoSclerotium rolfsiirdquo by the poisoned foodmethod using PotatoDextrose Agar (PDA) nutrient as themedium [14]The lineargrowth of fungus in control and treatment were recordedat different concentrations of the complexes The media wasprepared by dissolving dextrose and agar to the solution offresh potato starch The sterilization of media (PDA) wascarried out by autoclaving it at 15mm pressure per squareinch for 20 minutes in sterile conditions The test solutionswere prepared by dissolving the compounds in DMSO Thetest solutions were mixed in the PDA and poured intoPetri plates in sterilized conditions inside laminar flow Aftersolidification the plates were inoculated with seven-day-oldculture of pathogen by placing 2mm bit in the centre ofplates The inoculated plates were incubated at 27∘C for 4days The linear growth of fungus in control and treatmentwere recorded at different concentrations of the complexes

The growth inhibition of ldquoSclerotium rolfsiirdquo over control wascalculated as

Inhibition (119868) = 119862 minus 119879119862

times 100 (3)

where I = percent inhibition C = mean growth of fungus in(mm) in control and T = mean growth of fungus in (mm) intreatment

52 Antibacterial Studies Qualitative analysis for screen-ing of antimicrobial activity of the complexes was carriedout by agar-well-diffusion method [15] with modificationsThe complexes were tested against two Gram positive bac-teria (Bacillus subtilis MTCC2389 Staphylococcus aureusMTCC7443) and three Gram negative bacteria (Micrococcusluteus MTCC4821 Escherichia coli MTCC2127 and Pseu-domonas fluorescens MTCC4828) 20mL of sterilized nutri-ent agar was inoculated with 100mL of bacterial suspension(108 CFUmL) and then poured onto sterilized Petri plateThe agar plate was left to solidify at room temperature Awell of 6mm was aseptically bored into the agar plate Then20mL of the complexes (diluted with DMSO 1 1) was addedin each well Chloramphenicol (10 120583g) was used as a positivereference to determine the sensitivity of bacteria The plateswere kept at 4∘C for 2 hours to allow the dispersal and thenincubated at 37∘C for 24 hours


Table 3 13C NMR data showing chemical shift (in ppm) values of the VO(SASSA) complexes with nitrogen donors

Codes Name of the complex Salicylatesulphosalicylate carbons Ligand carbons


[VO(C7H4O3)(C6H7N)2]

1195(C1) 1658(C2) 1165(C3)1333(C4) 1201(C5) 1326(C6)

1732(C7)

1511(C1) 1338(C2) 1344(C3)1230(C4) 1475(C5) 243(CH3)


[VO(C7H4O6S)(C6H7N)2]

1205(C1) 1635(C2) 1176(C3)1342(C4) 1224(C5) 1310(C6)

1720(C7)

1586(C1) 1241(C2) 1364(C3)1233(C4) 1475(C5) 223(CH3)


[VO(C7H4O6S)(C5H6N2)2]

1192(C1) 1664(C2) 1163(C3)1351(C4) 1210(C5) 1333(C6)

1744(C7)

1593(C1) 1201(C2) 1304(C3)1213(C4) 1425(C5)


[VO(C7H4O6S)(C12H8N2)]

1189(C1) 1658(C2) 1165(C3)1333(C4) 1222(C5) 1324(C6)

1723(C7)

1535(C2) 1461(C9) 1435(C4)1405(C6b) 1400(C4b) 1367(C7)1290(C6a) 1281(C4a) 1263(C6)1253(C5) 1243(C8) 1240(C3)



1193(C1) 1658(C2) 1165(C3)1333(C4) 1221(C5) 1332(C6)

1730(C7)34(C1 amp C2)

Table 4 In vitro evaluation of oxovanadium(IV) macrocyclic complexes against Sclerotium rolfsii

Codes Complex Concentration(ppm)

Colony diameter(mm)

inhibition119868 = [(119862 minus 119879)119862]times 100

MB-1 [VO(SSA)(o-MePy)2]100 35 6111200 11 8777300 7 9222

MB-2 [VO(SA)(m-MePy)2]100 35 6111200 33 6333300 7 9222

MB-3 [VO(SSA)(o-AmPy)2]100 33 6333200 30 6666300 8 9111

MB-4 [VO(SSA)(110-Phen)]100 37 588200 20 777300 5 944

MB-5 [VO(SSA)(en)]100 40 555200 22 755300 8 911

MB-6 [VO(tpp)(o-AmPy)]100 60 3334200 55 389300 53 412

Mean Colony diameter of control 119862 = 90mm

53 In Vitro Cytotoxicity against Human Cancer Cell Lines

531 Cell Lines and Cell Cultures The human cancer celllines were obtained either from the National Center forCell Science Pune India or the National Cancer InstituteFrederick MD USA The human prostrate (PC-3) lung(A-549) and acute lymphoblastic leukemia (THP-1) cellline were grown and maintained in RPMI-1640 mediumpH 74 whereas DMEM was used for Breast (MCF-7)The media were supplemented with FCS (10) penicillin(100 unitsmL) streptomycin (100 120583gmL) and glutamine

(2mM) and cells were grown in CO2incubator (Heraeus

GmbH Germany) at 37∘C with 90 humidity and 5 CO2

Cells were treated with samples dissolved in DMSOwhile theuntreated control cultures received only the vehicle (DMSOlt02)

532 Cytotoxicity Assay In vitro cytotoxicity against humancancer cell lines was determined using sulphorhodamine Bdye assay [16 17] Both test samples stock solutions wereprepared in DMSO and serially diluted with growth mediumto obtain the desired concentrations


Table5In

vitro

antib

acteria

levaluationof

oxovanadium(IV)m

acrocyclicc

omplexes

Cod

esMB-1

MB-2

MB-3

MB-4

MB-5

MB-6

Positivec

ontro

lBa

cterial

strains

Con

centratio

n[VO

(SSA

)(o-MeP

y)2][VO

(SA)(m-M

ePy)

2][VO

(SSA

)(o-AmPy

) 2][VO

(SSA

)(110-Ph

en)][VO

(SSA

)(o-MeP

y)2][VO

(tpp)(o-AmPy

)]Con

trolC

mp+

10120583g

Zoneso

finh

ibition

(mm)

Bsubtilis

10minus3

mdash6

1126

10mdash

1910minus4

mdashmdash

mdash23

6mdash

10minus5

mdashmdash

mdash8

mdashmdash

Mluteus

10minus3

mdash10

mdash56

mdashmdash

2010minus4

mdash7

mdash38

mdashmdash

10minus5

mdash5

mdash10

mdashmdash

Saureus

10minus3

mdash6

524

mdashmdash

2110minus4

mdashmdash

mdash18

mdashmdash

10minus5

mdashmdash

mdash6

mdashmdash

Pflu

orescences

10minus3

mdash11

630

mdashmdash

1810minus4

mdashmdash

mdash21

6mdash

10minus5

mdashmdash

mdash7

8mdash

Ecoli

10minus3

mdash8

mdash23

mdash8

2410minus4

mdashmdash

mdash18

mdashmdash

10minus5

mdashmdash

mdash12

mdashmdash


NH

+

C

Propionic acid

N

NH N

HN

Chromatographed on basic alumina

Recrystallized fromN

NH N

HN

OH

Refluxing 40mins

column using CHCl3 as an eluent

CHCl3pet ether

Pure H2TPPCrude H2TPP

Scheme 1 Synthetic route for the synthesis of meso-tetraphenylporphyrin

N

NH N

HN

+Reflux

N

N N

NV

O

N

N N

NV

O

VO(acac)2

Chromatographed on basic aluminacolumn using CHCl3 as an eluent

Oxovanadium(IV)meso-tetraphenylporphyrin(crude)

Oxovanadium(IV)meso-tetraphenylporphyrin(pure)

Scheme 2 Synthetic route for the synthesis of oxovanadium(IV) meso-tetraphenylporphyrin

