Structural and dynamical aspects of alkylammonium salts of a silicodecatungstate as heterogeneous epoxidation catalysts

The structural and dynamical aspects of alkylammonium salts of a silicodecatungstate [(CH(3))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C1], [(n-C(3)H(7))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C3], [(n-C(4)H(9))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C4], and [(n-C(5)H(11))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C5] were investigated. The results of sorption isotherms, XRD analyses, and solid-state NMR spectroscopy show that facile sorption of solvent molecules, flexibility of structures, and high mobility of alkylammonium cations are crucial to the uniform distribution of reactant and oxidant molecules throughout the bulk solid, which are related to the high catalytic activities for epoxidation of alkenes.     

Elucidation of the Active Conformation of Vancomycin Dimers with Antibacterial Activity against Vancomycin‐Resistant Bacteria

Covalently linked vancomycin dimers have attracted a great deal of attention among researchers because of their enhanced antibacterial activity against vancomycin‐resistant strains. However, the lack of a clear insight into the mechanisms of action of these dimers hampers rational optimization of their antibacterial potency. Here, we describe the synthesis and antibacterial activity of novel vancomycin dimers with a constrained molecular conformation achieved by two tethers between vancomycin units. Conformational restriction is a useful strategy for studying the relationship between the molecular topology and biological activity of compounds. In this study, two vancomycin units were linked at three distinct positions of the glycopeptide (vancosamine residue (V), C terminus (C), and N terminus (N)) to form two types of novel vancomycin cyclic dimers. Active NC‐VV‐linked dimers with a stable conformation as indicated by molecular mechanics calculations selectively suppressed the peptidoglycan polymerization reaction of vancomycin‐resistant Staphylococcus aureus in vitro. In addition, double‐disk diffusion tests indicated that the antibacterial activity of these dimers against vancomycin‐resistant enterococci might arise from the inhibition of enzymes responsible for peptidoglycan polymerization. These findings provide a new insight into the biological targets of vancomycin dimers and the conformational requirements for efficient antibacterial activity against vancomycin‐resistant strains.     

Chemoenzymatic synthesis of uridine diphosphate-GlcNAc and uridine diphosphate-GalNAc analogs for the preparation of unnatural glycosaminoglycans

Eight N-acetylglucosamine-1-phosphate and N-acetylgalactosamine-1-phosphate analogs have been synthesized chemically and were tested for their recognition by the GlmU uridyltransferase enzyme. Among these, only substrates that have an amide linkage to the C-2 nitrogen were transferred by GlmU to afford their corresponding uridine diphosphate(UDP)-sugar nucleotides. Resin-immobilized GlmU showed comparable activity to nonimmobilized GlmU and provides a more facile final step in the synthesis of an unnatural UDP-donor. The synthesized unnatural UDP-donors were tested for their activity as substrates for glycosyltransferases in the preparation of unnatural glycosaminoglycans in vitro. A subset of these analogs was useful as donors, increasing the synthetic repertoire for these medically important polysaccharides.     

Sensitivity and randomness in homogenization of periodic fiber-reinforced composites via the response function method

The main issue this paper addresses is the derivation and implementation of a general homogenization method, including the simultaneous determination of sensitivity gradients and probabilistic moments of the effective elasticity tensor. This is possible with an application of the perturbation method based on Taylor expansion and with the effective modules method. The computational procedure is implemented using plane strain analysis carried out with the finite element method (program MCCEFF) and the symbolic computations system MAPLE. The sensitivity gradients and probabilistic moments are commonly determined on the basis of partial derivatives for the homogenized elasticity tensor, calculated using the response function method with respect to some composite parameters. They are subjected separately to a normalization procedure (in deterministic analysis) and the relevant algebraic combinations (for the stochastic case). This enriched homogenization procedure is tested on a periodic fiber-reinforced two component composite, where the material parameters are taken as design variables and then, the input random quantities. The results of computational analysis are compared against the results of the central finite difference approach in the case of sensitivity gradients determination as well as the direct Monte-Carlo simulation approach. This numerical methodology may be further applied not only in the context of the homogenization method, but also to extend various discrete computational techniques, such as Boundary/Finite element and finite difference together with various meshless methods.     

