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Full-Text Articles in Physical Sciences and Mathematics

Charge-Mediated Recognition Of N-Terminal Tryptophan In Aqueous Solution By A Synthetic Host, Meghan E. Bush, Nicole D. Bouley, Adam R. Urbach Oct 2005

Charge-Mediated Recognition Of N-Terminal Tryptophan In Aqueous Solution By A Synthetic Host, Meghan E. Bush, Nicole D. Bouley, Adam R. Urbach

Chemistry Faculty Research

The molecular recognition of peptides and proteins in aqueous solution by designed molecules remains an elusive goal with broad implications for basic biochemical research and for sensors and separations technologies. This paper describes the recognition of N-terminal tryptophan in aqueous solution by the synthetic host cucurbit[8]uril (Q8). Q8 is known to form 1:1:1 heteroternary complexes with methyl viologen (MV) and a second aromatic guest. Here, the complexes of Q8·MV with (i) the four natural aromatic α-amino acids, (ii) four singly charged tryptophan derivatives, and (iii) four tryptophan-containing tripeptides were characterized by isothermal titration calorimetry, mass spectrometry, and UV−visible, fluorescence, and …


Origin Of Enantioselection In Chiral Alcohol Oxidation Catalyzed By Pd[(–)-Sparteine]Cl2, J. A. Mueller, Anne Cowell, Bert D. Chandler, M. S. Sigman Sep 2005

Origin Of Enantioselection In Chiral Alcohol Oxidation Catalyzed By Pd[(–)-Sparteine]Cl2, J. A. Mueller, Anne Cowell, Bert D. Chandler, M. S. Sigman

Chemistry Faculty Research

A kinetic investigation into the origin of enantioselectivity for the Pd[(–)-sparteine]Cl2-catalyzed aerobic oxidative kinetic resolution (OKR) is reported. A mechanism to account for a newly discovered chloride dissociation from Pd[(–)-sparteine]Cl2 prior to alcohol binding is proposed. The mechanism includes (1) chloride dissociation from Pd[(–)-sparteine]Cl2 to form cationic Pd(–)-sparteine]Cl, (2) alcohol binding, (3) deprotonation of Pd-bound alcohol to form a Pd-alkoxide, and (4) β-hydride elimination of Pd–alkoxide to form ketone product and a Pd–hydride. Utilizing the addition of (–)-sparteine HCl to control the [Cl] and [H+] and the resulting derived rate law, …


Low-Temperature Activation Conditions For Pamam Dendrimer Templated Pt Nanoparticles, Anil Singh, Bert D. Chandler Aug 2005

Low-Temperature Activation Conditions For Pamam Dendrimer Templated Pt Nanoparticles, Anil Singh, Bert D. Chandler

Chemistry Faculty Research

Surface immobilized polyamidoamine (PAMAM) dendrimer templated Pt nanoparticles were employed as precursors to heterogeneous catalysts. CO oxidation catalysis and in situ infrared spectroscopy were used to evaluate conditions for dendrimer removal. Infrared spectroscopy showed thatPAMAMdendrimer amide bonds begin decomposing at temperatures as low as 75 °C. Although the amide stretches are completely removed after 3 h of oxidation at 300 °C, 16 h were required to reach maximum catalytic activity. Further treatment under oxidizing or reducing atmospheres did not cause substantial changes in activity. Infrared spectroscopy of the activated materials indicated that organic residues, probably surface carboxylates, are formed during …