Module1:PolyanilineNanofibers

TeacherResourcesandBackground

Introduction:
Conductingpolymersthatareabletochangecolorinresponsetoelectronicsignalsarelikelyto
spreadintomanyapplications.Forexample,windowsthatchangefromtransparenttoopaque
atthetouchofabuttonandgreetingcardsthatdisplayflashingmessages.Chemistshave
openedthedoortonewapplicationsforcolorchangingpolymers.

ConductiveChameleons:
Inrecentyearschemistshaveworkedhardtomake
polymers
thatconductelectricityaswellas
metals.Why?Becausepolymershavepropertiesthatareadvantageoustomanufacturingand
processingofproductsonalargescale.Plus,byusingpolymers,thiseliminatestheuseof
sometoxicmetals(i.e.Cadmium,etc)inourenvironment.Thebestpolymersproducedcan
6,7
conductelectricityalmostaswellascopperoneofthebestconductingmetals.

Someconductivepolymersareconsideredelectrochromicsubstancesbecausetheyrespondto
burstofelectricalchangeby
reversiblychangingcolor.
Thisisduetotheelectrochemicalredox
reactionsthatoccurwiththeapplicationofelectricalpotential(current).
Thepropertiesofthese
electroactivepolymersarealteredas
theiroxidationstatechangeswiththe
additionalorremovalofelectrons.
Electrochromicpolymerslike
polyaniline
(PAni)
areveryimportantbecausetheir
colorcanbecontrolledelectricallyaswell
asbyalteringtheirchemical
9
environment.

Figure1
belowshowshow
thecolorofPAniisalteredbyapplying
voltagesbetween0.2Vand1.2V.

Figure1:
The PAni device exhibits light
green color at 0.2 V, green at 0.4 V,
dark green at 0.6 V, green/blue at 0.8
V, dark blue at 1.0 V and blue/purple at
1.2 V

PolyanilineTheChosenOne:
Duetoitshighstabilityanduniquecomplexofproperties,PAniwasthefirstamongconducting
polymerstobeusedinpractice.ThestudiesofPAniandotherconductingpolymers
(polyacetylene,polythiophene,polypyrrole,polyp(phenylenevinylene)haveshownthatthey
possesssemiconductingproperties.Thesepolymerscanexistindifferentoxidationstatesand,
incommonwithinorganicsemiconductors,respondtoexternalinfluencesbychangingsome
characteristics
(conductivity,color,density,magneticproperties,hydrophilicityorhydrophobicity,
permeabilitytogasesandliquids)
.Therefore,conductingpolymers(whicharesometimescalled
smartpolymers)mayserveasanalternativetoinorganicsemiconductors.

10
1
1
Polyanilinepossessescontrolledconductivitywithinthe10
10
Scm
(Siemensper
centimeter)rangecombinedwithionicandprotonconductivity,redoxactivity,electroand
solvatochromism,andparamagnetism.Inaddition,thepolymerisnontoxic,stableinaggressive
chemicalenvironments,hashighthermalstabilityandlowmanufacturingcost.

PAnipropertiesaredeterminedbytheregularstructureofpolymerchains.

Figure2:Twoversionsofdimersofanilineinblue(doped)andred(dedoped)

Thepolymerconsistsalmostentirelyof
parasubstitutedmonomerunits
coupledinthe
headtotailmanner(see
Figure2
above).Theformationoforganized
supramolecular
structures
isalsoofgreatimportance(basically,supramolecularstructurescaninteractwithone
another,actingasalargeunit).Boththesefactorsareresponsiblefortheexistenceof
elongatedpolyconjugatedsystemandhighconductivityofmacroscopicsample(Skotheim&
Reynolds,2007).

StructureandFunction:
Asarule,nanostructuredmaterials,likePAni,possesshighhomogeneity,uniquesurface
propertiesandhighchargecarriermobility,makingthesematerialsforidealformolecular
electronics.PAnicantakeonadiversityofnanostructuredforms,makingitaversatilecandidate
formanyapplications.Thepolymerchainscanform:
onedimensionalstructures(nanofibers,nanorodsandnanotubes)
planartwodimensionalobjects(ribbons,nanobeltsandnanoplates)
threedimensionalparticles(microspheres,nanospheresandgranules).
Thesemainarchitecturalelementsmayserveasabaseformorecomplicatedhierarchical
formations.

