A silanediol inhibitor of the metalloprotease thermolysin: synthesis and comparison with a phosphinic acid inhibitor

A silanediol inhibitor of the metalloprotease thermolysin was prepared for comparison to a known phosphinic acid inhibitor, providing the first comparison of these second-row element based transition-state analogues. Inhibition of thermolysin by the silanediol (K(i) = 41 nM) was comparable to that of the phosphinic acid (K(i) = 10 nM) even though the silanediol is uncharged and thereby lacks the intrinsic Coulombic attraction of the phosphinate anion to the active-site zinc cation. This silanediol protease inhibitor is the least sterically encumbered example prepared to date and, therefore, the most prone toward polymerization. Hydrolysis of a difluorosilane intermediate to the silanediol leads cleanly to a monomeric product.     

Enhancive Synthesis of ‐lβ, 11‐Diol‐4‐en‐eudesmol

An enhancive synthesis of ?1β, 11‐diol‐4‐en‐eudesmol, starting from 2‐chloroacrylonitrile, is described. The effect of temperature on the Diels‐Alder reaction of 2‐chloroacrylonitrile with 2‐methylfuran and the condition of cationic cyclization of diene were discussed in detail.     

Sensitivity in Supramolecular Architectures of Polyaromatic Salts Containing Two Singly‐Pimerized Bipyridines

Three novel supramolecular arrays of zigzag polyaromatic salts are reported. Both the conformation and disposition of the dications are subjected to various noncovalent interactions. Thus, the presence or absence of the π‐π interacting enclathrated molecules, the efficient packing and the involved hydrogen bonding interactions of anions, as well as the increased hydrophobic property of the dications themselves exert influence.     

Chiral attachment of styrene mediated by surface dimers on Ge100

We have investigated the chiral adsorption configurations of styrene on Ge(100) using scanning tunneling microscopy at 300 K. The chemisorbed styrene on a single Ge dimer reduces the symmetry of the molecule, which produces a chiral center, and leads to the (S) or (R) chiral on-top configuration. We have found that the dimeric adsorption of styrene induced by the Ge surface dimer structure forms the enantiomeric and diastereomeric paired end-bridge configurations. We determine the absolute chirality of adsorbed styrene on Ge(100) and demonstrate a novel method for the achiral molecule to produce dimeric enantiomers and diastereomers attached to the semiconductor surface.     

Calix[4]crown in dual sensing functions with FRET

A new calix[4]crown chemosensor based on dual sensing probes reveals Pb²⁺ ion selectivity over other metal ions, which arises from a hypsochromic shift of azo units in UV spectrum as well as a fluorescence enhancement of pyrenyl parts in fluorescence spectrum via a suppressed FRET.     

Mononuclear nonheme ferric-peroxo complex in aldehyde deformylation

A mononuclear nonheme ferric-peroxo complex bearing a macrocyclic tetradentate N4 ligand, [(TMC)Fe(III)-O2]+, was prepared and used in mechanistic studies of aldehyde deformylation; a catalytic aldehyde deformylation by a nonheme iron(II) complex, [Fe(II)(TMC)]2+, and molecular oxygen is reported as well.     

H-NMR studies of duplex DNA decamer containing a uracil cyclobutane dimer: implications regarding the high UV mutagenecity of CC photolesions

To determine the origin of the UV-specific CC to TT tandem mutation at the CC site, we made a duplex DNA decamer containing a uracil cis-syn cyclobutane dimer (CBD) as the deaminated model of a cytosine dimer. Two-dimensional 1H-NMR spectroscopy studies were performed on this sequence where two adenines (Ade) were opposite to the uracil dimer. Two imino protons of the uracil dimer were found to retain Watson-Crick hydrogen bonding with the opposite Ade, although the 5'-U(NH) of the dimer site showed unusual upfield shift like that of the 5'-T(NH) of the TT dimer, which seemed to be associated with deshielding by the flanking base rather than with reduced hydrogen bonding. (McAteer et al. 1998, J. Mol. Biol. 282:1013-1032). Hydrogen bondings at the dimer site were also supported by detecting typical strong nuclear Overhauser effects (NOE) between two imino protons and the opposite Ade H2 or NH2. But sequential NOE interactions of base protons with sugar protons were absent at the two flanking nucleotides of the 5' side of the uracil dimer and at the intradimer site, contrasting with its thymine analog where sequential NOE was absent only at the A4-T5 step. In addition, NOE cross peak for U5(NH) <--> A4(H2) was detected, although the NOE interactions of U6(NH) with A7(H2) and A17(H2) were not observed in contrast to the thymine dimer duplex. This different local structural alteration may be affected by the induced right-hand twisted puckering mode of cis-syn cyclobutane ring of the uracil dimer in the B-DNA duplex, even though the isolated uracil dimer had left-hand twisted puckering rigidly. In parallel, these observations may be correlated with observed differences in mutagenic properties between cis-syn UU dimer and cis-syn TT dimer.     

Studies on Chemical Constituents of Polygonum Ciliinerve Ohwi

Three new apianen lactones Maomailiaoine I ( 1 ), Maomailiaoine II ( 2 ) and Maoimaliaoine III ( 3 ), together with one known apianen lactone, five known flavonoids and three other known compounds were isolated from Polgonum ciliinerve Ohwi. Their structures were deduced from spectroscopic methods and 2D NMR techniques.     

Enhancement of facilitated olefin transport by amino acid in silver-polymer complex membranes

Silver ions dissolved in a polymer matrix are additionally coordinated by carbonyl oxygens of asparagines and their counter anions interact with cationic sites, resulting in the enhanced activity of the silver ion as an olefin carrier for facilitated olefin transport.     

Incorporation of quadruply-bonded units into solid-state materials

The thirtieth anniversary of the quadruple bond marks a time in science when synthetic inorganic chemists are exploring molecular routes to new solid-state materials. Dinuclear transition metal complexes possessing , , and components to their M-M bonding present exciting opportunities for the design of macromolecular compounds with interesting optical, electronic, and magnetic properties. This brief review reports recent progress in the area of ordered molecular arrays incorporating quadruply bonded and other multiply bonded M₂ units.