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Development of a chemical means to mimic nucleo-cytoplasmic transport and catalytic reduction of secondary alkyl monohalides by cobalt(I) salen and nickel(I) salen electrogenerated at vitreous carbon electrodes

Posted on:2017-07-05Degree:Ph.DType:Dissertation
University:Indiana UniversityCandidate:Bird, Sean PatrickFull Text:PDF
GTID:1461390014465330Subject:Analytical Chemistry
Abstract/Summary:
Polymer chemistry has spawned many modern-day materials that have found utility in nearly all aspects of life. One aspect of importance to analytical and material chemists is how polymers in the form of hydrogels may selectively respond to their chemical environment for the purpose of detection or purification. Much work has been done on the development of responsive hydrogels, and recently a focus has been placed on incorporating biological motifs into abiotic hydrogels for the use of highly selective molecular recognition. The work herein describes how a hydrogel derived from protein found the nuclear pore complex (NPC) was characterized and subsequently mimicked on a synthetic platform.;The first half of this document provides an introduction to the field of responsive hydrogels and discusses how one aspect of the Nsp1 hydrogel was characterized. Specifically, attention is given to the measurement of diffusional processes of nuclear transport receptor (NTRs) with the Nsp1 hydrogel and how these compare to other macromolecular diffusional processes in additional, chemically inert hydrogels. These processes were measured by means of spatial frequency analysis of fluorescence recovery after photobleaching data obtained by confocal microscopy.;Later chapters focus on how an abiotic analog of the NPC was created. Briefly, moieties critical for selective transport within Nsp1 hydrogels were synthesized and grafted on a polyacrylamide backbone. Confocal microscopy was then utilized to determine the selectivity of the modified polyacrylamide gel. Lastly, characteristics of polyacrylamide gels and Nsp1 gels were compared.;In the final chapter, a divergence is made from the study of the nuclear pore complex and a discussion of the catalytic reduction of cyclohexyl monohalides by electrogenerated cobalt(I) salen and nickel(I) salen. Mechanistic aspects of the catalytic reduction of cyclohexyl halides by cobalt(I) are also discussed.
Keywords/Search Tags:Catalytic reduction, Salen, Cobalt, Transport
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