SynthesisofPAni:
Polyanilineissynthesizedby
oxidativepolymerization
ofaniline(Higashimura&Kobayashi,
2004).
4(C
H
NHCl)+5(NH
)
S
O
(C
H
N
2HCl)x++5(NH
)
SO
+2HCl+5H
SO
6
7
4
2
2
8
24
18
4
4
2
4
2
4


Thisprocesscanbeseenbelowin
Figure3
.Inthepresenceofacidsolution,theaniline
monomerisaddedtoammoniumpersulfate(oxidant)andpolymerizestoPAniinanexothermic
reaction.

Figure3.Inthepresenceofacidsolution,theanilinemonomerisaddedtoammoniumpersulfate
(oxidant)andpolymerizestoPAnipolymer

ThereareotherwaystosynthesizePAni,butoxidativepolymerizationhighlightstheredox
chemistryincurrentcurriculum.

FYI:WhatfactorscanaffecttheoxidativepolymerizationofPAninanofibers?
TheidentityandpKaoftheacid
ThebulkconductivitytrendseemstosuggestthatthepKaoftheacidplaysan
importantroleindeterminingtheamountofdopingsitesordopinglevelalongthe
polymersbackbone,astheHCl(withlowestpKaof9.0)andHNO
(withhighest
3
pKaof1.5)exhibitedthehighestandlowestbulkconductivity,respectively.
Concentrationofanilinemonomer
Lowerconcentrationstendtomakebetternanofibers
Rateofadditionofoxidant
Alloxidantshouldbeaddedatoncetotheacidifiedanilinesolution(not
dropwise)

Polyaniline:Structure,formsandtheirproperties

Table1:FormsofPAniwithdescriptionsofelectricalconductivity,spectroscopymeasurements,and
chemicalstructures.

TheDetails:

Leucoemeraldine
white/clear&colorless(C
H
NH)
6
4
n

Fullyreduced(allthenitrogenatomsareamine)

electricallyinsulating

Emeraldine
greenfortheemeraldinesalt,bluefortheemeraldinebase
([C
H
NH]
[C
H
N]
)
6
4
2
6
4
2
n

ratioofabout0.5amineandimine

electricallyconductive(salt),nonconductive(base)

Pernigraniline
blue/violet(C
H
N)
6
4
n

fullyoxidized(allthenitrogenatomsareimine)

insulatingmaterial

TransitionofformsofPAni:Doping
Althoughsimilartothecaseofdopingwithinorganicsemiconductors,thedopingofconductive
polymersexhibitsatotallydifferentchemicalnature.Twotypesofdopingscanbedistinguished:
the
redoxdoping
andthe
acidbasedoping
.Bothcanbeappliedtopolyanilineasisdepicted
in
Figure4
below.

RedoxDopingbyremovalofelectrons,representedby2e

AcidBaseDopingbyprotonation,representedbythepositivechargeontheNatom(+)

Figure4:Diagramofoxidativedopingandacidbasedoping

Itismorecommontoseeacidbasedopingduetotheairsensitivityofleucoemeraldine.
Figure
5
belowshowshowdifferentformsofPAniareformedbyvaryingthepHofthe
microenvironmentaroundPAninanofibers.Again,notethatthegreenconductiveformofPAni
predominatesinacidicenvironmentsunderoxidizingconditions.Thiscorrelateswiththe
oxidativepolymerizationsynthesisproceduredescribedabove.


Figure5:pHdependentformsofPAninanofibers

LeucoemeraldineEmeraldine
|occursbyoxidation(chemicalorelectrochemical)

addingacidicsolutionservestoprotonate(i.e.dope)theLeucoemeraldine
structureandoxidationallowsforrearrangementofelectrondensitytothe
conjugatedpatternofEmeraldineSalt

EmeraldineSalt(conductive)EmeraldineBase(nonconductive)
|occursin
neutralorbasicmedia

removingtheacidsolutionservestopartiallydeprotonate(i.e.dedope)the
EmeraldineSaltstructure,leavingitnonconductive

EmeraldinePernigraniline
|occursbyfurtheroxidation

Iminegroupsareprotonated

oxidationremovesallprotonsandrearrangestheelectrondensity

WhyisEmeraldineSaltconductiveandEmeraldineBaseinsulating?

Inthediagramabove,itisnotedthattherearedifferenceinbandgapenergybetweenthe
1,2
EmeraldineBaseandEmeraldineSaltform,leadingtothedifferencesinconductivity.

Asyouprobablyhypothesized,thepropertiesofthesepolymersarealteredunderthesevarious
conditions.Inadditiontotheconductivitychanges,thesedifferentformsofPAnipolymerhave
4
differentmaximumwavelengthabsorbances,ascanbeseenonthegraphsbelow
.