6 Results and Discussion

The analytical and spectroscopic results showed that thecomplexes of [VO(SASSA)]with unidentate nitrogen donorshave general formula [VO(SA)(L)

2][VO(SSA)(L)

2] where

L = substituted pyridines and with bidentate nitrogendonors the general formula is [VO(SA)(L-L)][VO(SSA)(L-L)] where (L-L = ethylene diamine 221015840-bipyridyl and 110-phenanthroline) The general formula for [VO(tpp)] com-plexes is [VO(tpp)(L)] (where L = substituted pyridines)

61 Conductance and Magnetic Measurements The [VO(SASSA)(LL-L)] complexes in DMSO have shown the molarconductance values in the range of 2ndash9Ωminus1 cm2molminus1revealing their neutral character and they exhibit magneticmoments in the range 173ndash179 BM which is in accordancewith the square pyramidal geometry around the metal atomin the complex and also the monomeric nature of thesecomplexes (Table 1) [18]

62 Electronic Spectra The electronic spectrum in the visibleregion of the complexes attributed to d-d transitions is altered

in intensity and shifts in position of the absorption bandsrelative to the corresponding oxovanadium(IV) ions dueto which all these complexes exhibit only one absorptionband in the range of 410ndash430 nm corresponding to d-dtransition

The characteristic absorption peak of the salicylic acidand sulfosalicylic acid occurs at 298 and 295 nm while inthe complex this peak exhibits bathochromic (red) shift to326 and 327 nm respectively The absorption maxima of thefree phenanthroline and in the complexed form appears inthe ultraviolet region at 229 and 263 nm which are assignedto the 120587-120587lowast transitions of the aromatic ring belonging tothe K band and for free 221015840-bipyridine and in the complexthe absorption maxima appear in the ultraviolet region at204 and 239 nm The bands due to these ligands exhibitred shift on complexation [19] The complexes with differentnitrogen donors are red shifted The electronic spectra ofthe complexes were also recorded in different concentrationsof DMSO and these spectra show that absorbance goes onincreasing with the increase in concentration of the solutionThese spectra were quite similar to one another and wereinterpreted on the basis of a 4-coordinate square-pyramidal


N

N N

NV

O

N

N N

NV

OL

L

NOrtho-aminopyridine

Where L(axial ligand) = H2N

Scheme 3 Synthetic route for the synthesis of axially ligated VO(IV)porphyrin

geometry around vanadium metal The spectra gave 120582maxvalues as shown in Table 1

The data for axially ligated [VO(tpp)L] is given in thesynthesis section It was observed from the data that the Q-band and B-band of six coordinated [VO(tpp)L] complexesare red shifted (bathochromic shifts) with different pyridines(nitrogen ligands) due to the basic nature of pyridines Thenonbonding electron present on heteroatom nitrogen can beeasily donated and hence it requires less energy for transitionand therefore shows bathochromic shifts There is also aformation of new band around 610 nm in axially ligated[VO(tpp)]L] complex showing their octahedral geometryaround the metal ion

63 IR Spectra The IR spectra of the complexes containingsubstituted pyridines as ligands show bands in the range of1640ndash1602 cmminus1 which are attributed to 120592

(C=N) vibrationsTheband is shifted to lower frequency region in all the complexesindicating that the bond formation is taking place throughthe nitrogen of pyridine ring [20 21] The 120592

(CminusO) phenolicstretching frequencies of the salicylate ligand are observedin the region 1259ndash1228 cmminus1 for the free ligands which getsshifted to higher region 1395ndash1350 cmminus1 in the complexes It isindicative of the bonding through the phenolic oxygen of thesalicylic acid The 120592

(COO) band of salicylic acid appears in therange of 1631ndash1620 cmminus1 which indicates the involvement ofcarboxylate oxygen in the complex formation It also provesthe bidentate chelating nature of the salicylate ionThe SO

3H

group of the 5-SSA shows bands for 120592(S=O) asymmetric and

120592(S=O) symmetric vibrations at 1350 cmminus1 and 1150 cmminus1 Boththese bands are lowered in frequency in the complexes

The bands appearing in the 681ndash673 cmminus1 range corre-spond to 120592

(VminusO) and bands about 470 cmminus1 correspond to120592(VminusN) respectively The characteristic band at 950 plusmn 35 cmminus1of the complexes is that of 120592

(V=O) [21]The spectrum of [VO(tpp)] shows shift in values of

absorption peaks as compared to their corresponding free-base porphyrins In [VO(tpp)] aromatic 120592

(CminusH) occurs at2961 cmminus1 120592

(CminusN) at 1088 cmminus1 120592(C=N) at 1348 cmminus1 [22

23] and 120592(C=C) at 1634 cm

minus1 There is the disappearance of

NndashH band stretch and appearance of an additional V=Ostretching vibration in the frequency range between 900 and1030 cmminus1 which confirms the presence of vanadium metalin porphyrin the value of vibrational frequencies of axiallyligated [VO(tpp)] is shown in Table 2 After the incorpora-tion of pyridine ligand in [VO(tpp)] complexes the V=Oband gets displayed to lower frequencies in comparison to[VO(tpp)] complexes For example for [VO(tpp)(o-NH

2Py)]

porphyrins there is additional stretching vibration due topresence of NH

2group which lies at 3274 cmminus1 for NH

2

symmetric and 3362 cmminus1 for NH2asymmetric stretching

frequencies in addition to vibration for aromatic 120592(C=C) at

1652 cmminus1 120592(CminusN) at 1094 cm

minus1 120592(C=N) at 1344 cm

minus1 120592(V=O)

at 1010 cmminus1 NH2symmetric stretching at 3280 cmminus1 and

asymmetric stretching at 3450 cmminus1 respectively The othervibrational frequencies that are not assigned in Table 2 areattributed to vibration of porphyrin and pyridine rings

64 1HNMRSpectra The 1HNMR spectra show four signalsfor the salicylate protons in the region below 60 ppm whichare merged into each other The chemical shift values forpyridine protons were observed in the region below 72 ppmas a multiplet with their usual splitting pattern The chemicalshift for the aryl protons of the bipyridyl moiety appearedin the region 80ndash86 ppm The complexes containing 110-phenanthroline show the characteristic resonances for thephenyl protons of 110-phenanthroline in the region 78ndash90 ppm All these signals had been found to merge with thesignals of salicylate protons The protons for the ndashCH

3and

ndashNH2groups occur at 32ndash34 and 38 ppm respectively The

protons of the pyridine ring attached to the central metal aremerged with the protons of the salicylate ring

The 1H NMR spectra of axially ligated [VO(tpp)L] arehighly characteristic and provide structural information ofthese compounds in solution The presence of VO(IV) metalion in porphyrin ring results in the shift of resonancestowards low-field (at higher frequency) accompanied bymarginal changes in the 1H NMR spectra All the free-base porphyrin reveals characteristic resonances of iminoprotons while metallated derivatives show the absence of


V

N

N

O

O

O

V

N

N

O

O

O

5

6 7

4 32

1

23

4

54a

66a7

89

4b6b

1

2

2

2

33

3

4 4

45

55

6 7

1

1

OO

HO3SHO3S

H2N

NH2

Figure 1 Figure showing labelled carbon atoms

imino signals The 120573-pyrrole protons of [VO(tpp)L] resonateas a singlet at 98 ppm which are downfield relative to H

2tpp

(where these are found at 86 ppm) and meso-aryl protonsresonate as doublet at 84 ppm of ortho- and 79 ppm of meta-protons which are also deshielded as compared to H

2tpp

(where these are found at 817 ppm) due to the presence ofelectron releasing oxo-group The 1H NMR and 13C NMRspectral data of axially ligated [VO(tpp)(o-AmPy)] is givenin experimental section

The 13C NMR spectral data of the complexes along withthe possible assignments were recorded in DMSO-d

