New membrane technologies--nanotube membranes for biotechnological applications and polyaniline films for corrosion inhibition

123 Pages·2003·4.7 MB·English

by  Gasparac, Rahela

NEWMEMBRANETECHNOLOGIES-NANOTUBEMEMBRANESFOR
BIOTECHNOLOGICALAPPLICATIONSANDPOLYANILINEFILMSFOR
CORROSIONINHIBITION
By
RAHELAGASPARAC
ADISSERTATIONPRESENTEDTOTHEGRADUATESCHOOL
OFTHEUNIVERSITYOFFLORIDAINPARTIALFULFILLMENT
OFTHEREQUIREMENTSFORTHEDEGREEOF
DOCTOROFPHILOSOPHY
UNIVERSITYOFFLORIDA
2003
Thisdissertationisdedicatedtomyparents,MaricaandZeljkoGasparac.
ACKNOWLEDGMENTS
IwouldliketothankDr.CharlesR.Martinforhisguidanceandsupport
throughoutmycareerattheUniversityofFlorida. Dr.Martinneverstoppedthinkingof
applicationsformyresearch. Hetaughtmehowtoeffectivelycommunicateand
successfullywritescientificpapers.
TheMartingrouphasbeenmorethansupportive. CharlesPatrissihelpedin
obtainingscanningelectronimagesformymaster'sthesis. LacramioaraTrofinand
MiguelOmarMotaPaulinospentmanyhoursgrowingaluminumoxideformy
experiments. PunitKohliandDavidT.Mitchelldiscussedtheexperimentswithmeand
providedmanyhelpfulinsights. MyungchanKanggaveexcellenttraininginatomic
forcemicroscopy.
KarenKellyandTimVaughtgavetrainingintunnelingelectronmicroscopyand
confocalmicroscopy. EricS.LambershelpedinobtainingAugerandXPSdata.
Mylifeduringgraduateschoolwouldhavebeenmuchlessinterestingwithoutthe
influencesofallDNRpeople,GordanaMatijasic,BorisLabudovic,StjepanPosavec,
IrenaLabazan,SandraNedeljko,IvanaKrobot,LidijaandJosipPosavec,Dawnand
TrevorByrne,EdMendel,AnaMatkovic,KyleH.Goodwin,MarisaScottandGabriel
KiplingTyner.
Finally,myfamilyprovidedenormousmoralsupportthroughoutmygraduate
career. ForthissupportIthankMandicaandMileJergovic,Katica,Mile,Kresimirand
DamirUgarkovicandRobertGasparac. Myparents,ZeljkoandMaricaGasparac,
111
deservesomuchofthecreditformysuccess. Theirconstantencouragementhasalvv^ays
givenmethedesiretopushon. Aboveall,thanksgotomyparentsforinstallinginmea
loveoflearning.
IV
1
TABLEOFCONTENTS
Page
ACKNOWLEDGMENTS
iii
LISTOFFIGURES vii
ABSTRACT x
CHAPTER
1 INTRODUCTIONTOTEMPLATESYNTHESIS
Introduction 1
Background 2
TemplateSynthesis 2
PolycarbonateTemplateMembranes 5
Track-etchtechnique 8
Electrolessgoldtemplatemethod 9
Gasfluxmeasurements 11
AluminaTemplateMembranes 14
Sol-gelchemistry 18
Silanecouplingchemistry 20
ElectronicallyConductivePolymers 23
Overview 23
Polyaniline(PANI) 25
ChapterSummaries 26
2 DNATRANSPORTINANANOPOREMEMBRANE
Introduction 28
Backgroimd 28
Experimental 29
PolycarbonateMembranes 29
ElectrochemicalSetup 3
ResultsandDiscussion 32
Nemst-PlanckEquation 33
ConicalPoresandMassTransfer 37
Conclusions 40
3 PREPARATIONANDMODIFICATIONOFSILICANANO-TEST-TUBES
Introduction 42
V
1
Background 42
NanoparticlesinBiomedicalResearchandDevelopment 42
DrugdeliveryandDNAtransfection 44
Experimental 46
TemplateSynthesis 48
SilanizationandAntibodyModification 48
FillingtheNano-Test-Tubes 51
ResultsandDiscussion 51
DifferentialInside/OutsideModification 5
Fluorescentlymodifiednano-test-tubes 55
Antibodymodifiednano-test-tubes 63
Conclusions 65
4 CHARACTERIZATIONOFPOLYANILINE(PANI)PROPERTIES
Introduction 66
Background 66
Experimental 68
Materials 68
PolymerSynthesis 68
EleetrodePreparation 69
ElectrochemicalMethods 70
Opencircuitpotentialmeasurements(OCP)andscanning
referenceelectrodetechnique(SRET) 70
Scanningelectronmicroscopy(SEM),augerelectron
spectroscopy(AES),andUV/visspectroscopy 72
ResultsandDiscussion 73
CharacterizationofthePolyanilineFilms 73
Open-CircuitPotentialMeasurements 73
AugerSpectroscopy 84
ScanningReferenceElectrodeTechnique(SRET) 92
Conclusions 93
5 CONCLUSIONS 95
LISTOFREFERENCES 97
BIOGRAPHICALSKETCH 110
VI
8
1
LISTOFFIGURES
Figure page
-1. Structureofpolycarbonatematerial 6
1-2. Scanningelectronmicrograph(SEM)ofthesurfaceofamicroporous
polycarbonatemembranepreparedviathe“track-etch”method 7
11--3. Schemeoftracketchprocess 9
2-
1-4. Schemeofelectrolessgoldtemplatemethod 12
1-5. SideviewofschemeshowedinFigure1-4 13
