Highly regio- and stereoselective asymmetric bromoazidation of chiral alpha,beta-unsaturated carboxylic acid derivatives: scope and limitations

Lewis acid catalyzed asymmetric bromoazidation of chiral alpha,beta-unsaturated carboxylic acid derivatives was performed using N-bromosuccinimide (NBS) and trimethylsilyl azide (TMSN3) as the bromine and azide sources. Among the Lewis acids, Yb(OTf)3 was found to be the best catalyst. Regio- and anti-selectivity of 100% and moderate to good diastereoselectivity (up to 89:11) with good yields were obtained when Oppolzer's bornane sultam chiral auxilairy was used. Diastereoselectivity of >95:05 was observed when (2S,5S)-2,5-diphenylpyrrolidine was used as the chiral auxiliary.     

13-Nuclear Magnetic Resonance Studies of Polyetherurethaneureas

A series of linear polyurethaneureas was prepared by a two-step solution polymerization method. The prepolymer formed by the reaction of 4,4′-diphenyl methane diisocyanate with polyethylene glycol/polypropylene glycol was further chain extended with ethylene diamine/propane diamine/hexane diamine. The chemical shift values of various carbon species of the block copolymer were analyzed and assigned. The products formed due to the presence of water at different stages of polymerization were also characterized.     

Multi-instrument characterization of HiPIMS and DC magnetron sputtered tungsten and copper films

In this work, copper and tungsten were sputtered onto silicon wafers by direct current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HiPIMS). The resulting films were characterized by energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and X-ray diffraction (XRD). By EDX and XPS, all the sputtered films showed only the expected metal peaks. By XPS, the surfaces sputtered by DCMS were richer in oxygen than those produced by HiPIMS. By AFM, the surfaces were quite smooth. The root mean square (RMS) roughness values are as follows: 0.83 nm (W, HiPIMS), 1.10 nm (W, DCMS), 0.85 nm (Cu, HiPIMS), and 1.78 nm (Cu, DCMS). By SEM, the HiPIMS films exhibited smaller grain sizes, which was confirmed by XRD. The crystallite sizes estimated by XRD are as follows: 4 nm (W, body-centered cubic, HiPIMS), 13 nm (W, body-centered cubic, DCMS), 7 nm (W, cubic, HiPIMS), 14 nm (W, cubic, DCMS), 25 nm (Cu, HiPIMS), and 35 nm (Cu, DCMS). By SE, the HiPIMS surfaces showed higher refractive indices, which suggested that they were denser and less oxidized than the DCMS surfaces.     

Thermomechanical transitions in doubly-clamped micro-oscillators

The small size and low damping of MEMS oscillators give rise to phenomena that are not observed routinely at the macroscopic scale. In this work we document and explain an experimentally observed transition in the response of a doubly clamped micromechanical oscillator with pretension. The transition from softening to hardening is repeatedly observed upon increasing the power of an incident sensing laser beam, a procedure routinely used to improve signal strength during optical detection of resonant motion of microstructures. At intermediate laser power, a novel resonant response that displays characteristics of both softening and hardening in the same sweep, is observed experimentally. Increased laser heating of a structure in tension may be expected to increase softening behavior. Using tools from non-linear dynamics and continuum mechanics, we show that the observed counter-intuitive behavior can be explained by a competition between the opposing responses of linear and non-linear stiffnesses to a change in temperature.     

Influence of number of functional groups of hyperbranched polyol on cure kinetics and physical properties of polyurethanes

Curing of polyurethane prepolymer with three hyperbranched polyol was studied using FTIR spectroscopy. The disappearance of the strong isocyanate absorption peak was followed with time and temperature to determine the reaction kinetics. It was shown that all the hyperbranched polyols followed the second order kinetic equation and the reaction rate enhanced with increase in the number of the functional groups of the hyperbranched polyol. Activation energy, activation enthalpy, and activation entropy were also measured. The swelling character of the polyurethanes was investigated with the help of gel fraction, degree of crosslinking, and average molecular weight between crosslinks. Atomic force microscopy indicated phase separated morphology of the cured polyurethanes. The thermal, mechanical, and thermomechanical properties were enhanced when the number of the functional groups in the hyperbranched polyols was increased. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 731–745, 2009     

