Substrate flexibility of a 2,6-dideoxyglycosyltransferase

We report the first 2,6-dideoxysugar-O-glycosyltransferase with substrate flexibility at the 2 position, confirm the function of a putative NDP-hexose 2,3-dehydratase in the jadomycin B biosynthetic gene cluster and deduce the substrate flexibility of downstream enzymes in l-digitoxose assembly, enabling reprogramming of biosynthetic gene clusters to modify sugar substituents.     

Silver(I) 3-aminomethylpyridine complexes, part 2: effect of ligand ratio, hydrogen bonding, and pi-stacking with an interacting anion

Reaction of 3-aminomethylpyridine (3-amp) with silver(I) salts of triflate (OTf-) and trifluoroacetate (tfa-) produce a variety of multidimensional coordination networks whose structures depend on the stoichiometry of the components present. A 1:1 ratio of 3-amp to AgX produces a linear polymer, 1, when X = tfa- and a planar sheet, 2, when X = OTf-. Addition of a second equivalent of ligand increases the dimensionality of both structures by one to form a two-dimensional sheet, 3, and a three-dimensional system, 4, for their respective anions. Addition of 2,2'-bipyridine (bipy) to solutions of any of the previous compounds produces the fixed-ratio complexes 5 (tfa- salt) and 6 (OTf- salt). The bipyridyl ligand halts the polymerization of compounds 1-4 by cutting the chain after each silver(I) link and forcing a 1:2:2 ratio of 3-amp to AgX to bipy. Compound 5, however, remains polymeric in nature due to the closed-shell Ag-Ag interactions of the planar metals holding the monomers together. Differences between structures of each ratio stem from the differences in basicity and in the extra degree of H-bonding ability that the OTf- anion has over tfa-.     

FeCl3-Catalyzed aminohalogenation of arylmethylenecyclopropanes and arylvinylidenecyclopropanes and corresponding mechanistic studies

[reaction: see text] The aminochlorination of methylenecyclopropanes (MCPs) 1 and vinylidenecyclopropanes (VCPs) has been explored with use of FeCl(3) (20 mol %) as a Lewis acid catalyst in acetonitrile under convenient mild conditions. The stereochemistry has been unambiguously confirmed by X-ray structural analysis. The aziridinium-based mechanism, accounting for both regio- and stereoselectivity, has been carefully studied. A linear free-energy relationship study of this reaction confirms consistency with the Hammet equation.     

Star coloring planar graphs from small lists

A star coloring of a graph is a proper vertex‐coloring such that no path on four vertices is 2‐colored. We prove that the vertices of every planar graph of girth 6 (respectively 7, 8) can be star colored from lists of size 8 (respectively 7, 6). We give an example of a planar graph of girth 5 that requires 6 colors to star color. © 2009 Wiley Periodicals, Inc. J Graph Theory 63: 324–337, 2010     

Preparation of nanocomposites by reversible addition‐fragmentation chain transfer polymerization from the surface of quantum dots in miniemulsion

Herein, we report the synthesis of quantum dots (QDs)/polymer nanocomposites by reversible addition‐fragmentation chain transfer (RAFT) polymerization in miniemulsions using a grafting from approach. First, the surfaces of CdS and CdSe QDs were functionalized using a chain transfer agent, a trisalkylphosphine oxide incorporating 4‐cyano‐4‐(thiobenzoylsulfanyl)pentanoic acid moieties. Using a free radical initiator (AIBN) to activate the RAFT process, a polystyrene (PS) block was grafted from the surface of the QDs. Quantum confinement effects were identified for the nanocomposite obtained, so attesting to the integrity of the QDs after the polymerization. Free PS chains were also present in the final nanocomposite, indicating that the RAFT polymerization from the surface of the QDs was accompanied by conventional free radical polymerization. After isolating the nanocomposite particles, a second poly(n‐butyl acrylate) block was tentatively grown from the initial PS block. The first results indicated a successful polymerization of the second polymer and show the potential of the current strategy to prepare block copolymers from the surface of the RAFT‐modified QDs. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5367–5377, 2009     

Exponential absorption edge in hydrogenated α-Si films

Optical and photoelectric measurements demonstrate that hydrogenated amorphous silicon prepared by glow discharge decomposition of silane has an exponential optical absorption edge, over the photon energy range 1.4–1.8 eV with a slope of 0.05–0.08 eV. Evidence is presented that the photogeneration efficiency is unity at room temperature and independent of electric field (10²?10⁴ V/cm^?1) and photon energy (1.2–2.2 eV).     

Vibrational spectra of crystalline H2SeO3 in the O-H stretching region

IR transmission, near-normal IR reflection and polarized Raman spectra of single crystals of selenious acid (H₂SeO₃) have been obtained at temperatures between 77°K and 335°K. The observed bands in the O-H stretching region have been assigned to two types of O-H….O bonds in the crystal structure. The spectral results appear to rule out correlation field splittings, intramolecular coupling, or Fermi resonance as explanations for the observed splitting. A proposed model based on intermolecular coupling of O-H….O vibrations to explain the splitting of the O-H stretching region is given.