21--6. Seamingelectronmicrographsofalumiamembrane 16
1-7. Schemeofaporousaluminaoxidefrilmgrownonaluminum 1
3-8. Rangeofconductivitiesoforganicconductingpolymers 24
1. Schemeofpolycarbonatemembranesandwichedbetweentwo
scotchtapes 30
2-2. ElectrochemicalU-tubepermeationcell 31
2-3. Plotsofnanomolestransportedvs.tunewithandwithouttheapplied
transmembraneioniccurrent 35
4. TEMimageofAunanowireplatedwithinaporeofthemembrane
showingtheconically-shapedend 38
3-1 Scanningelectronmicrographofhomegrownaluminatemplate
membrane 47
2. Structuresofsilanesusedformodifications 50
3-3. Theconceptofchemicalandbiochemicaltest-tubefunctionalization 52
3-4. TEMimageofsilicanano-test-tubepreparedwithinhomegrown
aluminamembrane 57
3-5. TEMimageofroundpartofsilicanano-test-tube 57
vii
3-6. TEMimagesofdifferentsizesofsilicanano-test-tubes 58
3-7. Scanningelectronmicrographimageofpolystyrenetubes 60
33--8. Confocalmicroscopeimageof70nmdiasilicanano-testtube 61
43--9, Theconceptofantibodyattachmentstrategy 63
10.TEMimageofsilicanano-test-tubewithout(A)andwith
attachedantibody(B) 64
1. UV/visiblespectrafortheemeraldine-saltandemeraldine-base
formsofPANI 74
4-2. Cyclicvoltammogramforastainlesssteelelectrodecoatedwitha
0.5pmthickPANIfilmin1MH2SO4 75
4-3. SEMimageofa0.5pm-thickPANIfilmcoveringastainlesssteel
electrodesurface 76
4-4. Opencircuitpotentialvs.timedataforanuncoatedstainless
steelelectrode 78
4-5. Opencircuitpotentialvs.timedataforstainlesssteelelectrodescoated
withPANIfilmsoftheindicatedthickness 79
4-6. Opencircuitpotentialvs.timedataforstainlesssteelelectrodescoated
with0.5pmthickPANIfilmsinH2SO4solutionshavingtheindicated
concentration 80
4-7. OewlipetechntrOco2id,recasuiiri,tnop1rotMNen2tHi2aSlOvs4.stoilmuetidoantsatfhoartPweArNeIpcuoragteeddstainlesssteel 82
4-8. eSlEecMtriomdeagseurafa0c.e8apfmt-erth2i0cdkaPyAsNoIfefxiplomscuoraetetodo1nMtoHa2sStaOi4nless-steel 85
4-9. Openeircuitpotentialvs.timedatain1MH2SO4forastainlesssteel
electrodewhosesurfacewasonlyhalfeoatedwithaPANIfilm 86
4-10.EffectsofremovinghalfofthePANIfilmandofscratchingonthe
opencircuitpotentialvs.timedataforastainlesssteelelectrode
thatwascoatedwitha0.8pm-thickPANIfilm 87
4-11.Augerspectrumforanuncoatedstainlesssteelelectrodethathadbeen
exposedtolMH2SO4for48hours 89
4-12.AugerdepthprofiledatafortheelectrodeinFigure4-11 89
Vlll
4-12.AugerdepthprofiledatafortheelectrodeinFigure4-11 89
4-13.Augerdepthprofiledataforastainlesssteelelectrodethathad
b1eMenHco2SatOe4dfwoirth5ami0n.u8tpems-thickPANIfilmandexposedto 90
4-14.DataasperFigure4-12butafter48hourexposureto1MH2SO4 91
4-15.DataasperFigure4-12butafter7dayexposureto1MH2SO4 91
4-16.SRETimagesforastainlesssteelelectrodecoatedwitha2pm-thick
PANIfilmcontaininga1mm-diameterpinhole 94
IX
AbstractofDissertationPresentedtotheGraduateSchool
oftheUniversityofFloridainPartialFulfillmentofthe
RequirementsfortheDegreeofDoctorofPhilosophy
NEWMEMBRANETECHNOLOGIES-NANOTUBEMEMBRANESFOR
BIOTECHNOLOGICALAPPLICATIONSANDPOLYANILINEHLMSFOR
CORROSIONINHIBITION
By
RahelaGasparac
December2003
Chair: JohnR.Reynolds
MajorDepartment: Chemistry
Chapter1providesbackgroimdinformationonthetemplatesynthesisof
nanomaterials. Adescriptionofthetypesofmembranesusedfortemplatesynthesisis
given. Differentchemistriesthathavebeenusedtopreparetemplate-synthesized
structuresareprovided. Templatesynthesishasbeenusedtopreparesomeimportant
nanostructures. Polycarbonatemembraneswereusedtopreparegoldnanotubesusing
electrolessgoldtemplatemethod. Si02nano-test-tubesweremadebydippingthe
aluminatenplatemembraneinthesolandheating. Anintroductiontoconductiveis
presentedhereaswell.
Chapter2describesthetransportofDNAmoleculesthroughnanoporemembranes.
Weareinterestedinhowporediameterofthemembraneaffectsrateandseleetivityof
DNAtransportofdifferentsizeandcharge. Commerciallyavailablemicroporous
polycarbonatemembranefilterswereused. DNAchainscanbedriventhroughthe
nanoporeviatheelectrokinetictransportprocessesofelectrophoresisandelectroolsmotic
X