The self‐assembling zwitterionic form of L‐phenylalanine at neutral pH

The title zwitterion (2S)‐2‐azaniumyl‐1‐hydroxy‐3‐phenylpropan‐1‐olate, C₉H₁₁NO₂, also known as L‐phenylalanine, was characterized using synchrotron X‐rays. It crystallized in the monoclinic space group P2₁ with four molecules in the asymmetric unit. The 0.62 Å resolution structure is assumed to be closely related to the fibrillar form of phenylalanine, as observed by electron microscopy and electron diffraction. The structure exists in a zwitterionic form in which π–π stacking and hydrogen‐bonding interactions are believed to form the basis of the self‐assembling properties.     

Novel routes to epoxy functionalization of PHA‐based electrospun scaffolds as ways to improve cell adhesion

Straightforward and versatile routes to functionalize the surface of poly(3‐hydroxyalkanoate) (PHA) electrospun fibers for improving cell compatibility are reported under relatively mild conditions. The modification of nanofibrous PHAs is implemented through two different methodologies to introduce epoxy groups on the fiber surface: (1) preliminary chemical conversion of double bonds of unsaturated PHAs into epoxy groups, followed by electrospinning of epoxy‐functionalized PHAs blended with nonfunctionalized PHAs, (2) electrospinning of nonfunctionalized PHAs, followed by glycidyl methacrylate grafting polymerization under UV irradiation. The latter approach offers the advantage to generate a higher density of epoxy groups on the fiber surface. The successful modification is confirmed by ATR‐FTIR, Raman spectroscopy, and TGA measurements. Further, epoxy groups are chemically modified via the attachment of a peptide sequence such as Arg‐Gly‐Asp (RGD), to obtain biomimetic scaffolds. Human mesenchymal stromal cells exhibit a better adhesion on the latter scaffolds than that on nonfunctionalized PHA mats. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 816–824     

Perturbed Laguerre unitary ensembles,Hankel determinants,and information theory

This article investigates a key information‐theoretic performance metric in multiple‐antenna wireless communications, the so‐called outage probability. The article is partly a review, with the methodology based mainly on [10], while also presenting some new results. The outage probability may be expressed in terms of a moment generating function, which involves a Hankel determinant generated from a perturbed Laguerre weight. For this Hankel determinant, we present two separate integral representations, both involving solutions to certain non‐linear differential equations. In the second case, this is identified with a particular σ‐form of Painlevé V. As an alternative to the Painlevé V, we show that this second integral representation may also be expressed in terms of a non‐linear second order difference equation. Copyright © 2014 John Wiley & Sons, Ltd.     

Characterization of the drastic increase in molecular mobility of a deformed amorphous polymer

Original experiments of dynamic mechanical analysis and small angle x-ray scattering on a deformed amorphous polymer below its glass transition temperature are reported. The mechanical treatment reveals high mobility zones induced by shearing and leads to a drastic increase in the molecular mobility of the system. These domains are evidenced by small angle x-ray scattering measurements, and their geometrical characteristics are independent of the applied deformation. An experimental procedure is proposed to determine an apparent activation energy associated with high mobility domains. The energy values obtained for intermediate modes rise from the beta to the alpha relaxation ones.     

EFFECT OF VACUUM ENERGY ON THE ATOMIC SPECTRA

The effect of vacuum energy on the spectrum of atomic H is investigated using a Schrödinger equation and Higgs mechanism. It is shown that the effect of the latter is to decrease the energy level of the ground state of the H atom emitting energy in the process. This mechanism has been observed empirically in recently reported reproducible and repeatable experiments.     

Increasing the inhibitory potency of l-arabino-imidazolo-[1,2]-piperidinose towards β-d-glucosidase and β-d-galactosidase

The synthesis of some potent inhibitors of two retaining β-glycosidases was achieved by introducing aglycon-mimics into the imidazole moiety of l-arabino azasugar 1. The strongest inhibition was observed with the phenyl-ethyl substituent at C(2) of 1 against β-d-galactosidase and β-d-glucosidase, whereas the hydroxymethyl group at C(2) increased only slightly the inhibitory properties.     

Site-isolated porphyrin catalysts in imprinted polymers

A meso-tetraaryl ruthenium porphyrin complex having four polymerizable vinylbenzoxy groups (2) has been synthesized by reaction of pyrrole with 4-(vinylbenzoxy)benzaldehyde and subsequent metalation with [Ru3(CO)12]. The porphyrin complex was immobilized by copolymerization with ethylene glycol dimethacrylate. The resulting polymer P2 was found to catalyze the oxidation of alcohols and alkanes with 2,6-dichloropyridine N-oxide without activation by mineral acids. Under similar conditions, the homogeneous catalyst 2 was completely inefficient. By using diphenylaminomethane and 1-aminoadamantane as coordinatively bound templates during the polymerization procedure, the molecularly imprinted polymers P3 and P4 have been synthesized. Compared with the polymer P2, the imprinted catalysts displayed a significantly increased activity with rate enhancements of up to a factor of 16.     

Heat inhibited reactions

Acyl transfer from p-nitrophenyl trimethylacetate to hydrogen peroxide in millimolar aqueous solutions of an amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer slows down as the temperature is raised due to partitioning of the hydrophobic ester into heat-induced micelles.     

Cascade cyclization: an easy access to highly unsaturated polycyclic ring systems through a tandem stille/[4 + 2] reaction under mild conditions

The synthesis of several polycyclic compounds 1a-c, 2, and 3 has been performed through a tandem Stille/[4 + 2] cascade reaction from cyclic bis(enoltrifluomethanesulfonate) 4a-c, 5, and 6, respectively. The reaction proceeds very efficiently in a one-pot operation at roomtemperature in DMF in the presence of a catalytic amount of Pd(CH(3)CN)(2)Cl(2) and LiCl.[reaction: see text]     

Synthesis and esterolytic activity of catalytic peptide dendrimers

Peptide dendrimers were prepared by solid-phase peptide synthesis. Monomeric dendrimers were first obtained by assembly of a hexapeptide sequence containing alternate standard alpha-amino acids with diamino acids as branching units. The monomeric dendrimers were then dimerized by disulfide-bridge formation at the core cysteine. The synthetic strategy is compatible with functional amino acids and different diamino acid branching units. Peptide dendrimers composed of the catalytic triad amino acids histidine, aspartate, and serine catalyzed the hydrolysis of N-methylquinolinium salts when the histidine residues were placed at the outermost position. The dendrimer-catalyzed hydrolysis of 7-isobutyryl-N-methylquinolinium followed saturation kinetics with a rate constant of catalysis/rate constant without catalysis (k(cat)/k(uncat)) value of 3350 and a rate constant of catalysis/Michaelis constant (k(cat)/K(M)) value 350-fold larger than the second-order rate constant of the 4-methylimidazole-catalyzed reaction; this corresponds to a 40-fold rate enhancement per histidine side chain. Catalysis can be attributed to the presence of histidine residues at the surface of the dendrimers.