Polyelectrolyte Complexes Based on Poly(acrylic acid)

170 Pages·2017·10.2 MB·English

by  Xiaoyan Lu

UUnniivveerrssiittyy ooff CCeennttrraall FFlloorriiddaa
SSTTAARRSS
Electronic Theses and Dissertations
2018
PPoollyyeelleeccttrroollyyttee CCoommpplleexxeess BBaasseedd oonn PPoollyy((aaccrryylliicc aacciidd))::
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Xiaoyan Lu
University of Central Florida
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Electronic Theses and Dissertations. 5769.
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POLYELECTROLYTECOMPLEXBASEDONPOLY(ACRYLICACID):MECHANICSAND
APPLICATIONS
by
XIAOYANLU
M.S.BeijingInstituteofTechnology,2012
B.S.TaishanUniversity,2009
Adissertationsubmittedinpartialfulfilmentoftherequirements
forthedegreeofDoctorofPhilosophy
intheDepartmentofChemistry
intheCollegeofScience
attheUniversityofCentralFlorida
Orlando,Florida
SpringTerm
2018
MajorProfessor:LeiZhai
(cid:13)c 2018XiaoyanLu
ii
ABSTRACT
Poly(acrylic acid) (PAA) is a weak polyelectrolyte presenting negative charge at basic condition
when the carboxylic group loses a proton. These carboxylate group can interact with polycations
and metal ions to form stable polyelectrolyte complexes (PECs), leading to tunable properties
and multifunctional nanoscale structures through chemical reactions. This research focuses on
nanofiber and nanoparticle fabricated by PAA-based PECs. We demonstrated the effect of ferric
ionconcentrationonthemechanicalpropertiesofPAA-basedsinglenaonofiberbyusingdarkfield
microscopy imaging and persistence length analysis. The application of PAA-based nanofiber
mats loaded with MnO for supercapacitors was also explored. As a free-standing and flexible
2
supercapacitorelectrode,thenanofibermatexhibitedoutstandingpropertiesincludinghighspecific
capacitance,excellentreversibleredoxreactions,andfastcharge/dischargeability. SincePAAisa
biocompatible polymer, PAA-based PEC was applied as a drug-carrier in a drug delivery system.
In this project, core-shell nanoparticles were fabricated with chitosan as the core and PAA as the
shell to incorporate with the drug gemcitabine. Several parameters were investigated to obtain
the optimal nanoparticle size. The as-prepared drug delivery system shows prolonged releasing
profile.
iii
ACKNOWLEDGMENTS
I am extremely thankful to Dr. Lei Zhai for being my dissertation advisor. I do not have enough
wordstodescribemyrespectandgratitudeforhim. Hisconstantsupporttowardsmyresearchand
academics in general made me more professional. I feel extremely thankful to to have him as my
mentorandsupervisor. Heisnotonlyanadvisor,butalsoagoodfriend.
I am also very grateful to Dr. Shengli Zou, Dr. Demitry Kolpashchikov, Dr. Karin Chumbimuni-
Torres, and Dr. Yajie Dong for being part of my dissertation committee and for their encouraging
andvaluablecommentsandremarks. Eachoneofthemismyrolemodelforstudyandresearch.
I gratefully acknowledge the support provided by the department of Chemistry, Nanoscience and
TechnologyCenter(NSTC),andAdvancedMaterialsProcessingandAnalysisCenter(AMPAC).I
am also thankful to Ernie, Ted, Kirk, Matt, Mikhail and Karen for their help in the usages of
instrumentations.
I would also like to thank all my lab-mates Astha Malhotra, Jean Calderon, Matthew McInnis,
Chen Shen, Nilab Azim, Zeyang Zhang, Elizabeth Barrios; my undergraduate researchers Ruginn
CatarataandOliviaMcClellanandthecolleagues,likeAngieDiazfromcollaboratinglabs. Itwas
apleasureworkingwiththem.
I am also immensely thankful to my friends who helped my stay here more enjoyable and my
friends in China and around whose encouragement has really been a great support to me here in a
foreignland.
Words or expressions are not enough to thank my husband and parents, back home for their pa-
tience,support,understandingandsacrifices. Ihavetothankmysistersforbeingthereformeand
encouragingme. MybabyDanielhighlymotivatesmetoacheivethestudyaccomplishement.
iv
I would also like to express my thanks and sincere regards to everyone else whose help, encour-
agementandprayersmusthavestrengthenedmeandhelpedmeachievethingsinlife.
Finally but most importantly, I have to thank GOD for his continuous love and amazing grace.
Withouthim,Icouldn’tdoanything.
v
TABLE OF CONTENTS
LISTOFFIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
LISTOFTABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xx
CHAPTER1: INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Polyelectrolyte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Polyelectrolytecomplex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
NanostructureofpolyelectrolyteandPEC . . . . . . . . . . . . . . . . . . . . . . . . . 8
PECnanoparticle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
PECnanofiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
PECmembrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
PEChydrogel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Applicationofpolyelectrolytecomplex . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Biotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Tissueengineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Drugdelivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Genedelivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
vi
Woundself-healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Actuator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Energystorage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Themeoftheresearch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
CHAPTER2: TUNABLEEFFECTOFMETALIONSONPOLYELECTROLYTENANOFIBER
MECHANICALPERFORMANCE . . . . . . . . . . . . . . . . . . . . . . 31
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
MaterialsandMethods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Nanofibersynthesisbyelecrospinning . . . . . . . . . . . . . . . . . . . . . . . . 35
Scanningelectronmicroscopyandtransmissionelectronmicroscopy . . . . . . . . 35
FourierTransformInfraredSpectroscopy(FTIR) . . . . . . . . . . . . . . . . . . 36
Confocalmicroscopyimagingandbendingmechanicsdataanalysis . . . . . . . . 36
ResultsandDiscussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Ferric ions modulate the mechanical properties and average length of polyacrylic
acidnanofibers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
ChitosanhelpsferricionsmodulatethemechanicalpropertiesofPAAnanofibers. . 43
ElectrospunPAA:CSnanofiberscouldexistinhydratedstates. . . . . . . . . . . . 45
vii
Characterization sheds light on how ferric metal ions affect individual PAA:CS
nanofiberstructure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
CHAPTER3: FLEXIBLE CORE-SHELL COMPOSITE FIBERS FOR HIGH PERFOR-
MANCESUPERCAPACITORELECTRODES . . . . . . . . . . . . . . . . 52
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
ExperimentalProcedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Materialssynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
FabricationofNanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . 56
CreatingMnO NanoparticlesonPAANanofibers . . . . . . . . . . . . . 56
2
DepositingthePolypyrroleShellontheSurfaceofMnO @PAANanofibers
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
ResultsandDiscussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Preparationofsupercapacitorelectrodes . . . . . . . . . . . . . . . . . . . . . . . 59
ElectrochemicalCharacterization . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
viii
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
CHAPTER4: GEMCITABINELOADEDPOLY(ACRYLICACID)-CHITOSANNANOPAR-
TICLESFORTARGETEDTHERAPYOFPANCREATICCANCER . . . . 84
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
ExperimentalProcedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
FabricationofNanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Characterizationofthenanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . 89
Incubationandencapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Invitrodrugreleasing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
ResultsandDiscussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
EffectofCS:TPPratioonCS/TPPnanoparticleproperties . . . . . . . . . . . . . 91
EffectofPAA:CSratioonCS/TPPnanoparticleproperties . . . . . . . . . . . . . 93
EffectofCS:EDCratioonCS/TPP-PAAnanoparticleproperties . . . . . . . . . . 95
EffectofpHvalueonCS/TPP-PAAnanoparticleproperties . . . . . . . . . . . . . 97
Invitrodrugreleasingstudy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
ix