Photoemission from solid surfaces in intense laser fields

We present a Floquet analysis of photoemission of electrons from a solid surface due to its interaction with a laser beam. The method we use is based on a three-dimensional quasifree electron model. The model takes account of the changes in the effective mass of the electron inside and outside the solid and in the reflected and refracted beams due to the presence of the surface. It is shown that the photoemission of electrons from the solid surface may take place not only with no absorption of photons but also along with the emission of extra photons.     

Corrigendum to “Convexity and concavity constants in Lorentz and Marcinkiewicz spaces” [J. Math. Anal. Appl. 343 (2008) 337-351]

In this note we state the accurate formulas of convexity and concavity constants in Lorentz spaces, correcting the formulas from Kamińska and Parrish (2008) [2].     

Circularly polarized luminescence (CPL) characteristics of hydrophobic pyrene derivatives/γ-cyclodextrin (γ-CD) complexes in aqueous solution dissolved by grinding

Circularly polarized luminescence (CPL) organic dyes are currently receiving a great interest, but there are still not many reported observations of CPL spectra of hydrophobic dyes from aqueous solution. We have prepared hydrophobic pyrene derivatives and dissolved them into aqueous solutions with γ-cyclodextrin (γ-CD) by using grinding technique. Among these derivatives, (pyrene-1-carbonyl)serine (PySer) forms a spatially restricted dimer in the hydrophobic chiral cavity of γ-CD and exhibits excimer emission with a high quantum yield of Φ_f?=?0.68. In addition, circular dichroism and CPL signals were induced for the complex. The strong g_CPL value of g_CPL?=?+?2.2?×?10^?3 was obtained, which may be attributed to the interaction between the hydroxyl groups in the side chain of PySer with those of γ-CD and it strengthens the chiral dimeric structure.

Graphic abstract

     

Water sorption,glass transition,and freeze-concentrated glass-like transition properties of calcium maltobionate–maltose mixtures

Journal of Thermal Analysis and Calorimetry - The water sorption, glass transition, and freeze-concentrated thermal transition properties of calcium maltobionate (MBCa)–maltose mixtures were...     

Properties of a special class of doubly stochastic measures

Summary A measure on the unit squareI } I is doubly stochastic if(A } I) = (I } A) = the Lebesgue measure ofA for every Lebesgue measurable subsetA ofI = [0, 1]. By the hairpinL L ^–1, we mean the union of the graphs of an increasing homeomorphismL onI and its inverseL ^–1. By the latticework hairpin generated by a sequence {x _n :n Z} such thatx _n-1 < x_n (n Z), x _n = 0 and x _n = 1, we mean the hairpinL L ^–1 , whereL is linear on [x _n-1 ,x _n ] andL(n) =x _n-1 forn Z. In this note, a characterization of latticework hairpins which support doubly stochastic measures is given. This allows one to construct a variety of concrete examples of such measures. In particular, examples are given, disproving J. H. B. Kemperman's conjecture concerning a certain condition for the existence of doubly stochastic measures supported in hairpins.     

Synthesis of [6]helicene-based sulfonic acid,sulfonamide, and disulfonimides

The synthesis of helically chiral [6]helicene-based sulfonic acid and sulfonamide from enantiomerically pure 1-acetylthio-5,6,9,10-tetrahydro[6]helicene is reported. The first helically chiral disulfonimides were developed as a synthetic application of [6]helicene-based sulfonamide. This new class of organocatalysts was tested in an asymmetric Mukaiyama aldol reaction to obtain up to quantitative yields and enantioselectivities up to 24%.