6(of

vanadium salicylate complexes) and CDCl3(of VO(tpp)) and

reported in Section 2 All the carbons were found in theexpected region and the present studies are well supportedby their IR and 1HNMR spectral dataThe salicylate carbons(C1and C

6) appeared in the region at 119ndash133 ppm and

C7appeared around 173 ppm Similarly the carbons (C

1ndash

C5and C

1ndashC5) of all the pyridine ligands were found in

the region at 123ndash151 ppm In addition methyl methylenecarbons were observed at 23-24 and 34 ppm respectivelyThe110-phenanthroline carbons are found in the range of 124ndash153 ppm Furthermore the expected values of carbon atomsagreed well with the number of carbons in the proposedstructures (Table 3)The labelled carbon atoms have also beenshown in Figure 151V NMR of complexes were also performed and found

to be NMR silent in +4 oxidation state

65 Mass Spectral Studies The mass spectra of thesecomplexes show molecular ion peaks which are in goodagreement with the structure suggested by elemental anal-ysis and spectral and magnetic studies For examplefor molecular ions [VO(SSA)(o-MePy)

2]+ [VO(SA)(m-

MePy)2]+ [VO(SSA)(o-AmPy)

2]+ [VO(SSA)(110-Phen)]+

[VO(tpp)(o-AmPy)2]+ and [VO(tpp)(o-AmPy)] mz values

are observed at 388811 468543 471123 462999 439000and 7749 respectively (Table 1)

66 Thermogravimetric Analysis Thermogravimetric anal-ysis of two representative samples was carried out in anair atmosphere at a heating rate of 10∘Cmin to examinethermal stability of the compound The TG curve of thecomplex [VO(SSA)(o-NH

2Py)2] shows a continuous weight

loss starting from 200 to 600∘Cwhen a stable V2O5is formed

at 5137119900CThe curve shows an initial weight loss of a ndashSO3H

group at 2334∘C (Obs wt loss = 179 Calc wt loss =1724)This is followed by a loss of ndashC

7H3O3group at 3771∘C

(Obs wt loss 302 Calc wt loss = 2893) At 3951∘C theloss of two molecules of ndashN

2C5H6(Obs wt loss 401 Calc

wt loss = 399) had been observed and finally stable V2O5

oxide of vanadium is formed There are some exothermalpeaks observed in the range of 380ndash480∘C showing majorweight loss in this region

The thermal stability curve of the complex [VO(tpp)(N2C5H6)] shows an initial weight loss of ndashN

2C5H6moiety

at 852∘C (Obs wt loss = 118 Calc wt loss = 121) Thisis followed by a loss of four ndashC

6H5groups at 4085∘C (Obs

wt loss 402 Calc wt loss = 392) And finally at 5835∘Cthe stable oxide of vanadium that is VO

2(Obs wt loss

892Calc wt loss = 893) is formed Simultaneously thereare some overlapped exothermal peaks on DTA curve in therange of 450ndash600∘Ccorresponding to themajorweight loss ofthe complex especially that the peak on DTA curve at 505∘Ccorresponds to the porphyrin skeleton [24]

67 Antifungal Activity From the results found it has beenconcluded that on increasing the concentration of the com-plexes [VO(SASSA)] the colony diameter of the fungusdecreases (Table 4) and hence percent inhibition increasesOn doubling the concentration of the complexes and the per-cent inhibition also doubles which shows linear relationshipbetween concentration and percent inhibition The increasein antimicrobial activity is due to faster diffusion of metalcomplexes as a whole through the cell membrane or due tocombined activity effect of the metal and the ligand

Such increased activity of the metal complexes canbe explained on the basis of Overtonersquos concept [25] andTweedyrsquos chelation theory [26] The lipid membrane thatsurrounds the cell favours passage of only lipid solublematerials due to lipophilicity being an important factorwhichcontrols the antimicrobial activity On chelation the polarityof the metal ion will be reduced to a greater extent due tooverlap of the ligand orbital and partial sharing of the positivecharge of the metal ion with donor group

Antifungal activities of all compounds were studiedagainst one fungal strain (Sclerotium rolfsii) It is concludedthat all the synthesized compounds showed overall goodactivity against this antifungal strain up to 90 Among thesecomplexes [VO(SSA)(110-Phen)] was found to be moreactive than other complexes whereas [VO(tpp)(o-AmPy)]was found to be inactive


020406080

100

Gro

wth

inhi

bitio

n (

)

against MCF-7 (breast) human cancer cell line Effect of oxovanadium (IV) macrocyclic complexes

Gro

wth

inhi

bitio

n (

)

0102030405060708090

100

MB-1 MB-2 MB-3 MB-4 MB-5 MB-6 Paclitaxel

Effect of oxovanadium (IV) macrocyclic complexes against A549 (lung) human cancer cell line

10120583M50120583M

100120583M1120583M

MB-1 MB-2 MB-3 MB-4 MB-5 MB-6

10120583M50120583M

100120583M1120583M

Gro

wth

inhi

bitio

n (

)

020406080

100120

Effect of oxovanadium (IV) macrocyclic complexes against PC-3 (prostate) human cancer cell line

10120583M50120583M

100120583M1120583M


Adriamycin 0102030405060708090

100

Gro

wth

inhi

bitio

n (

)

Effect of oxovanadium (IV) macrocyclic complexes against THP-1(leukemia) human cancer cell line

10120583M50120583M 20120583M

100120583M

MB-1 MB-2 MB-3 MB-4 MB-5 MB-6 5 fluorouracil

Figure 2 In vitro cytotoxicity of oxovanadium(IV) macrocyclic complexes against human cancer cell lines where MB-1 is [VO(SSA)(o-MePy)

2] MB-2 is [VO(SA)(m-MePy)

2] MB-3 is [VO(SSA)(o-AmPy)

2] MB-4 is [VO(SSA)(110-Phen)] MB-5 is [VO(SSA)(o-MePy)

2] and

MB-6 is [VO(tpp)(o-AmPy)]

68 Antibacterial Activity Antibacterial activity of thesynthesized compounds [VO(SSA)(o-MePy)

2] [VO(SA)(m-

MePy)2] [VO(SSA)(o-AmPy)

2] [VO(SSA)(110-Phen)]

and [VO(tpp)(o-AmPy)] was tested by agar-well-diffusionmethod (Table 5) Each oxovanadium(IV) macrocycliccomplex was tested at three concentrations 10minus3 10minus4 and10minus5M against five bacterial strains namely Bacillus subtilisMicrococcus luteus Staphylococcus aureus Pseudomonasfluorescensand Escherichia coli The antibacterial activityof each compound has been summarized in Table 5Among all compound [VO(SSA)(110-Phen)] showed thestrongest antibacterial activity against all the bacterial strainseven to the low concentrations Compound [VO(SA)(m-MePy)

2] was found to be active against all the strains but

only at higher concentration that is 10minus3M Compound[VO(SSA)(o-AmPy)

2] was found sensitive to B subtilis

S aureus and P fluorescens at high concentration that is10minus3M whereas compound [VO(SSA)(en)] was found tobe active against only B subtilis and P fluorescens All thebacterial strains were found to be resistant to compound[VO(SSA)(o-MePy)

2] followed by [VO(tpp)(o-AmPy)] that

showed activity only against E coli (Table 5)Hence the results showed that [VO(SSA)(110-Phen)]

complex shows high potential for antibacterial activitywhereas [Vo(tpp)(o-AmPy)] complex shows the least activityas shown in Table 5

69 In Vitro Cytotoxicity against Human Cancer Cell LinesEvaluation of in vitro cytotoxicity of oxovanadium(IV)macrocyclic complexes was observed against four humancancer cell lines namely breast (MCF-7) leukemia (THP-1) prostate (PC-3) and lung (A549) at different con-centrations as shown in Figure 2 Dose-dependent per-cent growth inhibition was observed against all the can-cer cell lines Among the five complexes [VO(SA)(m-MePy)

