Developing Dirhodium-Complexes for Protein Inhibition and Modification & Copper-Catalyzed Remote Chlorination of Alkyl-Hydroperoxides

dc.contributor.advisorBall, Zachary T.
dc.contributor.committeeMemberMarti, Angel A.
dc.contributor.committeeMemberBiswal, Sibani Lisa
dc.creatorKundu, Rituparna
dc.date.accessioned2013-09-16T15:31:41Z
dc.date.accessioned2013-09-16T15:31:48Z
dc.date.available2013-09-16T15:31:41Z
dc.date.available2013-09-16T15:31:48Z
dc.date.created2013-05
dc.date.issued2013-09-16
dc.date.submittedMay 2013
dc.date.updated2013-09-16T15:31:48Z
dc.description.abstractThe work describes the development of a new class of protein-inhibitors for protein-protein interactions, based on metallopeptides comprised of a dirhodium metal center. The metal incorporation in the peptide sequence leads to high increase in binding affinity of the inhibitors. The source of this strong affinity is the interaction of histidine on the protein surface with the rhodium center. In addition to this work, rhodium-based small molecule inhibitors for FK-506 binding proteins are investigated. Also, methodology for rhodium-catalyzed modification of proteins containing surface cysteine has been developed where a simple rhodium(II) complex catalyzes cysteine modification with diazo reagents. The reaction is marked by clean cysteine selectivity and mild reaction conditions. The resulting linkage is significantly more stable in human plasma serum, when compared to common maleimide reagents. Apart from this body of work in chemical-biology, the thesis contains the discussion of development of copper-catalyzed remote chlorination of alkyl hydroperoxides. The atom transfer chlorination utilizes simple ammonium chloride salts as the chlorine source and the internal redox process requires no external redox reagents.
dc.format.mimetypeapplication/pdf
dc.identifier.citationKundu, Rituparna. "Developing Dirhodium-Complexes for Protein Inhibition and Modification & Copper-Catalyzed Remote Chlorination of Alkyl-Hydroperoxides." (2013) Diss., Rice University. <a href="https://hdl.handle.net/1911/71980">https://hdl.handle.net/1911/71980</a>.
dc.identifier.slug123456789/ETD-2013-05-368
dc.identifier.urihttps://hdl.handle.net/1911/71980
dc.language.isoeng
dc.rightsCopyright is held by the author, unless otherwise indicated. Permission to reuse, publish, or reproduce the work beyond the bounds of fair use or other exemptions to copyright law must be obtained from the copyright holder.
dc.subjectMetallopeptides
dc.subjectProteins
dc.subjectProtein interactions
dc.subjectInhibitors
dc.subjectCysteine modification
dc.subjectRhodium
dc.subjectSp3 remote C-H activation
dc.titleDeveloping Dirhodium-Complexes for Protein Inhibition and Modification & Copper-Catalyzed Remote Chlorination of Alkyl-Hydroperoxides
dc.typeThesis
dc.type.materialText
thesis.degree.departmentChemistry
thesis.degree.disciplineNatural Sciences
thesis.degree.grantorRice University
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy
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