13
CurrentApplicationsofConductivePolymers:

(http://www.mdpi.com/20794991/3/3/498/htm#B112nanomaterials0300498)
Thegrowinginterestinnanostructuredconductingpolymersiscausedbyexpandingareaof
theirpracticalapplication.
Electrochromicmaterials
areusedineBooks(Kindle,Nook,etc)andMobilephones
aselectronicink.
Lightemittingpolymers
arealsoimportantandareusedindevicesknownasorganic
lightemittingdiodes(OLEDs)whicharebeginningtobeusedinmoderndisplays.This
dependsonconductivepolymerspropertiesofconvertingappliedcurrentintolight
energythroughemission.
OrganicPhotovoltaicCells
(solarcells)alsoutilizetheconductivepropertiesofsuch
polymersintheabsorptionandconversionofphotonsintoelectricalenergy.
GasSensors
adetectionsystembasedonmonitoringconductivitychanges
Usedin/for:
biosensors
new
electronicdevices
(transistors,displays,sensors,energystorageand
memorycells)
materials
forshieldingelectromagneticirradiation
polymernanolithography
inhibitionofcorrosion
membraneconstruction
catalysis
medicine(cancertreatment)

2,3
HighlightPAnitheGasSensor:

TheconductiveandinsulatingpropertiesofvariousformsofPAnilendittobeusedasasensor
deviceforoxidizingandreducingagents,gases,andmore!Incomparisontootherconductive
polymersthathavebeenstudied,PAniservesasareliablesensorduetoits
sensitivity
and
selectivity
tospecifictypesofmolecules.Itisthe
fastandreversiblereactions
ofPAniwith
bases(whenitisindopedstateemeraldinesalt,ES)andacids(whenitisinundopedstate
emeraldinebase,EB)thatarethechemicalbasisofthisclaim.Correspondingchemical,color
andconductivitychangesinPAniduringsuchsensorreactionsareshowninthisscheme:

Mostcommerciallyavailablegassensorsarebasedonmetaloxidesemiconductingmaterials
operatingathightemperaturestoincreasesensitivity.TheuseofPAniasanalternativeto
inorganicsemiconductingmaterialsforthegassensitivelayeroffersmanyadvantagessuchas
lowcost,easeofsynthesis,tunableconductivity,fastresponse,andhighsensitivityatroom
temperature.PAniisnotonlyusedasthegassensingagent,butalsoasamembranethat
protectsgassensorsfromunwantedchemicalbindingagents.ThisbecausePAninanofiber
membraneporositycanbetailoredtocontrolthelevelofdopinganddedopingofsubstance.
FurtherresearchonoptimizingtheresponsetimeandincreasingthelongevityofPAnibased
chemicalsensorsneedstobeaddressedbeforeanyrealisticcommercialdevelopmentcanbe
2,3
made
.

Howdoesthiswork?
Uponexposuretoacidicvapors,theresistanceofPAninanofibersreducesthroughthe
dopingprocess.
Uponexposuretobasicvapors,theresistanceincreasedthroughthededopingprocess.

13
Hereareafewexamplesofgasesthatconductivepolymersensorscandetect:

PotentialasaBiosensor?
Thedevelopmentofbiosensorshasemergedasatopicofgreatimportanceduetotheir
applicationinmedicaldiagnosis,environmentalmonitoring,foodsafety,andbiologicalwarfare
defense.Forabiosensortobereliable,itmusthavethesecharacteristics:
highselectivityinordertomonitorandrecognizemoleculesandspecificantigens
amethodofsignalingthedetectionofaspecificmaterialforexample,changingits
conductivityorelectricalresistance.
Forthisparticularexample,itisidealifthesensorsconductivitychangedby
severalordersofmagnitudeuponoxidationorreduction
PAnihasbeenappliedasabiosensormaterialinthedetectionof
Bacilluscereus,
afoodborne
pathogen.IthasalsobeenusedforthedetectionofmicroRNAs,urea,E.coli,andH
O
.
2
2

SeeexampleofhowconductivepolymersareusedassinglestrandedDNAbiosensors.


