Review Paper

7/18/2019 Review Paper

http://slidepdf.com/reader/full/review-paper-5696ba3a2d31f 1/7

Review on Composite Based Materials as Analytical tools for Detection

of Pesticides in Water and Food SamplesSanjan Choudhary,

Department of Chemistry, Manipal University Jaipur, Jaipur

sanjanchoudharyyahoo!com Nitu Bhatnagar

Department of Chemistry, Manipal University Jaipur, Jaipur

nitur"hatna#ar#mail!com

A"stract Organic pollutants lie Organochlorine pesticide !OC" and #olychlorinated $iphenyls !#CBs" are major environmental

concern due to their persistence, long%range transporta$ility, $io%accumulation and potentially adverse effects on living

organisms& 'nalytical chemistry plays an essential role in the measurement of such persistent compound and provides

important information on their distri$ution and environmental transformations& Much effort has $een devoted during the

last t(o decades to the development of faster, safer, more relia$le and more sensitive techni)ues for their determination

in (ater, feed, food, and in comple* environmental matrices& Ne( materials lie conductive $oron%doped diamond thin%

film electrodes (ere used for the electrochemical detection of selected pesticide lie car$aryl, car$ofuran& +his revie(

article introduces recent analytical techni)ues used for detection of Organic pollutants lie OC and #CBs in

environmental and $iota samples in field (ithin time, space and compare (ith convention techni)ues lie gas

chromatography, li)uid chromatography& 'lso, this revie( covers development of novel smart material lie silica $ased

composite materials (hich are a$le to entrap these pesticides through adsorption& Since convention techni)ue (as not

found effective enough to deal (ith such specific pro$lem, there is need to develop specific adsor$ents (hich are

efficient and economical enough to deal (ith such organic persistent pollutants&

$ey Words% Pesticides& Polychlorinated "iphenyls 'PCBs(& Silica

)ntroduction+he (orld population is e*pected to cross $illion $y the end of this century& -ith the increase in population, there is an

ever gro(ing need to feed the population, (hich can $e achieved only $y having $umper yield& +his has necessitated the

use of pesticides to protect crops and increase crop yields& .o(ever, presence of traces of these pesticides in the food

supply cannot $e avoided and the effect of long term e*posure to these materials is not (ell understood& /nterest in

monitoring pesticide levels in soil, (ater and food matrices has risen (ith increased use of pesticides and the availa$ility

mailto:[email protected]






of highly sensitive analytical e)uipment& #esticides tend to $e active molecules that can $e very challenging to analy0e at

trace levels particularly in sample matrices lie food, (ater, air and soil& 1nvironmental pollution $y pesticides and other

pesticide lie compounds, polychlorinated $iphenyls !#CBs" continue to $e one of the most alarming challenges for

sustaina$le development& +hese are considered to $e persistent organic pollutants due to their long half lives 234&

'lthough #CBs are u$i)uitous environmental contaminants that have $een $anned in most countries 254 $ut

considera$le amounts continue to cycle in the ecosphere& +he consumers are e*posed to pesticides and #CBs, in

several food groups including fruits, vegeta$les, mutton, chicen, fish, egg and mil& .o(ever, e*tensive study on

pesticides and #CBs residue in less fatty food and more fatty food lie mutton, chicen, egg, fish and mil and their

implications are lacing in /ndia& 'ulah et al& 264 reported that, residues of pesticide are present despite complete

prohi$it on poultry muscle and egg in /ndia& 7ie(ise some scientists also found the residues of organophosphate and

synthetic pyrethroids in addition to organochlorine compounds in seasonal vegeta$les from .aryana, /ndia 28, 94& /ndia is

the second largest producer of vegeta$les after China and accounts for 36&8 : of the (orld vegeta$le production and

animal hus$andry constitutes $ac$one of /ndian farming, (here animals are used as source of draft po(er as (ell as

food in the form of mil, meat and eggs 2;4& /n /ndia, 58< pesticides of various chemical groups are registered for the

control of undesira$le pests and (eeds in food crops 2, =4& More than ><: of the average human intae of #CBs

originate from food, especially food of animal origin and $io accumulate in the food chain due to their lipophilicity and

hence gets $iomagnified in human $eings 2>4& 's #CBs are stored mainly in the adipose tissues, these compounds can