Rapid upregulation of cytoprotective nitric oxide in breast tumor cells subjected to a photodynamic therapy-like oxidative challenge

Many tumor cells produce nitric oxide (NO) as an antiapoptotic/progrowth molecule which also promotes antiogenesis and tumor expansion. This study was designed to examine possible antagonistic effects of endogenous NO on tumor eradication by photodynamic therapy (PDT). Using COH-BR1 breast cancer cells sensitized in mitochondria with 5-aminolevulinic acid (ALA)-generated protoporphyrin IX as a model for ALA-based PDT, we found that caspase-9 activation and apoptotic death following irradiation were strongly enhanced by 1400W, an inhibitor of inducible nitric oxide synthase (iNOS). RT-PCR and Western analyses revealed a substantial upregulation of both iNOS mRNA and protein, beginning ca 4 h after irradiation and persisting for at least 20 h. Accompanying this was a strong 1400W-inhibitable increase in intracellular NO, as detected with the NO probe, DAF-2-DA. Short hairpin RNA-based iNOS knockdown in COH-BR1 cells dramatically reduced NO production under photostress while enhancing caspase-9 activation and apoptosis. These findings suggest that cytoprotective iNOS/NO induction in PDT-treated tumor cells could reduce treatment efficacy, and point to pharmacologic intervention with iNOS inhibitors for counteracting this.     

Surface modification of argon/oxygen plasma treated vulcanized ethylene propylene diene polymethylene surfaces for improved adhesion with natural rubber

Vulcanized ethylene propylene diene polymethylene (EPDM) rubber surface was treated in a radio frequency capacitatively coupled low pressure argon/oxygen plasma to improve adhesion with compounded natural rubber (NR) during co-vulcanization. The plasma modified surfaces were analyzed by means of contact angle measurement, surface energy, attenuated total reflection-infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, energy dispersive X-ray sulfur mapping and atomic force microscopy. Several experimental variables such as plasma power, length of exposure time and composition of the argon-oxygen gas mixture were considered. It was delineated that plasma treatment changed both surface composition and roughness, and consequently increased peel strength. The change in surface composition was mainly ascribed to the formation of C-O and -CO functional groups on the vulcanized surfaces. A maximum of 98% improvement in peel strength was observed after plasma treatment.     

On generalized cluster sets of functions and multifunctions

This paper introduces and studies generalized cluster sets (g-cluster sets) of functions and multifunctions on GTS, which unifies the existing notions of cluster sets, θ-cluster sets, δ-cluster sets, S-cluster sets, s-cluster sets, p-cluster sets and many more. Several properties of the functions and multifunctions as well as their range and domain spaces are observed via degeneracies of their g-cluster sets. Characterizations of g-cluster sets through filterbases and grills on a typical class of GTS’s are also obtained. Moreover, μ-compactness of a GTS is characterized through g-cluster sets of multifunctions.     

Spin-Crossover Assisted Spin-Switching and Rectification Action in Half-Metallic Graphitic Carbon Nitride(g-C4N3)

Herein, we report on the potential multifunctional spintronic action of half-metallic graphitic carbon nitride (g-C₄N₃). We observed electrostatic spin-crossover action at an applied electric field of −0.77 V nm⁻¹, which eventually leads to spin-switching action and change in sign of bias dependent spin injection coefficient. The system also acts as a spin polarized charge current rectifier with rectification ratio of 65.41 in spin-up channel only. This electric field-controlled spin switching action and simultaneous existence of rectification action makes graphitic carbon nitride a perfect multifunctional spintronic system-an ideal material for quantum logic gate design. Results obtained have been substantiated through transmission spectra and transmission pathways analyses. An analysis of projected device density of states of the system and molecular projected self consistent Hamiltonian states analysis reveals that the electron flow of the system is mainly facilitated by 2p orbitals of C and N atoms.