2] complex showed prominent activity against all

the human cancer cell lines Growth percent inhibitionof [VO(SA)(m-MePy)

2] complex observed was 70 and 83

against breast 85 and 95 against leukemia 77 and 92 againstprostate and 82 and 93 against lung cancer cell at 50 and100 120583M respectively (Figure 2) [VO(SSA)(110-Phen)] and[VO(SSA)(o-MePy)

2] complexes showed prominent activity

against three human cancer cell lines namely leukemiaprostate and lung [VO(SSA)(en)] showed activity againstpercent growth inhibition against two human cancer celllines namely leukemia and lung whereas [VO(SSA)(o-AmPy)

2] showed activity only against lung cancer cell line

at 100 120583M only (Figure 2) Effect of [VO(tpp)(o-AmPy)] wasnegligible against all the human cancer cell lines at all theconcentrations

Hence all the five complexes of [VO(SASSA)LL-L]complex show prominent activity against the human cancercell lines whereas complex of vanadiumwith porphyrin that


is [VO(tpp)(2-AmPy)] does not exhibit growth inhibitionagainst human cancer cell lines

7 Conclusion

On the basis of the above elemental analysis and spectralstudies confirmed by mass spectra showing characteristicmolecular ion peak at their mz value for their monomericform square pyramidal structure is proposed for thesecomplexesDefinite structure for the fascinating complexes insolid state would be possible only after X-ray crystallographicstudies which have not been successful so far

Further few complexes of [VO(SASSA)] complex wereevaluated for biological activities and it was found that theyshowed prominent antifungal antibacterial and anticanceractivity when compared to the porphyrin complex

Acknowledgments

The authors are indebted to IIIM Jammu and the Departmentof Biotechnology University of Jammu for providing theirhelp to carry out the bioassays

References

[1] R Sellappan S Prasad P Jayaseelan and R Rajavel ldquoSynthesisspectral characterization electrochemical and antimicrobialactivity of macrocyclic schiff base vanadyl complexesrdquo RasayanJournal of Chemistry vol 3 no 3 pp 556ndash562 2010

[2] P Sengupta R Dinda S Ghosh and W S Sheldrick ldquoSyn-thesis and characterization of some biologically active ru-thenium(II) complexes of thiosemicarbazones of pyridine2-aldehyde and thiophene 2-aldehyde involving some ringsubstituted 4-phenylthiosemicarbazides and 4-Cyclohexylthi-osemicarbazide Crystal Structure of Cis-[Ru(Pph

3)2(L6H)

2]

(Clo4)2∙2H2O [L6H=4-(Cyclohexyl) Thiosemicarbazone of

Pyridine 2-Aldehyde]rdquo Polyhedron vol 22 no 3 pp 447ndash4532003

[3] M A Pujar B S Hadimani S Meenakumari S M Gaddadand Y F Neelgund ldquoAzo and schiff bases and their metalcomplexes as antibacterial compoundsrdquoCurrent Science vol 55no 7 pp 353ndash354 1986

[4] L Mishra A Jha and A K Yadaw ldquoSynthesis spectro-scopic and antifungal studies of transition metal trinuclearpolynuclear complexes with azolo-24-pentane-dione part IIIrdquoTransition Metal Chemistry vol 22 no 4 pp 406ndash410 1997

[5] L J Mishra ldquoChelation and ungitoxicityrdquo Indian ChemicalSociety vol 76 no 4 pp 175ndash181 1999

[6] M Formica V Fusi M Micheloni R Pontellini and PRomani ldquoCryptand ligands for selective lithium coordinationrdquoCoordination Chemistry Reviews vol 184 no 1 pp 347ndash3631999

[7] V Stavila J C Fettinger and K H Whitmire ldquoSynthesisand characterization of new phenylbis(salicylato)bismuth(III)complexesrdquoOrganometallics vol 26 no 14 pp 3321ndash3328 2007

[8] R M Smith A E Martell and R S Motekaitis NIST CriticallySelected Stability Constants of Metal Complexes Database Ver-sion 40 Texas A and M University College Station Tex USA1997

[9] A E Martell R J Motekaitis and R M Smith ldquoAluminiumcomplexes of hydroxyaliphatic and hydroxyaromatic ligandsin aqueous systems-some problems and solutionsrdquo Polyhedronvol 9 no 2-3 pp 171ndash187 1990

[10] T K Saha Y Yoshikawa H Yasui and H Sakurai ldquoOxova-nadium(IV)-porphyrin complex as a potent insulin-mimeticTreatment of experimental type 1 diabetic mice by thecomplex [meso-tetrakis(4-sulfonatophenyl)porphyrinato]oxo-vanadate(IV)(4-)rdquo Bulletin of the Chemical Society of Japan vol79 no 8 pp 1191ndash1200 2006

[11] H Sakurai T Inohara Y Adachi K Kawabe H Yasui and JTakada ldquoA new candidate for insulinomimetic vanadium com-plex synergism of oxovanadium(IV)porphyrin and sodiumascorbaterdquo Bioorganic and Medicinal Chemistry Letters vol 14no 5 pp 1093ndash1096 2004

[12] A D Longo F R Longo J D Finarelli J Goldmacher JAssour and L Korsakoff ldquoA Simplified Synthesis for meso-tetraphenylporphinerdquoThe Journal of Organic Chemistry vol 32no 2 pp 476ndash476 1967

[13] A RMenotti ldquoPorphyrin studies IV 1The Synthesis of120572120573120574120575-Tetraphenylporphinerdquo Journal of the American Chemical Soci-ety vol 63 no 1 pp 267ndash270 1941

[14] J M Vincent ldquoDistortion of fungal hyphae in the presence ofcertain inhibitorsrdquo Nature vol 159 p 850 1927

[15] F Oke B Aslim S Ozturk and S Altundag ldquoEssential oil com-position antimicrobial and antioxidant activities of Saturejacuneifolia Tenrdquo Food Chemistry vol 112 no 4 pp 874ndash8792009

[16] A Thiantanawat B J Long and A M Brodie ldquoSignalingpathways of apoptosis activated by aromatase inhibitors andantiestrogensrdquo Cancer Research vol 63 no 22 pp 8037ndash80502003

[17] X Tong S Lin M Fujii and D X Hou ldquoEchinocysticacid induces apoptosis in HL-60 cells through mitochondria-mediated death pathwayrdquo Cancer Letters vol 212 no 1 pp 21ndash32 2004

[18] S Singh D P Rao A K Yadava and H S Yadava ldquoSynthesisand characterisation of oxovanadium (IV) complexes withtetradentate schiff base ligands having thenil as precursormoleculerdquo Current Research in Chemistry vol 3 no 2 pp 106ndash113 2011

[19] R Murugavel and R Korah ldquoStructural diversity and supra-molecular aggregation in calcium strontium and barium sali-cylates incorporating 110-phenanthroline and 441015840-bipyridineprobing the softer side of group 2 metal ions with pyridinicligandsrdquo Inorganic Chemistry vol 46 no 26 pp 11048ndash110622007

[20] E Akalin and S Akyuz ldquoThe FT-IR spectroscopic investigationof transition metal(II) 4-aminopyridine tetracyanonickelatecomplexesrdquo Journal of Molecular Structure vol 482 pp 171ndash1741999

[21] V K Monga K H Thompson V G Yuen et al ldquoVanadiumcomplexes with mixed OS anionic ligands derived frommaltolsynthesis characterization and biological studiesrdquo InorganicChemistry vol 44 no 8 pp 2678ndash2688 2005

[22] Z-C Sun Y-B She Y Zhou X-F Song and K Li ldquoSyn-thesis characterization and spectral properties of substitutedtetraphenylporphyrin iron chloride complexesrdquoMolecules vol16 no 4 pp 2960ndash2970 2011


