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

dc.contributor.advisorBall, Zachary T.en_US
dc.contributor.committeeMemberMarti, Angel A.en_US
dc.contributor.committeeMemberBiswal, Sibani Lisaen_US
dc.creatorKundu, Rituparnaen_US
dc.date.accessioned2013-09-16T15:31:41Zen_US
dc.date.accessioned2013-09-16T15:31:48Zen_US
dc.date.available2013-09-16T15:31:41Zen_US
dc.date.available2013-09-16T15:31:48Zen_US
dc.date.created2013-05en_US
dc.date.issued2013-09-16en_US
dc.date.submittedMay 2013en_US
dc.date.updated2013-09-16T15:31:48Zen_US
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.en_US
dc.format.mimetypeapplication/pdfen_US
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>.en_US
dc.identifier.slug123456789/ETD-2013-05-368en_US
dc.identifier.urihttps://hdl.handle.net/1911/71980en_US
dc.language.isoengen_US
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.en_US
dc.subjectMetallopeptidesen_US
dc.subjectProteinsen_US
dc.subjectProtein interactionsen_US
dc.subjectInhibitorsen_US
dc.subjectCysteine modificationen_US
dc.subjectRhodiumen_US
dc.subjectSp3 remote C-H activationen_US
dc.titleDeveloping Dirhodium-Complexes for Protein Inhibition and Modification & Copper-Catalyzed Remote Chlorination of Alkyl-Hydroperoxidesen_US
dc.typeThesisen_US
dc.type.materialTexten_US
thesis.degree.departmentChemistryen_US
thesis.degree.disciplineNatural Sciencesen_US
thesis.degree.grantorRice Universityen_US
thesis.degree.levelDoctoralen_US
thesis.degree.nameDoctor of Philosophyen_US
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