$e transferred from mother to her ne($orn primarily via maternal mil and to some e*tent via the placenta 2>,3<4& /n

human populations e*posed to #CBs, several authors have reported elevations in triglycerides 233, 354 and total

cholesterol 236, 384 and occupationally e*posed persons also noted elevations in rates of cardiovascular deaths 239, 3;4&

.ence, monitoring studies to no( the actual status of contamination due to to*ic pesticide residues and #CBs in various

food commodities for the formation of legal guidance and for consumer satisfaction is necessary& +here are different

steps involved in the determination of pesticide residue as depicted in ?igure 3&



Physical separation ofFood parts

Combination of samplesChopping/Blending

Acetone

Water/Organic Phase

Gel PermeationCromatography

GLC

Adsorption ColumnChromatography

TLC

Other Procedures

PLC

!o clean"up

Acetonitrile

Water/Organic Phase

?ig 3@ Steps involved in pesticide analysis 234

1stimation of residual amounts of polychlorinated $iphenyls !#CBs" in more fatty food lie fish and mil re)uires the

use of specific techni)ues for sample preparation as (ell as instrumental analysis (hich are time consuming,

e*pensive and large volume of organic solvent utilised (hich are ha0ardous to humans and to the environment& /n

order to reduce such harmful effects, alternative techni)ue (ere developed $y many researchers& Sol%gel silica

materials are a$le to entrap these pesticides through adsorption& .ence adsorption has $een one of the techni)ues

for detection of polluted (ater& /t is not long $ac (hen activated car$on no(n to $e more versatile adsor$ents for

pollutants& But convention techni)ue (as not found effective enough to deal (ith such specific pro$lem& +here is

need to develop specific adsor$ents (hich are efficient and economical enough to deal (ith such organic persistent

pollutants& .ence synthesi0ing and using novel smart material is one of the stepping stone in technological

advancement& BAttcher et al& 23=4 have used the sol%gel matri* as an alternative to $iocide encapsulation& +hey

prepared sol%gel composite films (ith controlled release properties& aileanu et al& 23>4 had developed sol%gel

composites to improve the release of the pesticide from the silica matrices& Choudhary et al& 25<4 have prepared SiO5

sols using tetraethylorthosilicate as a source of SiO5& +he SiO5 thin films (ere o$tained using D+'B !", SDS !",

and +(een 5< !+( 5<" surfactants& +hey have reported that the SiO5 thin films (ith SDS sho(ed more surface

roughness and (ater repelling a$ility (hen compared to D+'B and least (ith +( 5<& udo and udo 5<<; 2534, +ran

and Nosaa 5<<; 2554, Chueh and .sieh 5<< 2564, Ehuang and -ang 5<3< 2584 have used silica and titanium o*ide

Clean%up

#artitioning

DeterminationSeparationDetection

1*traction

#urification

Sample #reparation



composite for analysis and degradation of to*ic su$stances& /t has $een o$served that the addition of SiO 5 to +iO5

films not only permits an increase of in%time persistence of the photo%induced super%hydrophilicity 2594, $ut also

creates an e*tremely large surface area 25;4& +a$le 3& represents comparative study of novel composite materials

developed for monitoring the concentration of pesticide lie to*ic compounds, mode of (oring and their potential

$enefit&

*a"le +!Comparative data of composite materials for monitoring the concentration of pesticide, mode of (oring andpotential $enefit

CompositematerialsFnanocompositeFthin film

Mode of Detection Su$stanceFen0ymeinhi$itor

#otential $enefit eference

'u nanoparticles 'mperometricGoltammetry

Car$aryl, car$ofuran 7arge effective surfacearea for en0ymeimmo$ili0ation

5

ErO5 nanoparticles 'mperometricGoltammetry

#ho*im, malathion 7arge effective surfacearea for en0ymeimmo$ili0ation

5=

Huantum dots!HDs% Cd+e"