[23] E J Baran A H Jubert and E G Ferrer ldquoInfrared ramanand pre-resonance raman spectra of vanadyl(1V) tetraphenyl-porphyrinrdquo Journal of Raman Spectroscopy vol 23 pp 489ndash494 1992

[24] N Dharmaraj P Viswanathamurthi and K Natarajan ldquoRuthe-nium(II) complexes containing bidentate Schiff bases and theirantifungal activityrdquo Transition Metal Chemistry vol 26 no 1-2pp 105ndash109 2001

[25] C Zhuang X Tang D Wang et al ldquoAn unsymmetrical por-phyrin and its metal complexes synthesis spectroscopy ther-mal analysis and liquid crystal propertiesrdquo Journal of the SerbianChemical Society vol 74 no 10 pp 1097ndash1104 2009

[26] L Mishra and V K Singh ldquoSynthesis structural and antifungalstudies of Co(II) Ni(II) Cu(II) and Zn(II) complexes withnew schiff bases bearing benzimidazolesrdquo Indian Journal ofChemistry vol 32 no 5 pp 446ndash457 1993

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


grating spectrophotometer using KBr discs Electronic spec-tra of [VO(SASSA)LL-L] complexes were run in DMSOand those of porphyrins in different solvents on a PerkinElmer spectrophotometer in the 200ndash600 nm range using10minus3M solution of the complexes The MALDI mass spectraof [VO(SASSA)LL-L] complexes were recorded on BrukerDaltonics spectrophotometer whereas those of [VO(tpp)L]complexes were recorded on Bruker Daltonics spectropho-tometer using positive linear high power of detection atan accelerating voltage of 20KV and laser power tuneddepending on the sample The 1H and 13C NMR spectrawere recorded on a Bruker Avans 400MHz spectrophotome-ter Molar conductivity of [VO(SASSA)LL-L] complexesin DMSO at room temperature was measured by DigitalConductivity Meter Century CC 601 having conductivity cellwith a cell constant of 11 using 10minus3M solution of complexesand also magnetic measurements at room temperature werecarried out by VSM method The thermogravimetric anal-yses (TGA) and differential thermal analyses (DTA) wereperformed on a Linseis STA PT-1000 in air atmosphere at aheating rate of 10∘Cmin

3 Procedure for Synthesis of[VO(SASSA)LL-L] Complexes

The VO(SASSA) precursors were prepared by the reactionof vanadyl sulphate (040 g 25mM) with salicylic acid (SA)(034 g 25mM)sulphosalicylic acid (SSA) (054 g 25mM)and granular zinc (mesh size 20 010 g 15mM) in 30mLmethanol The reaction mixture was refluxed for one hourThe refluxing led to the formation of [VO(SASSA)] precur-sor The complexes of [VO(SASSA)L] with pyridines hadbeen prepared by adding the appropriate ligand directly tothe solution of this [VO(SASSA)] precursor as

VOSO4+ SA + 2L Znmethanol

997888997888997888997888997888997888997888997888997888rarr [VO(SA)(L)2] (1)

where L = o-aminopyridine and o and m-methyl pyridinesThe complexes were also synthesized by using bidentate

nitrogen donors such as ethylene diamine 221015840-bipyridyland 110-phenanthrolineThe saturated solution of ligand wasadded dropwise to the hot reactionmixture of [VO(SASSA)]precursor The addition of ligand resulted in the precipita-tion of complex This reaction mixture obtained was againrefluxed for fifteen minutes The complex was filtered anddried The colour of complexes was muddy brown andphysical state was dry powder

Consider the following

VOSO4+ SA + L-L Znmethanol

997888997888997888997888997888997888997888997888997888rarr [VO(SA)(L-L)] (2)

where L-L = ethylene diamine and 110-phenanthrolineSpectroscopic characterisation has been given in Tables

1ndash5

4 Procedure for Synthesis of [VO(tpp)L]Complexes

41 Step I Synthesis of 5 10 15 and 20-Tetraphenylporphyrin[H2tpp] The metal-free-base H

2tpp was synthesized by the

conventional method of aldehyde condensation with pyrroleand was characterized by UV-Vis and 1H NMR spectro-scopies using Adler and longo method [12] and and thegeneral scheme was outlined by Menotti et al [13] for thesynthesis of H

2tpp (Scheme 1)

42 Physical Analytical and Spectral Data of 5 10 15 and20-Tetraphenylporphyrin [H

2tpp] Yield (purple crystalline

60) m p 453∘C IR (KBr cmminus1) 2963 (CH) 3450 (NH)1637 (C=C) 1095 (CndashN) and 1350 (C=N pyrrole) 1H NMR(CDCl

3) 120575 884 (s 8H 120573-pyrrole protons) 279 (s 2H imino

protons) 817 (s 8H Ho) and 76 (s 12H Hmp) for meso-arylprotons anal calcd for C

44H30N4(61475) C 8592 H 489

N 910 found C 8582 H 463 N 901

43 Step II Synthesis of Oxovanadium(IV)Porphyrin [VO(tpp)] Precursor 0114 gm of H

2tpp and 030 g of VO(acac)

2

over salt bath were stirred at 290∘C for ten minutes in along neck round bottom flask covered with a funnel Aftercompletion as indicated by TLC the reaction mixture wascooled at room temperature extracted with distilled waterand filtered through anhydrous sodium sulphateThe solventwas evaporated under vacuum to afford crude product whichwas purified by column chromatography recrystallized andcharacterized (Scheme 2)

Yield (greenish) UV-Vis(CHCl3) 120582max (in nm) (log 120576)

420(0846) for B-band and 550(0215) for Q-band IR (KBrcmminus1) 2961 (CH) 1634 (C=C) 1088 (CndashN) 1348 (C=N) 1015(V=O) 1H NMR (CDCl

3) 120575 98 (s 8H 120573-pyrrole protons)

849 (s 8H Ho) and 798 (m 12H Hmp) for meso-arylprotons anal calcd for (C

44H28N4)VO (679496) C 7776

H 415 N 824 V 749 found C 7773 H 414 N 820 V748

44 Step III Synthesis of [VO(tpp)L] Complexes Pyridine(3211 times 10minus2) (as axial ligand) and [VO(tpp)] in 1 1 molarratio were stirred without heating After completion ofreaction as again indicated by TLC the reaction mixture isextracted with distilled water The extracted portion con-taining compound was evaporated by vacuum pump andthe dried product was then dissolved in chloroform andfiltered through anhydrous sodium sulphate and evaporatedby vacuum pump Finally the purification of the productwas done by column chromatography through basic aluminausing chloroform as the eluent The dried product was crys-tallized with chloroform and recrystallized with petroleumether Finally the compound was characterized by UV-Visand 1H NMR spectra (Scheme 3)

UV-Vis(CHCl3) 120582max (in nm) (log 120576) 4276(4742) for B-

band and 5597(4284) and 6098(4109) forQ-bands IR (KBrcmminus1) 2965 (CH) 1652 (C=C) 1094 (CndashN) 1344 (C=N)1010 (V=O) 1H NMR (CDCl

3) 120575 93 (s 8H 120573-pyrrole

protons) 818 (d 10H J = 7 Ho) and 795 (m 14H Hmp) for









[VO(C7H4O3)(C6H7N)2]9 173 27313 32686

42009 388811 (388942)


[VO(C7H5O6S)(C6H7N)2]3 177 27213 32701

42001 468009 (469008)


[VO(C7H5O6S)(C5H6N2)2]4 174 27412 32794

42021 471123 (471008)


[VO(C7H5O6S)(C12H8N2)]7 173 27405 32732

42212 462999 (463008)


