BF3·Et2O promoted selective synthesis of benzimidazoles

Benzimidazoles 3 , 6 and 9 have been synthesized selectively in excellent yields by cyclocondensation of β‐(3‐methyl‐5‐styryl‐4‐isoxazolyl amido) benzoic acids, acrylic acids and propionic acids with 1,2‐phenylene diamines by employing BF₃·Et₂O as the catalyst. When the same reaction was carried out in pyridine it resulted in mixture of products in each case ( 3 & 4 , 6 & 7 and 9 & 10 ). Other methods tried by using polyphosphoric acid, HCl, TFA also led to mixtures of 3 & 4 , 6 & 7 and 9 & 10 in each case, similar to that of pyridine reaction.     

Solvation free energies calculated using the GB/SA model: Sensitivity of results on charge sets,protocols, and force fields

The sensitivity of aqueous solvation free energies (SFEs), estimated using the GB/SA continuum solvent model, on charge sets, protocols, and force fields, was studied. Simple energy calculations using the GB/SA solvent model were performed on 11 monofunctional organic compounds. Results indicate that calculated SFEs are strongly dependent on the charge sets. Charges derived from electrostatic potential fitting to high level ab initio wave functions using the CHELPG procedure and “class IV” charges from AM1/CM1a or PM3/CM1p calculations yielded better results than the corresponding Mulliken charges. Calculated SFEs were similar to MC/FEP energies obtained in the presence of explicit TIP4P water. Further improvements were obtained by using GVB/6-31G** and MP2/6-31+G** (CHELPG) charge sets that included correlation effects. SFEs calculated using charge sets assigned by the OPLSA* force field gave the best results of all standard force fields (MM2*, MM3*, MMFF, AMBER*, and OPLSA*) implemented in MacroModel. Comparison of relative and absolute SFEs computed using either the GB/SA continuum model or MC/FEP calculations in the presence of explicit TIP4P water showed that, in general, relative SFEs can be estimated with greater accuracy. A second set of 20 mono- and difunctional molecules was also studied and relative SFEs estimated using energy minimization and thermodynamic cycle perturbation (TCP) protocols. SFEs calculated from TCP calculations using the GB/SA model were sensitive to bond lengths of dummy bonds (i.e., bonds involving dummy atoms). In such cases, keeping the bond lengths of dummy bonds close to the corresponding bond lengths of the starting structures improved the agreement of TCP-calculated SFEs with energy minimization results. Overall, these results indicate that GB/SA solvation free energy estimates from simple energy minimization calculations are of similar accuracy and value to those obtained using more elaborate TCP protocols. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 769–780, 1998     

Scalar Tensor Cosmology With Kinetic,Gauss-Bonnet and Nonminimal Derivative Couplings and Supersymmetric Loop Corrected Potential

We discuss a particular four-dimensional cosmology based on non-minimal scalar tensor theories characterized by a supersymmetric loop corrected potential and a Hubble parameter defined as a function of the scalar field. Power-law solutions are obtained in the FRW background giving rise to acceleratedly expanding universe characterized by a scale factor and a scalar field depending both on the non-minimal coupling parameter $\xi$. Based on SNeIa data and on Hubble data X-ray gas mass fraction measurements, we find $0.116<\xi <0.225$ which results on a universe dominated by vacuum energy.     

Nonlocal approach to nonequilibrium thermodynamics and nonlocal heat diffusion processes

We study some aspects of nonequilibrium thermodynamics and heat diffusion processes based on Suykens’s nonlocal-in-time kinetic energy approach recently introduced in the literature. A number of properties and insights are obtained in particular the emergence of oscillating entropy and nonlocal diffusion equations which are relevant to a number of physical and engineering problems. Several features are obtained and discussed in details.     

Nanoplasmonic directional couplers and Mach–Zehnder interferometers

We present a novel design and analysis of two nano-scale plasmonic devices: a directional coupler and a Mach–Zehnder interferometer. The designs of the two devices are based on our recent work on the air-gap coupler that resulted in high coupling efficiency between a dielectric waveguide and a plasmonic waveguide. The two devices are embedded between two dielectric waveguides and operate at optical telecom wavelengths. The overall efficiency was 37% for a 2×2 directional coupler switch and above 50% for the proposed designs for a Mach–Zehnder Interferometer. The efficiency in the proposed devices can be increased using broader plasmonic waveguides.     

Fractional dynamics, fractional weak bosons masses and physics beyond the standard model

I discuss the possibility of manifestation of the ultralight Hubble mass in the Affleck–Dine mechanism and the time-variation of the gauge-coupling constant beyond the standard electroweak model. Exceedingly small correction to the standard theory in terms of “fractional weak boson mass” of the same order of magnitude the mass uncertainties found in the Particle Data Group tables is obtained and thus related to the space-time fractionality. The mathematics is based on fractional action-like variational problems recently introduced by the author that generalize the d’Alembertian operator of conventional quantum field theory.     

