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Chemoselective synthesis of functional homocysteine residues in polypeptides and peptides

Eric G. Gharakhanian a and Timothy J. Deming* ab  a Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA b Department of Bioengineering, University of California, Los Angeles, CA 90095, USA.  http://pubs.rsc.org/en/Content/ArticleLanding/2016/CC/C6CC01253A#!divAbstract http://pubs.rsc.org/en/content/articlepdf/2016/cc/c6cc01253a   Abstract A methodology was developed for efficient, chemoselective transformation of methionine residues into stable, functional homocysteine derivatives. Methionine residues can undergo highly chemoselective alkylation reactions at low pH to yield stable sulfonium ions, which could then be selectively demethylated to give stable alkyl homocysteine residues. This mild, two-step process is chemoselective, efficient, tolerates many functional groups, and provides a means for creation of new functional biopolymers, site-specific peptide tagging, and s...

Mn(V)(O) versus Cr(V)(O) Porphyrinoid Complexes: Structural Characterization and Implications for Basicity Controlling H-Atom Abstraction

Journal of the American Chemical Society by Regina A. Baglia, Katharine A. Prokop-Prigge, Heather M. Neu, Maxime A. Siegler and David P. Goldberg  /  2d  //  keep unread  //  hide  //  preview   http://pubs.acs.org/doi/pdf/10.1021/jacs.5b05142 Isomorphous crystals of Mn V (O) and Cr V (O) corrolazines were characterized by single crystal X-ray diffraction. Reactivity studies with H atom donors and separated PCET reagents show a dramatic difference in H atom abstracting abilities for these two complexes. The implied large difference in driving force is opposite the trend in redox potentials, indicating that basicity is a key factor in determining the striking difference in reactivity for two metal-oxo species in identical ligand environments.  Journal of the American Chemical Society DOI: 10.1021/jacs.5b05142 Visit Website

Solid-State 17O NMR Spectroscopy of Paramagnetic Coordination Compounds

Angewandte Chemie International Edition  by Xianqi Kong, Victor V. Terskikh, Rahul L. Khade, Liu Yang, Amber Rorick, Yong Zhang, Peng He, Yining Huang, Gang Wu  /   11d   //   keep unread   //   hide   //   preview Abstract High-quality solid-state  17 O (I=5/2) NMR spectra can be successfully obtained for paramagnetic coordination compounds in which oxygen atoms are directly bonded to the paramagnetic metal centers. For complexes containing V III  ( S =1), Cu II  ( S =1/2), and Mn III  ( S =2) metal centers, the  17 O isotropic paramagnetic shifts were found to span a range of more than 10 000 ppm. In several cases, high-resolution  17 O NMR spectra were recorded under very fast magic-angle spinning (MAS) conditions at 21.1 T. Quantum-chemical computations using density functional theory (DFT) qualitatively reproduced the experimental  17 O hyperfine shift tenso...