[VO(C7H5O6S)(C2H8N2)]7 173 27421 32682

41232 439000 (439008)



sym asym 120592V=O


[VO(C7H4O3)(C6H7N)2]13923 16624 16065 15833 4673 5402 mdash 9503


[VO(C7H4O6S)(C6H7N)2]13956 16638 16250 15627 4501 5512 11312

13254 9548


[VO(C7H4O6S)(C5H6N2)2]13905 16802 16050 15588 4702 6792 11286

13179 9155


[VO(C7H4O6S)(C12H8N2)]13963 16860 16027 15600 4533 5323 11263

13331 9459


[VO(C7H4O6S)(C2H8N2)]13802 16801 16019 15706 4700 6760 11240

13161 9476




44H30N4

(61475) C 7605 H 442 N 1086 found C 7602 H 440N 1082





times 100 (3)








1195(C1) 1658(C2) 1165(C3)1333(C4) 1201(C5) 1326(C6)

1732(C7)

1511(C1) 1338(C2) 1344(C3)1230(C4) 1475(C5) 243(CH3)



1205(C1) 1635(C2) 1176(C3)1342(C4) 1224(C5) 1310(C6)

1720(C7)

1586(C1) 1241(C2) 1364(C3)1233(C4) 1475(C5) 223(CH3)



1192(C1) 1664(C2) 1163(C3)1351(C4) 1210(C5) 1333(C6)

1744(C7)

1593(C1) 1201(C2) 1304(C3)1213(C4) 1425(C5)



1189(C1) 1658(C2) 1165(C3)1333(C4) 1222(C5) 1324(C6)

1723(C7)




1193(C1) 1658(C2) 1165(C3)1333(C4) 1221(C5) 1332(C6)

1730(C7)34(C1 amp C2)



Colony diameter(mm)


MB-1 [VO(SSA)(o-MePy)2]100 35 6111200 11 8777300 7 9222

MB-2 [VO(SA)(m-MePy)2]100 35 6111200 33 6333300 7 9222

MB-3 [VO(SSA)(o-AmPy)2]100 33 6333200 30 6666300 8 9111

MB-4 [VO(SSA)(110-Phen)]100 37 588200 20 777300 5 944

MB-5 [VO(SSA)(en)]100 40 555200 22 755300 8 911

MB-6 [VO(tpp)(o-AmPy)]100 60 3334200 55 389300 53 412









Table5In

vitro

antib

acteria

levaluationof

oxovanadium(IV)m

acrocyclicc

omplexes

Cod

esMB-1

MB-2

MB-3

MB-4

MB-5

MB-6

Positivec

ontro

lBa

cterial

strains

Con

centratio

n[VO

(SSA

)(o-MeP

y)2][VO

(SA)(m-M

ePy)

2][VO

(SSA

)(o-AmPy

) 2][VO

(SSA

)(110-Ph

en)][VO

(SSA

)(o-MeP

y)2][VO

(tpp)(o-AmPy

)]Con

trolC

mp+

10120583g

Zoneso

finh

ibition

(mm)

Bsubtilis

10minus3

mdash6

1126

10mdash

1910minus4

mdashmdash

mdash23

6mdash

10minus5

mdashmdash

mdash8

mdashmdash

Mluteus

10minus3

mdash10

mdash56

mdashmdash

2010minus4

mdash7

mdash38

mdashmdash

10minus5

mdash5

mdash10

mdashmdash

Saureus

10minus3

mdash6

524

mdashmdash

2110minus4

mdashmdash

mdash18

mdashmdash

10minus5

mdashmdash

mdash6

mdashmdash

Pflu

orescences

10minus3

mdash11

630

mdashmdash

1810minus4

mdashmdash

mdash21

6mdash

10minus5

mdashmdash

mdash7

8mdash

Ecoli

10minus3

mdash8

mdash23

mdash8

2410minus4

mdashmdash

mdash18

mdashmdash

10minus5

mdashmdash

mdash12

mdashmdash


NH

+

C

Propionic acid

N

NH N

HN



NH N

HN

OH

Refluxing 40mins


CHCl3pet ether



N

NH N

HN

+Reflux

N

N N

NV

O

N

N N

NV

O

VO(acac)2







2][VO(SSA)(L)

2] where







N

N N

NV

O

N

N N

NV

OL

L










3H









23] and 120592(C=C) at 1634 cm



2Py)]



2




minus1 120592(C=N) at 1344 cm

minus1 120592(V=O)




3and





V

N

N

O

O

O

V

N

N

O

O

O

5

6 7

4 32

1

23

4

54a

66a7

89

4b6b

1

2

2

2

33

3

4 4

45

55

6 7

1

1

OO

HO3SHO3S

H2N

NH2



2tpp


2tpp



6(of





1ndash

C5and C





2]+ [VO(SA)(m-


2]+ [VO(SSA)(110-Phen)]+














2C5H6moiety




2(Obs wt loss






020406080

100

Gro

wth

inhi

bitio

n (

)


Gro

wth

inhi

bitio

n (

)

0102030405060708090

100



10120583M50120583M

100120583M1120583M


10120583M50120583M

100120583M1120583M

Gro

wth

inhi

bitio

n (

)

020406080

100120


10120583M50120583M

100120583M1120583M


Adriamycin 0102030405060708090

100

Gro

wth

inhi

bitio

n (

)


10120583M50120583M 20120583M

100120583M






2] and



2] [VO(SA)(m-























7 Conclusion



Acknowledgments


References



3)2(L6H)

2]





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of









[VO(C7H4O3)(C6H7N)2]9 173 27313 32686

42009 388811 (388942)


[VO(C7H5O6S)(C6H7N)2]3 177 27213 32701

42001 468009 (469008)


[VO(C7H5O6S)(C5H6N2)2]4 174 27412 32794

42021 471123 (471008)


[VO(C7H5O6S)(C12H8N2)]7 173 27405 32732

42212 462999 (463008)


[VO(C7H5O6S)(C2H8N2)]7 173 27421 32682

41232 439000 (439008)



sym asym 120592V=O


[VO(C7H4O3)(C6H7N)2]13923 16624 16065 15833 4673 5402 mdash 9503


[VO(C7H4O6S)(C6H7N)2]13956 16638 16250 15627 4501 5512 11312

13254 9548


[VO(C7H4O6S)(C5H6N2)2]13905 16802 16050 15588 4702 6792 11286

13179 9155


[VO(C7H4O6S)(C12H8N2)]13963 16860 16027 15600 4533 5323 11263

13331 9459


[VO(C7H4O6S)(C2H8N2)]13802 16801 16019 15706 4700 6760 11240

13161 9476




44H30N4

(61475) C 7605 H 442 N 1086 found C 7602 H 440N 1082





times 100 (3)








1195(C1) 1658(C2) 1165(C3)1333(C4) 1201(C5) 1326(C6)

1732(C7)

1511(C1) 1338(C2) 1344(C3)1230(C4) 1475(C5) 243(CH3)



1205(C1) 1635(C2) 1176(C3)1342(C4) 1224(C5) 1310(C6)

1720(C7)

1586(C1) 1241(C2) 1364(C3)1233(C4) 1475(C5) 223(CH3)



1192(C1) 1664(C2) 1163(C3)1351(C4) 1210(C5) 1333(C6)

1744(C7)

1593(C1) 1201(C2) 1304(C3)1213(C4) 1425(C5)



1189(C1) 1658(C2) 1165(C3)1333(C4) 1222(C5) 1324(C6)

1723(C7)




1193(C1) 1658(C2) 1165(C3)1333(C4) 1221(C5) 1332(C6)

1730(C7)34(C1 amp C2)



Colony diameter(mm)