Goltammetric #ho*im, malathion 7uminescentfluorophores, possesssi0e dependentproperties

5>

Car$on nanotu$esS-CN+sM-CN+s

'mperometriGoltammetry

Monocrotophos Uni)ue surface area,conformation sta$ility,high $ioactivity andsu$strate $iocatalystinteraction

6<

CdS%decoratedgarphenenanocomposite

'mperometric car$aryl +he high surface areafavora$le for immo$ili0ation of en0yme and have small$and gap (hich isresponsi$le for conducting the electrons(ith high efficiency

63

SiO5 Surface adsorption Monocrotophos .igh visi$le transparencyand hardness

65

+iO5 Surface adsorption Monocrotophos UG protective effect 66

Detection techni,ues-old versus recently developed composite materials for detection of pesticides

+he actual trend for detection of pesticides residue lie pollutants in several different matri* (as $ased on the use of

li)uid chromatography coupled to mass spectrometry techni)ues !7C%MS" and gas chromatography !IC" (ith selective

detection as electron capture !1CD", flame photometric !?#D", nitrogen phosphorus !N#D" and thermal conductivity

!+CD" detectors (hich represented the state of%the%art at the end of the last century& +hey are intended for lipophillic !in

many cases o$solete" pesticides lie most organochlorine !i&e& p,p%DD+, aldrin, dieldrin, lindane"& Moreover, the targeted

compounds monitored $y such methods sometimes are neither pesticides of to*icological relevance or the most

commonly found in a particular sample& 'lso the e*isting methods need much time for sample preparation, large amount



of organic solvent is used and una$le to monitor directly field sample& +a$le 5 sho(s a comparative study of old versus

ne( analytical techni)ues developed (ith their potential $enefit and dra($ac*a"le .! Comparative 'nalytical methods for monitoring the concentration of pesticide lie to*ic compounds, #otential$enefit and Dra($ac

'nalytical methods #otential $enefit Dra($ac eferences

Ias chromatography #o(erful techni)ue for thedetermination of multipesticideresidues

Comple* Samplepreparation procedure, timeconsuming, re)uirese*pensive e)uipments, onlyvolatile compound cananalyse

68

.igh performance li)uidchromatography !.#7C"

#o(erful techni)ue for thedetermination of multipesticideresidues

Comple* Samplepreparation procedure, timeconsuming, re)uirese*pensive e)uipments

69

+hin layer chromatography Gery Simple operatingprocedure

Una$le to )uantify at ppmlevel

6;, 6

Capillary electrophoresis Comple* Samplepreparation procedure, time

consuming, re)uirese*pensive e)uipment

6=

Mass spectrometry !MS" #o(erful techni)ue for thedetermination of pesticideresidues due to its ro$ustness,and e*cellent sensitivity andselectivity

Comple* Samplepreparation procedure, timeconsuming, re)uirese*pensive e)uipment

6>

Colorimetry ?luorescence $iosensor Only possi$le incolour changingcompounds

8<

/mmunoassays .ighly selectivity, sensitivityand reproduci$ility

+hey re)uirecorrespondinganti$odies

83

'Ch1 electrochemicals sensor Based on acetylcholinesteraseimmo$ili0ed, selective andsensitive

Onlyorganophosphoruspesticide can assay

85

+he ne( trends in pesticide residue analysis have $een focused on the miniaturi0ation of the sample preparation

methodology, moving to the development of straightfor(ard, faster, cost%effective, and environmentally friendly

procedures, adapta$le for routine use in la$oratories as (ell as in field& +he $i$liographical survey covering the period