ElectrochemicalDNAHybridizationSensorsBasedonConductingPolymers
http://www.mdpi.com/14248220/15/2/3801/htm

ConductiveBiomaterialforScaffolds:
FromthePublicationProtocolandcellresponsesinthreedimensionalconductivecollagengel
scaffoldswithconductivepolymernanofibresfortissueregeneration

In2013,itwasfoundthatconductivePAninanofiberscouldbesuccessfullysynthesizedand
reconstitutedwithcollagenandlivingcells
invitro
.Thisconductivepolymerbiomaterialwas
appliedtoanetworkinvolvingneurons.Theuseofthismaterialnotonlyresultedinspecificcell
proliferationonthenanofibercontainingcollagenscaffold,butalsoanincreaseinelectrical
conductivity(morethan400%).Importantly,thefindingsofthisstudysuggestedthatthe
presenceofPAninanofibresinthethreedimensionalcollagengelscaffoldincreasedneuron
growthandcouldbestimulatedwithelectricalsignals,whichmightresultinevenhighercell
densityanddifferentiation.Theresultssuggestthatthesematerialscouldbepotentiallyuseful
asconductive,biomimeticscaffoldsfornerveandskeletalmuscleregeneration.


Immunofluorescencedetectionofcellsstainedafter7daysofculture:(a)positivecollagen
control,(b)Collagen0.5PANI,(c)Collagen1.5PANI,(d)Collagen3.0PANI,(e)
Collagen0.5PEDOT,(f)Collagen1.5PEDOTand(g)Collagen3.0PEDOT.Cellnucleiare
stainedblue.Scalebars,50mm.

TeacherReading
ShakeandMakePolyaniline
http://pubs.acs.org/doi/pdfplus/10.1021/ja056609n
AModernStudentLaboratoryPolyanilineAConductivePolymer{easyreading,short
introduction}
http://pubs.acs.org/doi/pdf/10.1021/ed071pA94
OxidativePolymerizationofAniline(MolecularSynthesis){indepthbackground,long
introduction}
http://cdn.intechopen.com/pdfswm/38965.pdf
Chromism
IntroductiontoChromism(Photo,Thermo,Electro,Halo,etc)
http://homepage.ntlworld.com/colin.pratt/Chromism.pdf
Tutorialonelectrochromism
http://lcp.elis.ugent.be/tutorials/tut_echrom
Examples
http://www.bpci.kiev.ua/echos/en/?Research:Electrochromism_of_ICP__and_ele
ctrochromic_devices

References:
1.Huang,J.,Virji,S.,Weiller,B.H.&Kaner,R.B.PolyanilineNanofibers:FacileSynthesisandChemical
Sensors.JournaloftheAmericanChemicalSociety125,314315(2003).
2.Virji,S.etal.Constructionofapolyanilinenanofibergassensor.JournalofChemicalEducation85,
11021104(2008).
3.Huang,J.,Virji,S.,Weiller,B.H.&Kaner,R.B.Nanostructuredpolyanilinesensors.ChemistryA
EuropeanJournal10,13141319(2004).
4.GustavoM.DoNascimento(2010).SpectroscopyofPolyanilineNanofibers,Nanofibers,AshokKumar
(Ed.),ISBN:9789537619862,InTech,DOI:10.5772/8162.Availablefrom:
http://www.intechopen.com/books/nanofibers/spectroscopyofpolyanilinenanofibers
5.
http://www.sciencebuddies.org/sciencefairprojects/multimeterstutorial.shtml#usingamultimeter
6."TheNobelPrizeinChemistry2000".Nobelprize.org.NobelMediaAB2014.Web.8Sep2015.
<
http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2000/
>
7.RoyalSocietyofChemists.ElectrochromicPolymersOutreach.2007.RoyalSocietyofChemistry
www.rsc.org/outreach
http://www.rsc.org/images/RSCelectro_tcm18159224.pdf
8.
http://www.nature.com/ncomms/2014/140923/ncomms5921/full/ncomms5921.html
9.MuhammadShahazmiMohdZambri,NoraniMutiMohamedandChongFaiKait,2011.Preparationof
ElectrochromicMaterialUsingCarbonNanotubes(CNTs).JournalofAppliedSciences,11:13211325.
10.
http://cnsi.ctrl.ucla.edu/nanoscience/pages/nanowire
11.SirivisootS,ParetaR,HarrisonBS.2014Protocolandcellresponsesinthreedimensionalconductive
collagengelscaffoldswithconductivepolymernanofibresfortissueregeneration.InterfaceFocus4:
20130050.
http://dx.doi.org/10.1098/rsfs.2013.0050
12.Electropolymerization
http://scialert.net/fulltext/?doi=jas.2011.1321.1325&org=11
13.
Sensors
http://www.nano.gov/sites/default/files/moyated_nnin_nsf_n5_moyated.pdf