MB-1 [VO(SSA)(o-MePy)2]100 35 6111200 11 8777300 7 9222

MB-2 [VO(SA)(m-MePy)2]100 35 6111200 33 6333300 7 9222

MB-3 [VO(SSA)(o-AmPy)2]100 33 6333200 30 6666300 8 9111

MB-4 [VO(SSA)(110-Phen)]100 37 588200 20 777300 5 944

MB-5 [VO(SSA)(en)]100 40 555200 22 755300 8 911

MB-6 [VO(tpp)(o-AmPy)]100 60 3334200 55 389300 53 412









Table5In

vitro

antib

acteria

levaluationof

oxovanadium(IV)m

acrocyclicc

omplexes

Cod

esMB-1

MB-2

MB-3

MB-4

MB-5

MB-6

Positivec

ontro

lBa

cterial

strains

Con

centratio

n[VO

(SSA

)(o-MeP

y)2][VO

(SA)(m-M

ePy)

2][VO

(SSA

)(o-AmPy

) 2][VO

(SSA

)(110-Ph

en)][VO

(SSA

)(o-MeP

y)2][VO

(tpp)(o-AmPy

)]Con

trolC

mp+

10120583g

Zoneso

finh

ibition

(mm)

Bsubtilis

10minus3

mdash6

1126

10mdash

1910minus4

mdashmdash

mdash23

6mdash

10minus5

mdashmdash

mdash8

mdashmdash

Mluteus

10minus3

mdash10

mdash56

mdashmdash

2010minus4

mdash7

mdash38

mdashmdash

10minus5

mdash5

mdash10

mdashmdash

Saureus

10minus3

mdash6

524

mdashmdash

2110minus4

mdashmdash

mdash18

mdashmdash

10minus5

mdashmdash

mdash6

mdashmdash

Pflu

orescences

10minus3

mdash11

630

mdashmdash

1810minus4

mdashmdash

mdash21

6mdash

10minus5

mdashmdash

mdash7

8mdash

Ecoli

10minus3

mdash8

mdash23

mdash8

2410minus4

mdashmdash

mdash18

mdashmdash

10minus5

mdashmdash

mdash12

mdashmdash


NH

+

C

Propionic acid

N

NH N

HN



NH N

HN

OH

Refluxing 40mins


CHCl3pet ether



N

NH N

HN

+Reflux

N

N N

NV

O

N

N N

NV

O

VO(acac)2







2][VO(SSA)(L)

2] where







N

N N

NV

O

N

N N

NV

OL

L










3H









23] and 120592(C=C) at 1634 cm



2Py)]



2




minus1 120592(C=N) at 1344 cm

minus1 120592(V=O)




3and





V

N

N

O

O

O

V

N

N

O

O

O

5

6 7

4 32

1

23

4

54a

66a7

89

4b6b

1

2

2

2

33

3

4 4

45

55

6 7

1

1

OO

HO3SHO3S

H2N

NH2



2tpp


2tpp



6(of





1ndash

C5and C





2]+ [VO(SA)(m-


2]+ [VO(SSA)(110-Phen)]+














2C5H6moiety




2(Obs wt loss






020406080

100

Gro

wth

inhi

bitio

n (

)


Gro

wth

inhi

bitio

n (

)

0102030405060708090

100



10120583M50120583M

100120583M1120583M


10120583M50120583M

100120583M1120583M

Gro

wth

inhi

bitio

n (

)

020406080

100120


10120583M50120583M

100120583M1120583M


Adriamycin 0102030405060708090

100

Gro

wth

inhi

bitio

n (

)


10120583M50120583M 20120583M

100120583M






2] and



2] [VO(SA)(m-























7 Conclusion



Acknowledgments


References



3)2(L6H)

2]





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






1195(C1) 1658(C2) 1165(C3)1333(C4) 1201(C5) 1326(C6)

1732(C7)

1511(C1) 1338(C2) 1344(C3)1230(C4) 1475(C5) 243(CH3)



1205(C1) 1635(C2) 1176(C3)1342(C4) 1224(C5) 1310(C6)

1720(C7)

1586(C1) 1241(C2) 1364(C3)1233(C4) 1475(C5) 223(CH3)



1192(C1) 1664(C2) 1163(C3)1351(C4) 1210(C5) 1333(C6)

1744(C7)

1593(C1) 1201(C2) 1304(C3)1213(C4) 1425(C5)



1189(C1) 1658(C2) 1165(C3)1333(C4) 1222(C5) 1324(C6)

1723(C7)




1193(C1) 1658(C2) 1165(C3)1333(C4) 1221(C5) 1332(C6)

1730(C7)34(C1 amp C2)



Colony diameter(mm)


MB-1 [VO(SSA)(o-MePy)2]100 35 6111200 11 8777300 7 9222

MB-2 [VO(SA)(m-MePy)2]100 35 6111200 33 6333300 7 9222

MB-3 [VO(SSA)(o-AmPy)2]100 33 6333200 30 6666300 8 9111

MB-4 [VO(SSA)(110-Phen)]100 37 588200 20 777300 5 944

MB-5 [VO(SSA)(en)]100 40 555200 22 755300 8 911

MB-6 [VO(tpp)(o-AmPy)]100 60 3334200 55 389300 53 412









Table5In

vitro

antib

acteria

levaluationof

oxovanadium(IV)m

acrocyclicc

omplexes

Cod

esMB-1

MB-2

MB-3

MB-4

MB-5

MB-6

Positivec

ontro

lBa

cterial

strains

Con

centratio

n[VO

(SSA

)(o-MeP

y)2][VO

(SA)(m-M

ePy)

2][VO

(SSA

)(o-AmPy

) 2][VO

(SSA

)(110-Ph

en)][VO

(SSA

)(o-MeP

y)2][VO

(tpp)(o-AmPy

)]Con

trolC

mp+

10120583g

Zoneso

finh

ibition

(mm)

Bsubtilis

10minus3

mdash6

1126

10mdash

1910minus4

mdashmdash

mdash23

6mdash

10minus5

mdashmdash

mdash8

mdashmdash

Mluteus

10minus3

mdash10

mdash56

mdashmdash

2010minus4

mdash7

mdash38

mdashmdash

10minus5

mdash5

mdash10

mdashmdash

Saureus

10minus3

mdash6

524

mdashmdash

2110minus4

mdashmdash

mdash18

mdashmdash

10minus5

mdashmdash

mdash6

mdashmdash

Pflu

orescences

10minus3

mdash11

630

mdashmdash

1810minus4

mdashmdash

mdash21

6mdash

10minus5

mdashmdash

mdash7

8mdash

Ecoli

10minus3

mdash8

mdash23

mdash8

2410minus4

mdashmdash

mdash18

mdashmdash

10minus5

mdashmdash

mdash12

mdashmdash


NH

+

C

Propionic acid

N

NH N

HN



NH N

HN

OH

Refluxing 40mins


CHCl3pet ether



N

NH N

HN

+Reflux

N

N N

NV

O

N

N N

NV

O

VO(acac)2







2][VO(SSA)(L)

2] where







N

N N

NV

O

N

N N

NV

OL

L










3H









23] and 120592(C=C) at 1634 cm



2Py)]



2




minus1 120592(C=N) at 1344 cm

minus1 120592(V=O)




3and





V

N

N

O

O

O

V

N

N

O

O

O

5

6 7

4 32

1

23

4

54a

66a7

89

4b6b

1

2

2

2

33

3

4 4

45

55

6 7

1

1

OO

HO3SHO3S

H2N

NH2



2tpp


2tpp



6(of





1ndash

C5and C





2]+ [VO(SA)(m-


2]+ [VO(SSA)(110-Phen)]+














2C5H6moiety




2(Obs wt loss






020406080

100

Gro

wth

inhi

bitio

n (

)


Gro

wth

inhi

bitio

n (

)

0102030405060708090

100



10120583M50120583M

100120583M1120583M


10120583M50120583M

100120583M1120583M

Gro

wth

inhi

bitio

n (

)

020406080

100120


10120583M50120583M

100120583M1120583M


Adriamycin 0102030405060708090

100

Gro

wth

inhi

bitio

n (

)


10120583M50120583M 20120583M

100120583M






2] and



2] [VO(SA)(m-























7 Conclusion



Acknowledgments


References



3)2(L6H)