5<3<%5<36 demonstrated that the predominant part of the recently developed nanostructured electrochemical $iosensors

for Organophosphorouss )uantification mae use of car$on nanotu$es !CN+s" or gold nanoparticles !IN#s"& #revious

studies are revised and reported in the comprehensive revie(s of 7iu et al& 254 and #eriasami et al& 25=4& IN#s are

e*tensively used in $iosensors application, due to their $iocompati$ility, catalytic activity, e*cellent conductivity, and high

surface area 25>, 6<4& Other composite materials modified devices for O#s determination (ere developed using

functionali0ed graphene structures& /t has $een demonstrated that the acetylcholinesterase sensors $ased on graphene

o*ide, IN#%graphene o*ide, and nanoparticles !NiO, #t, SnO 5"%graphene nanocomposites sho( high electron mo$ility,



catalytic activity, and sensitivity 263%694& +hey (ere successfully applied for methylparathion, chlorpyrifos, malathion, and

dichlorvos )uantification&Conclusion+his revie( addresses the recent trends in the development of composite $ased materials as analytical tool for detection

of different class of pesticides lie organophosphorus and organochlorine in food samples& +he included e*amples

demonstrate great potential of the car$on nanotu$es and the gold nanoparticles, as (ell as of the emerging graphene

structures, silica $ased composite materials& Current researches confirm that the ade)uate com$ination of

nanomaterials, $iological recognition events, and efficient electronic signal transduction result in $iosensors (ith

improved analytical performances, appropriate for the high sensitive determination of pesticide residue in difficult sample

matri*&

References

234 .ernande0, ?&, #o0o, O&J&, Sancho, J&G&, Bijlsma, 7&, Barreda, M&, #itarch, 1, 5<<;& J& Chromatogr& '& 33<>

585&254 Muccio, '& Di, Ienerali, +&, Bar$ini, D&'&, #elosi, #&, 'usili, '&, Gergori, ?&, Iirolimei, S&, 3>>& J

Chromatography ', ;9, ;3%;=&

264 'ulah, &S&, Iill, J&#&S&J&, Bedi, S&, Sharma, J&&, Joia, B&S&, Ocerman, .&-&, 5<<;, J Sci ?ood 'gric, =;

83%88

284 #odhornia, 7&G&, Negron, J&?&, Iriffith, ?&D&, 5<<3, J& 'O'C& /nt& =8, =6&

294 Caja, +&, .ajslova, J&, 7acina, O&, Mastovsa, &, 7ehotay, S&J&, 5<<=, J& Chromatogr& '& 33=;, 5=3&

2;4 #ihlstrom, +&, Blomvist, I&, ?riman, #&, #agard, U&, Osterdahl, B&I&, 5<<, 'nal& Bioanal& Chem& 6=>, 36&

24 7acina, O&, Ur$anova, J&, #ousta, J&, .ajslova, J&, 5<3<, J& Chromatogr& '& 353, ;8=&

2=4 Ion0Kle0%odrLgue0, &M&, ial%Otero, &, Cancho%Irande, B&, Simal%IKndara, J&, 5<<=, J Chromatogr '&

3<<, 33>;%33>&

2>4 &'rmisha(, #&, Millar, &I&, 3>>6, J 'O'C /nt, ;, 363%3655&23<4 &1rney, D&, 3>=6, J 'ssoc O& Chem, ;;, >;>%>6&2334 Campos, '&, 7ino, C&M&, Cardoso, S&M&, Silveira, M&/&, 5<<9, ?ood 'dditContam, 55, ;85%;8;&2354 Sinha, S&N&, Gasudev, &, ao, M&G&G&, 5<35, ?ood Chem& 365, 398&2364 Stan, .&J&, 5<<<, J& Chromatogr& '& =>5, 68&2384 .ernando, M&D&, 'gera, '&, ?ernKnde0%'l$a, '&&, #iedra, 7&, Contreras, M&, 5<<3, 'nalyst 35;, 8;&2394 'nastassiades, M&, 7ehotay, S&J&, Stajn$aher, D&, Schenc, ?&J&, 5<<6, J& 'O'C& /nt& =;, 835&