Trimerization of the HIV Transmembrane Domain in Lipid Bilayers Modulates Broadly Neutralizing Antibody Binding

The membrane‐proximal external region (MPER) of HIV gp41 is an established target of antibodies that neutralize a broad range of HIV isolates. To evaluate the role of the transmembrane (TM) domain, synthetic MPER‐derived peptides were incorporated into lipid nanoparticles using natural and designed TM domains, and antibody affinity was measured using immobilized and solution‐based techniques. Peptides incorporating the native HIV TM domain exhibit significantly stronger interactions with neutralizing antibodies than peptides with a monomeric TM domain. Furthermore, a peptide with a trimeric, three‐helix bundle TM domain recapitulates the binding profile of the native sequence. These studies suggest that neutralizing antibodies can bind the MPER when the TM domain is a three‐helix bundle and this presentation could influence the binding of neutralizing antibodies to the virus. Lipid‐bilayer presentation of viral antigens in Nanodiscs is a new platform for evaluating neutralizing antibodies.     

Piezoresistive fiber-reinforced composites: A coupled nonlinear micromechanical–microelectrical modeling approach

Piezoresistive composites are materials that exhibit spatial and effective electrical resistivity changes as a result of local mechanical deformations in their constituents. These materials have a wide array of applications from non-destructive evaluation to sensor technology. We propose a new coupled nonlinear micromechanical-microelectrical modeling framework for periodic heterogeneous media. These proposed micro-models enable the prediction of the effective piezoresistive properties along with the corresponding spatial distributions of local mechanical–electrical fields, such as stress, strain, current densities, and electrical potentials. To this end, the high fidelity generalized method of cells (HFGMC), originally developed for micromechanical analysis of composites, is extended for the micro-electrical modeling in order to predict their spatial field distributions and effective electrical properties. In both cases, the local displacement vector and electrical potential are expanded using quadratic polynomials in each subvolume (subcell). The equilibrium and charge conservations are satisfied in an average volumetric fashion. In addition, the continuity and periodicity of the displacements, tractions, electrical potential, and current are satisfied at the subcell interfaces on an average basis. Next, a one way coupling is established between the nonlinear mechanical and electrical effects, whereby the mechanical deformations affect the electrical conductivity in the fiber and/or matrix constituents. Incremental and total formulations are used to arrive at the proper nonlinear solution of the governing equations. The micro-electrical HFGMC is first verified by comparing the stand-alone electrical solution predictions with the finite element method for different doubly periodic composites. Next, the coupled HFGMC is calibrated and experimentally verified in order to examine the effective piezoresistivity of different composites. These include conductive polymeric matrices doped with carbon nano-tubes or particles. One advantage of the proposed nonlinear coupled micro-models is its ability to predict the local and effective electro-mechanical behaviors of multi-phase periodic composites with different conductive phases.     

Extended DLVO calculations expose the role of the structural nature of the adsorbent beads during chromatography

Protein adsorption onto hydrophobic interaction chromatography supports was studied by a surface-thermodynamics approach. To gather relevant experimental information, contact angle measurements and zeta potential determinations were performed on three different commercial adsorbent beads, Phenyl Sepharose 6 Fast Flow, Toyopearl Phenyl 650-C and Source 15 Phenyl, having soft to rigid backbone structure. Similar information was obtained for a collection of model proteins, lysozyme, bovine serum albumin (BSA), polygalacturonase, aminopeptidase, chymosin, aspartic protease, beta-galactosidase, human immunoglobulin G, and lactoferrin, were evaluated in the hydrated and in the dehydrated state. Based on the mentioned experimental data, calculations were performed to obtain the (interfacial) energy versus distance profiles of nine individual (model) proteins on (commercial) beads of three different types. All of these beads harbored the phenyl-ligand onto a matrix of differentiated chemical nature. Extended Derjaguin, Landau, Verwey, and Overbeek (DLVO) calculations were correlated with actual chromatographic behavior. Typical chromatography conditions were employed. The population of model proteins utilized in this study could be segregated into two groups, according to the minimum values observed for the resulting interaction energy pockets and the corresponding retention volumes (or times) during chromatography. Moreover, trends were also identified as a function of the type of adsorbent bead under consideration. This has revealed the influence of the physicochemical nature of the bead structure on the adsorption process and consequently, on the expected separation behavior.     

Spectroscopical splitting of Cu ion energy levels in magnesium lead fluoro silicate glasses

Homogeneous 40.0 MgO-(10-x) PbF₂-50.0 SiO₂: x CuO glasses were prepared using melt-quenching technique under controlled conditions. Spectroscopic studies (UV-vis absorption, ESR, FT-IR) are carried out for these glasses. One broad characteristic visible absorption band is observed around 700-850 nm in these glasses, the optical band gap decreases as the content of the CuO increases in the glass network up to 0.7 mol % then reversal trend is observed. ESR spectra of all these glasses show resonance peaks characteristic of Cu²⁺ ions and hyperfine splitting is resolved with increasing the CuO content in the glass network. From the observed ESR spectra, the spin-Hamiltonian parameters have been evaluated and indicate that Cu²⁺ ions have octahedral coordination with a strong tetragonal distortion in these glasses. By correlating ESR and optical absorption data, the molecular orbital coefficients have been evaluated. FT-IR spectra give important information about the nature of bonds in the glass matrix. The density of the glasses is also measured and is found to decrease with the increase CuO contents in the glass matrix. The physical parameters along with spectroscopic parameters are measured.