?url_ver=Z39.88-2004&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Adc&rft.relation=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F6339%2F&rft.title=ELECTROCHEMICAL+RECOGNITION+AND+TRANSPORT+OF+IONS+AT+LIQUID%2FLIQUID+INTERFACES+AS+A+PRINCIPLE+FOR+ENVIRONMENTAL+AND+BIOMEDICAL+ANALYSIS+AND+BEYOND&rft.creator=Rodgers%2C+Patrick+James&rft.description=Recognition+and+transport+of+important+species+at+the+membrane+of+a+biological+cell+are+critical+for+regulation+of+intracellular+communication%2C+metabolic+pathways%2C+vital+internal+conditions%2C+and+pharmaceutical+drug+up-take.+Both+processes+are+mediated+by+membrane-bound+proteins+functioning+as+pores%2C+channels%2C+and+transporters+that+recognize+and+facilitate+the+transport+of+ions%2C+nucleic+acids+and+sugars.+This+whole+process+can+be+driven+actively+by+membrane+potential+against+the+concentration+gradient+of+transported+species.+In+my+PhD+work%2C+I+fundamentally+characterized+dynamics+of+active+ion+transport%2C+both+in+the+presence+and+absence+of+recognition+events%2C+at+liquid%2Fliquid+interfaces+to+understand+electrochemically-controlled+interfacial+ion+recognition+and+transfer.+A+deeper+understanding+of+the+kinetic+and+thermodynamic+properties+is+achieved+to+realize+applications+in+biomedical+and+environmental+science%2C+sensor+technology+and+nanotechnology.+The+interface+between+two+immiscible+solutions+served+as+an+artificial+model+of+a+cell+membrane.+By+manipulation+of+the+interfacial+potential%2C+the+active+transport+of+ionic+species+was+mimicked%2C+which+was+monitored+by+an+ionic+current.+Micrometer+and+nanometer+sized+interfaces+were+formed+experimentally+at+the+orifice+of+micropipets+and+nanopipets+to+probe+ion-transfer+reactions.+Micropipet%2Fnanopipet+voltammetry+was+advanced+to+accurately+obtain+quantitative+kinetic+and+thermodynamic+parameters+through+numerical+simulations+of+ion+transfer+and+diffusion.+Ion+transfer+rates+for+reversible+and+nonreversible+reactions+were+determined+to+demonstrate+how+the+rate+controls+the+current%2C+which+affects+the+sensitivity+of+ion+transfer+as+a+sensing+principle.+Molecular+recognition+and+transport+of+biomedical+ionic+drugs+by+hydrophobic+receptors+was+examined+thermodynamically%2C+demonstrating+how+the+interfacial+interactions+influence+the+selectivity+of+the+sensing+principle.+Kinetic+and+thermodynamic+analysis+of+the+transfer+of+perfluoroalkyl+surfactants%2C+an+emerging+class+of+environmental+contaminants+that+accumulate+in+wildlife%2C+yielded+high+lipophilic+values+to+suggest+a+possible+origin+of+their+high+toxicity.+Although%2C+the+focus+of+my+research+was+primarily+fundamental+in+nature%2C+I+tested+the+ion+transfer+principle+practically+with+an+ion+selective+electrode%2C+developed+in+our+group.+Hexafluoroarsenate%2C+an+arsenical+biocide+found+recently+in+wastewater%2C+was+detected+at+sub-nanomolar+levels+to+confirm+a+thermodynamic+mechanism+that+controls+the+detection+limit.&rft.date=2010-06-24&rft.type=University+of+Pittsburgh+ETD&rft.type=PeerReviewed&rft.format=application%2Fpdf&rft.language=en&rft.identifier=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F6339%2F1%2FRodgersPatrickJ012210.pdf&rft.identifier=++Rodgers%2C+Patrick+James++(2010)+ELECTROCHEMICAL+RECOGNITION+AND+TRANSPORT+OF+IONS+AT+LIQUID%2FLIQUID+INTERFACES+AS+A+PRINCIPLE+FOR+ENVIRONMENTAL+AND+BIOMEDICAL+ANALYSIS+AND+BEYOND.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++