TY - BOOK
T1 - Covalent Organic
T2 - Metaloxide Modification of Nanostructure Surfaces for Protein and Intracellular Interaction Studies
AU - Vutti, Surendra
PY - 2016
Y1 - 2016
N2 - This thesis describes the development and applications of covalent functionalization onsilicon, GaAs and InAs semiconductor samples and their biological applications. The firstchapter is devoted to the introduction of one dimensional semiconductor materials, theirbiological applications, surface chemistry of silicon, InAs and GaAs materials, covalentsurface functionalization using organosilanes, liquid-phase, and vapor-phasefunctionalizations, diazo-transfer reaction, CuAAC click chemistry, different types ofbiorthogonal chemistries, SPAAC chemistry, and cellular interactions of chemically modifiednanostructures.The second chapter provides an overview of stable primary metal-surface functionalizationand its significant role in reliable secondary attachment of complex functional molecules. Inprinciple, this can be achieved through chemical reactions either in vapor-phase or in liquidphase.We compared these two methods for oxidized silicon surfaces and thoroughlycharacterized the functionalization steps by tagging and fluorescence imaging. Wedemonstrate that the vapor-phase functionalization only provides transient surfacemodification which was lost by extensive washing. For stable surface modification, a liquidphasemethod is developed. New versatile strategy for azide modification with AzPTES onsilicon, GaAs and InAs samples is presented. Using this method, silicon, GaAs and InAssamples are decorated with azides for having secondary attachment of complex functionalmolecules.Chapter three is devoted to the covalent immobilization of D-amino acid adhesion peptideson azide functionalized silicon, GaAs and InAs materials by using CuAAC-click chemistry.The covalent immobilization of penetration peptide (TAT) on gold nanotips of InAs NWs isalso demonstrated.In chapter four, the covalent immobilization of GFP on silicon wafers, GaAs wafers andGaAs NWs is demonstrated. Series of Fmoc-Pra-OH, NHS-PEG5-NHS and BCN-NHSfunctionalized silicon surfaces has been prepared, whereby GFP-N3 and GFP-bicyclononyneare immobilized by using CuAAC and SPAAC chemistry. The specific and covalentimmobilization of GFP-N3 on bicyclononyne functionalized GaAs samples (wafers and NWs)is presented in comparing the reaction with GFP-NH2. Anti-GFP antibody interaction is alsodemonstrated between the samples reacted with GFP-N3 and GFP-NH2. The efforts ofcovalent modification of GaAs NWs directed toward the synthesis and immobilization ofpeptide substrate on GaAs NWs, and its application in proteolytic hydrolysis withchymotrypsin enzyme are presented in chapter five.Finally, chapter six is devoted to the application of the silicon and InAs wafers immobilizedwith adhesion peptide. This enabled the study of cell adhesion to the Si and InAs metalsurface. In contrast to unmodified surfaces, the peptide-modified surfaces were able tomaintain cell adhesion during significant flow velocities in a micro flow reactor. For aboveall chemical modifications, the respective control experiments are demonstrated.
AB - This thesis describes the development and applications of covalent functionalization onsilicon, GaAs and InAs semiconductor samples and their biological applications. The firstchapter is devoted to the introduction of one dimensional semiconductor materials, theirbiological applications, surface chemistry of silicon, InAs and GaAs materials, covalentsurface functionalization using organosilanes, liquid-phase, and vapor-phasefunctionalizations, diazo-transfer reaction, CuAAC click chemistry, different types ofbiorthogonal chemistries, SPAAC chemistry, and cellular interactions of chemically modifiednanostructures.The second chapter provides an overview of stable primary metal-surface functionalizationand its significant role in reliable secondary attachment of complex functional molecules. Inprinciple, this can be achieved through chemical reactions either in vapor-phase or in liquidphase.We compared these two methods for oxidized silicon surfaces and thoroughlycharacterized the functionalization steps by tagging and fluorescence imaging. Wedemonstrate that the vapor-phase functionalization only provides transient surfacemodification which was lost by extensive washing. For stable surface modification, a liquidphasemethod is developed. New versatile strategy for azide modification with AzPTES onsilicon, GaAs and InAs samples is presented. Using this method, silicon, GaAs and InAssamples are decorated with azides for having secondary attachment of complex functionalmolecules.Chapter three is devoted to the covalent immobilization of D-amino acid adhesion peptideson azide functionalized silicon, GaAs and InAs materials by using CuAAC-click chemistry.The covalent immobilization of penetration peptide (TAT) on gold nanotips of InAs NWs isalso demonstrated.In chapter four, the covalent immobilization of GFP on silicon wafers, GaAs wafers andGaAs NWs is demonstrated. Series of Fmoc-Pra-OH, NHS-PEG5-NHS and BCN-NHSfunctionalized silicon surfaces has been prepared, whereby GFP-N3 and GFP-bicyclononyneare immobilized by using CuAAC and SPAAC chemistry. The specific and covalentimmobilization of GFP-N3 on bicyclononyne functionalized GaAs samples (wafers and NWs)is presented in comparing the reaction with GFP-NH2. Anti-GFP antibody interaction is alsodemonstrated between the samples reacted with GFP-N3 and GFP-NH2. The efforts ofcovalent modification of GaAs NWs directed toward the synthesis and immobilization ofpeptide substrate on GaAs NWs, and its application in proteolytic hydrolysis withchymotrypsin enzyme are presented in chapter five.Finally, chapter six is devoted to the application of the silicon and InAs wafers immobilizedwith adhesion peptide. This enabled the study of cell adhesion to the Si and InAs metalsurface. In contrast to unmodified surfaces, the peptide-modified surfaces were able tomaintain cell adhesion during significant flow velocities in a micro flow reactor. For aboveall chemical modifications, the respective control experiments are demonstrated.
UR - https://soeg.kb.dk/permalink/45KBDK_KGL/fbp0ps/alma99121958950805763
M3 - Ph.D. thesis
BT - Covalent Organic
PB - Department of Chemistry, Faculty of Science, University of Copenhagen
ER -