Inhibition and acceleration of deuterium exchange in amide-functionalized monolayer-protected gold clusters

Hydrogen/deuterium exchange rates in amide-functionalized monolayer protected gold clusters (MPCs) are controlled by the radial nature of the surface, with inhibition and catalysis observed at different chain lengths.     

Reaction of lithium dimethylcuprate with conformationally biased β-acyloxy enol esters - regio and stereocontrolled access to functionalized six-carbon chiral synthons

Alkyl 2-acyloxy α-D-erythro-hex-2-enopyranoside diesters, readily available from D-hexoses, are versatile intermediates fro the expeditious preparation of six-carbon chiral synthons containing alternating and/or consecutive C-methyl and hydroxyl groups.     

Arrested chloride abstraction from trans-RuCl2(DMeOPrPE)2 with TlPF6; formation of a 1-D coordination polymer having unusual octahedral coordination around thallium(I)

An "arrested" chloride abstraction occurs in the reaction of trans-RuCl(2)(DMeOPrPE)(2) with TlPF(6); the product is a 1-D coordination polymer in which the Tl(I) centers have an unusual octahedral coordination geometry with a stereochemically active 6s(2) lone pair.     

Modulation of the pK(a) of metal-bound water via oxidation of thiolato sulfur in model complexes of Co(III) containing nitrile hydratase: insight into possible effect of cysteine oxidation in Co-nitrile hydratase

The Co(III) complexes of N,N'-bis(2-mercaptophenyl)pyridine-2,6-dicarboxamide (PyPSH(4)), a designed pentadentate ligand with built-in carboxamide and thiolate groups, have been synthesized and studied to gain insight into the role of Cys-S oxidation in Co-containing nitrile hydratase (Co-NHase). Reaction of [Co(NH(3))(5)Cl]Cl(2) with PyPS(4)(-) in DMF affords the thiolato-bridged dimeric Co(III) complex (Et(4)N)(2)[Co(2)(PyPS)(2)] (1). Although the bridged structure is quite robust, reaction of (Et(4)N)(CN) with 1 in acetonitrile affords the monomeric species (Et(4)N)(2)[Co(PyPS)(CN)] (2). Oxidation of 2 with H(2)O(2) in acetonitrile gives rise to a mixture which, upon chromatographic purification, yields K(2)[Co(PyPSO(2)(OSO(2))(CN] (3), a species containing asymmetrically oxidized thiolates. The Co(III) metal center in 3 is coordinated to a S-bound sulfinate and an O-bound sulfonate (OSO(2)) group. Upon oxidation with H(2)O(2), 1 affords an asymmetrically oxidized dimer (Et(4)N)(2)[Co(2)(PyPS(SO(2)))(2)] (4) in which only the terminal thiolates are oxidized to form S-bound sulfinate groups while the bridging thiolates remain unchanged. The thiolato-bridge in 4 is also cleaved upon reaction with (Et(4)N)(CN) in acetonitrile, and one obtains (Et(4)N)(2)[Co(PyPS(SO(2)))(CN)] (5), a species that contains both coordinated thiolate and S-bound sulfinate around Co(III). The structures of 1-4 have been determined. The spectroscopic properties and reactivity of all the complexes have been studied to understand the behavior of the Co(III) site in Co-NHase. Unlike typical Co(III) complexes with bound CN(-) ligands, the Co(III) centers in 2 and 5 are labile and rapidly lose CN(-) in aqueous solutions. Since 3 does not show this lability, it appears that at least one thiolato sulfur donor is required in the first coordination sphere for the Co(III) center in such species to exhibit lability. Both 2 and 5 are converted to the aqua complexes [Co(PyPS)(H(2)O)](-) and [Co(PyPS(SO(2))(H(2)O)](-) in aqueous solutions. The pK(a) values of the bound water in these two species, determined by spectrophotometry, are 8.3 +/- 0.03 and 7.2 +/- 0.06, respectively. Oxidation of the thiolato sulfur (to sulfinate) therefore increases the acidity of the bound water. Since 2 and 5 promote hydrolysis of acetonitrile at pH values above their corresponding pK(a) values, it is also evident that a metal-bound hydroxide is a key player in the mechanism of hydrolysis by these model complexes of Co-NHase. The required presence of a Cys-sulfinic residue and one water molecule at the Co(III) site of Co-NHase as well as the optimal pH of the enzyme near 7 suggests that (i) modulation of the pK(a) of the bound water molecule at the active site of the enzyme could be one role of the oxidized Cys-S residue(s) and (ii) a cobalt-bound hydroxide could be responsible for the hydrolysis of nitriles by Co-NHase.     

Thermal and photochemical epimerization/equilibration of carbohydrate cobaloximes

Epimeric carbohydrate alkyl cobaloximes 4:5, 9:10, and 12:13 can be equilibrated thermally or photochemically. In each case, one isomer is strongly favored: exo-3-deoxy-3-pyridyldimethylglyoximatocobalt-1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose 4 for the 4:5 epimer pair, exo-3-deoxy-3-pyridyldimethylglyoximatocobalt-5-O-carboxymethyl-1,2-O-isopropylidene-alpha-D-xylofuranose 9 for the 9:10 epimer pair, and equatorial 1-deoxy-1-pyridyldimethylglyoximatocobalt-2,3,4,6-tetra-O-benzyl-beta-D-glucopyranose 12 for the 12:13 epimer pair. These data indicate that there is a strong facial preference for the coupling of py(dmgH)(2)Co(*) radicals with alkyl R(*) free radicals, with the preferred kinetic path leading to the more stable product.     

Moduli of twisted spin curves

In this note we give a new, natural construction of a compactification of the stack of smooth -spin curves, which we call the stack of stable twisted -spin curves. This stack is identified with a special case of a stack of twisted stable maps of Abramovich and Vistoli. Realizations in terms of admissible -spaces and -line bundles are given as well. The infinitesimal structure of this stack is described in a relatively straightforward manner, similar to that of usual stable curves.

We construct representable morphisms from the stacks of stable twisted -spin curves to the stacks of stable -spin curves and show that they are isomorphisms. Many delicate features of -spin curves, including torsion free sheaves with power maps, arise as simple by-products of twisted spin curves. Various constructions, such as the -operator of Seeley and Singer and Witten's cohomology class go through without complications in the setting of twisted spin curves.

     

Applying the silver‐tube introduction method for thermal conversion elemental analyses and a new δ2H value for NBS 22 oil

The δ²H_VSMOW–SLAP value of total hydrogen of the international measurement standard NBS 22 oil was determined by a new method of sealing water in silver tubes for use in a thermal conversion elemental analysis (TC/EA) reduction unit. The isotopic fractionation of water due to evaporation is virtually non‐existent in this silver‐tube method. A new value for the δ²H_VSMOW–SLAP of NBS 22 oil, calibrated with isotopic reference waters, was determined to be ?116.9 ± 0.8‰ (1σ and n = 31). Published in 2010 by John Wiley & Sons, Ltd.