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Full-Text Articles in Physical Sciences and Mathematics

Porphyrin As A Spectroscopic Probe Of Net Electric Fields In Heme Proteins, Hannah Elizabeth Wagie Dec 2015

Porphyrin As A Spectroscopic Probe Of Net Electric Fields In Heme Proteins, Hannah Elizabeth Wagie

Theses and Dissertations

Heme proteins have diverse functions as well as varied structures but share the same organic, conjugated cofactor. Similarly varied approaches have been taken to deduce how heme can take on different roles based on its protein environment. A unique approach is to view the protein matrix as a constellation of point charges that generates a defined, reproducible, net internal electric field that has influence over the electronic properties of the heme cofactor. This work considers how porphyrins, the basic chromophore building block of heme, can be used as a native spectroscopic sensor of internal electric field at the active site …


Chiral Modification Of The Pd(111) Surface By Small Organic Molecules, Mausumi Mahapatra May 2015

Chiral Modification Of The Pd(111) Surface By Small Organic Molecules, Mausumi Mahapatra

Theses and Dissertations

Chiral modification of a metal surface is one of the most successful approaches of achieving enantioselective catalysis in heterogeneous phase. In this approach, an active metal surface is directly modified by adsorption of a chiral molecule (chiral modifier), the metal is responsible for catalytic activity while the adsorbed modifier controls the stereochemistry of adsorption and subsequent reactions through substrate interactions. So far, there are three types of widely recognized metal/modifier catalytic systems: tartaric acid modified Ni catalysts for the hydrogenation of β-ketoesters, cinchona modified Pt catalysts for hydrogenation of α-ketoesters and Pd catalysts modified with cinchona for selective activated alkene …