23;4 ang, &, Ehang, .&, 7iu, &, -ang, J&, Ehang, &C&, Dong, '&J&, Ehao, .&+&, Sun, C&.&, J& Cui, 5<33, ?ood

Chem&35, =99&

234 'm$rus '&, and +hler, .&#&, 3>=;, #ure and 'pplied Chemistry 9;!", 3<69%3<;5

23=4 BAttcher, .&, Jagota, C&, +repte, J&, allies & .&,&and .aufe, .&, 3>>>, Journal of Controlled elease, ;<!3",

9%;9&



23>4 aileanu, M&, +odan, 7&, Crisan, M&, Braileanu, '&, usu, '&, Bradu, C&, Carpov, '&, Eaharescu, M&, 5<3<, J&

1nviron&#rotec, 3, 6<5%636, doi@3<&856;Fjep&5<3<&36<6;

25<4 Choudhary, S&, Singh, M&, 5<36, J'S+ !J'S+%D%36%<<<39", 5, !58"

2534 udo, +&, udo, &, 5<<;, Chem& 7ett& 69, 36><

2554 +ran, +&.&, and Nosaa, '&&, 5<<;, J& #hys& Chem& B, 33<, 59959

2564 &Chueh, &7&, and&.sieh, C&.&, 5<<, 'dv& Mater&P 3>@386

2584 e, H&&, Ehuang, .&S&, Ehou, C&, -ang, H&1&, 5<3<, J 1nviron Scien,P 55@>;%%=<<

2594 Iuan, &, 7u, B&, in, &, 5<<6, Surf& Coat& +ech&P 36@53>%556

25;4 1nomoto, N&, a(asai, &, oshida, M&, 7i, &, Uehara, M&, .ojo, 5<<5, J& Solid State /onics&P 393@33%39

254 Shulga, O&, irchhoff, J&&, 5<<, 1lectrochem CommunP >@>69%8<&

25=4 Song, &, Ehang, M&, -ang, 7& 5<33, 1lectrochim 'ctaP 9;@5;%3

25>4 -ang, D&, ogach, '&7&, Caruso, ?& 5<<5, Nano 7ettP 5@=9%;3&

26<4 Dy, J&S&G&, #letsche, B&, 5<33, ChemosphereP=5@5>3%6<

2634 Du, D&, Chen, S&, Cai, J&, Ehang '& 5<<, Biosens BioelectronP56@36<

2654 #undir, C&S&, Chauhan, N&, 5<35, 'nal BiochemP85>@3>%63

2664 -ang, &, 7i, .&N&, -u, J&, 5<33, 'nalystP36;@668>%98

2684 .off, I&&, Eoonen, #&G&, 3>>>, J Chromatogra 'P=86@6<3

2694 Mito$e, .&, /$arai, +&, +ana$e, '&, a(ata, &, asuhara, 5<<3, +o*icol 1nviron ChemP =3@>%33<&

26;4 Sherma, 5<<9, J&'cta ChromatograP 39@9%6<&

264 Sutherland, +&D&, .orne, /&, ussell, &J&, 5<<5, Oaeshott JI,'ppl 1nviron Micro$iolP ;=@;56%89

26=4 7u, -&J&, Chen, &7&, Ehu, J&.&, Chen, &I&, 5<<>, 1lectrophorP 6<@=6%>3

26>4 .ernande0, ?&, Sancho, J&G&, #o0o, O&, 7ara, '&, #itarch, 1&, 5<<3, J Chromatogra 'P>6>@3%33

28<4 1llman, I&7&, Courtney, &D&, 'ndres, G&, ?eatherstone, &M&, 3>;3, Biochem #harmacolP @==%>9

2834 -ang, C&, 7i, &B&, 7iu, &.&, Iuo, &&, ie, &, Iui, -&J&, et al, 5<3<, J 'gric ?ood ChemP 9=@9;9=%;6

2854 Mauri0, 1&, Calle, '&, Montoya, '&, 7echuga, 7&M&, 5<<;, +alantaP ;>@69>%;8

Review Paper

Documents

Transcript of Review Paper