2]





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table5In

vitro

antib

acteria

levaluationof

oxovanadium(IV)m

acrocyclicc

omplexes

Cod

esMB-1

MB-2

MB-3

MB-4

MB-5

MB-6

Positivec

ontro

lBa

cterial

strains

Con

centratio

n[VO

(SSA

)(o-MeP

y)2][VO

(SA)(m-M

ePy)

2][VO

(SSA

)(o-AmPy

) 2][VO

(SSA

)(110-Ph

en)][VO

(SSA

)(o-MeP

y)2][VO

(tpp)(o-AmPy

)]Con

trolC

mp+

10120583g

Zoneso

finh

ibition

(mm)

Bsubtilis

10minus3

mdash6

1126

10mdash

1910minus4

mdashmdash

mdash23

6mdash

10minus5

mdashmdash

mdash8

mdashmdash

Mluteus

10minus3

mdash10

mdash56

mdashmdash

2010minus4

mdash7

mdash38

mdashmdash

10minus5

mdash5

mdash10

mdashmdash

Saureus

10minus3

mdash6

524

mdashmdash

2110minus4

mdashmdash

mdash18

mdashmdash

10minus5

mdashmdash

mdash6

mdashmdash

Pflu

orescences

10minus3

mdash11

630

mdashmdash

1810minus4

mdashmdash

mdash21

6mdash

10minus5

mdashmdash

mdash7

8mdash

Ecoli

10minus3

mdash8

mdash23

mdash8

2410minus4

mdashmdash

mdash18

mdashmdash

10minus5

mdashmdash

mdash12

mdashmdash


NH

+

C

Propionic acid

N

NH N

HN



NH N

HN

OH

Refluxing 40mins


CHCl3pet ether



N

NH N

HN

+Reflux

N

N N

NV

O

N

N N

NV

O

VO(acac)2







2][VO(SSA)(L)

2] where







N

N N

NV

O

N

N N

NV

OL

L










3H









23] and 120592(C=C) at 1634 cm



2Py)]



2




minus1 120592(C=N) at 1344 cm

minus1 120592(V=O)




3and





V

N

N

O

O

O

V

N

N

O

O

O

5

6 7

4 32

1

23

4

54a

66a7

89

4b6b

1

2

2

2

33

3

4 4

45

55

6 7

1

1

OO

HO3SHO3S

H2N

NH2



2tpp


2tpp



6(of





1ndash

C5and C





2]+ [VO(SA)(m-


2]+ [VO(SSA)(110-Phen)]+














2C5H6moiety




2(Obs wt loss






020406080

100

Gro

wth

inhi

bitio

n (

)


Gro

wth

inhi

bitio

n (

)

0102030405060708090

100



10120583M50120583M

100120583M1120583M


10120583M50120583M

100120583M1120583M

Gro

wth

inhi

bitio

n (

)

020406080

100120


10120583M50120583M

100120583M1120583M


Adriamycin 0102030405060708090

100

Gro

wth

inhi

bitio

n (

)


10120583M50120583M 20120583M

100120583M






2] and



2] [VO(SA)(m-























7 Conclusion



Acknowledgments


References



3)2(L6H)

2]





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NH

+

C

Propionic acid

N

NH N

HN



NH N

HN

OH

Refluxing 40mins


CHCl3pet ether



N

NH N

HN

+Reflux

N

N N

NV

O

N

N N

NV

O

VO(acac)2







2][VO(SSA)(L)

2] where







N

N N

NV

O

N

N N

NV

OL

L










3H









23] and 120592(C=C) at 1634 cm



2Py)]



2




minus1 120592(C=N) at 1344 cm

minus1 120592(V=O)




3and





V

N

N

O

O

O

V

N

N

O

O

O

5

6 7

4 32

1

23

4

54a

66a7

89

4b6b

1

2

2

2

33

3

4 4

45

55

6 7

1

1

OO

HO3SHO3S

H2N

NH2



2tpp


2tpp



6(of





1ndash

C5and C





2]+ [VO(SA)(m-


2]+ [VO(SSA)(110-Phen)]+














2C5H6moiety




2(Obs wt loss






020406080

100

Gro

wth

inhi

bitio

n (

)


Gro

wth

inhi

bitio

n (

)

0102030405060708090

100



10120583M50120583M

100120583M1120583M


10120583M50120583M

100120583M1120583M

Gro

wth

inhi

bitio

n (

)

020406080

100120


10120583M50120583M

100120583M1120583M


Adriamycin 0102030405060708090

100

Gro

wth

inhi

bitio

n (

)


10120583M50120583M 20120583M

100120583M






2] and



2] [VO(SA)(m-























7 Conclusion



Acknowledgments


References



3)2(L6H)

2]





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

N N

NV

O

N

N N

NV

OL

L










3H









23] and 120592(C=C) at 1634 cm



2Py)]



2




minus1 120592(C=N) at 1344 cm

minus1 120592(V=O)




3and





V

N

N

O

O

O

V

N

N

O

O

O

5

6 7

4 32

1

23

4

54a

66a7

89

4b6b

1

2

2

2

33

3

4 4

45

55

6 7

1

1

OO

HO3SHO3S

H2N

NH2



2tpp


2tpp



6(of





1ndash

C5and C





2]+ [VO(SA)(m-


2]+ [VO(SSA)(110-Phen)]+














2C5H6moiety




2(Obs wt loss






020406080

100

Gro

wth

inhi

bitio

n (

)


Gro

wth

inhi

bitio

n (

)

0102030405060708090

100



10120583M50120583M

100120583M1120583M


10120583M50120583M

100120583M1120583M

Gro

wth

inhi

bitio

n (

)

020406080

100120


10120583M50120583M

100120583M1120583M


Adriamycin 0102030405060708090

100

Gro

wth

inhi

bitio

n (

)


10120583M50120583M 20120583M

100120583M






2] and



2] [VO(SA)(m-























7 Conclusion



Acknowledgments


References



3)2(L6H)

2]





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


V

N

N

O

O

O

V

N

N

O

O

O

5

6 7

4 32

1

23

4

54a

66a7

89

4b6b

1

2

2

2

33

3

4 4

45

55

6 7

1

1

OO

HO3SHO3S

H2N

NH2



2tpp


2tpp



6(of





1ndash

C5and C





2]+ [VO(SA)(m-


2]+ [VO(SSA)(110-Phen)]+














2C5H6moiety




2(Obs wt loss






020406080

100

Gro

wth

inhi

bitio

n (

)


Gro

wth

inhi

bitio

n (

)

0102030405060708090

100



10120583M50120583M

100120583M1120583M


10120583M50120583M

100120583M1120583M

Gro

wth

inhi

bitio

n (

)

020406080

100120


10120583M50120583M

100120583M1120583M


Adriamycin 0102030405060708090

100

Gro

wth

inhi

bitio

n (

)


10120583M50120583M 20120583M

100120583M






2] and



2] [VO(SA)(m-























7 Conclusion



Acknowledgments


References



3)2(L6H)

2]





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


020406080

100

Gro

wth

inhi

bitio

n (

)


Gro

wth

inhi

bitio

n (

)

0102030405060708090

100



10120583M50120583M

100120583M1120583M


10120583M50120583M

100120583M1120583M

Gro

wth

inhi

bitio

n (

)

020406080

100120


10120583M50120583M

100120583M1120583M


Adriamycin 0102030405060708090

100

Gro

wth

inhi

bitio

n (

)


10120583M50120583M 20120583M

100120583M






2] and



2] [VO(SA)(m-























7 Conclusion



Acknowledgments


References



3)2(L6H)

2]





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



7 Conclusion



Acknowledgments


References



3)2(L6H)

2]





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Research Article Oxovanadium(IV) Complexes with Nitrogen...

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Transcript of Research Article Oxovanadium(IV) Complexes with Nitrogen...