Substituent electronic effects on the persistence and absorption spectra of (Z)-o-xylylenols. A nanosecond laser flash photolysis study

[reaction: see text] A systematic investigation on a broad set of aldehydes reveals that the lifetimes of (Z)-photoenols can be modulated by variation of the substituents. We have found that the lifetimes of (Z)-enols (in benzene) can be varied by more than 1 order of magnitude with a judicious choice of the substituents that exert mesomeric and inductive effects as, for example, in the case of pentamethylbenzaldehyde (tau = 35 ns) and dicyanomesitaldehyde (tau = 760 ns). This study thus points to the fact that the electronic factors in conjunction with hydrogen bonding stabilization can considerably broaden the uni- as well as bimolecular chemistry based on photoenolization. Further, we have shown that the photoenols exhibit dramatic shifts in their absorption properties with variation of the substituents; although the photoenols have long been considered to be colored, their absorption properties have not been heretofore comprehensively examined.     

A General Vehicle Routing Problem

In this paper, we study a rich vehicle routing problem incorporating various complexities found in real-life applications. The General Vehicle Routing Problem (GVRP) is a combined load acceptance and generalised vehicle routing problem. Among the real-life requirements are time window restrictions, a heterogeneous vehicle fleet with different travel times, travel costs and capacity, multi-dimensional capacity constraints, order/vehicle compatibility constraints, orders with multiple pickup, delivery and service locations, different start and end locations for vehicles, and route restrictions for vehicles. The GVRP is highly constrained and the search space is likely to contain many solutions such that it is impossible to go from one solution to another using a single neighbourhood structure. Therefore, we propose iterative improvement approaches based on the idea of changing the neighbourhood structure during the search.     

An expedient protocol for conversion of olefins to α-bromo/iodoketones using IBX and NBS/NIS

A variety of olefins have been shown to undergo conversion to the corresponding α-bromo/iodoketones when reacted with NBS/NIS and IBX in DMSO at room temperature. While the reaction is found to occur rapidly with e-rich arylolefins leading to the corresponding haloketones in 65-95% yields in 0.3-3.0 h, those containing e-withdrawing groups are found to yield diketones concomitantly, such that the latter are the exclusive products over extended duration of the reactions.     

An efficient transient Navier–Stokes solver on compact nonuniform space grids

In this paper, we propose an implicit higher-order compact (HOC) finite difference scheme for solving the two-dimensional (2D) unsteady Navier–Stokes (N–S) equations on nonuniform space grids. This temporally second-order accurate scheme which requires no transformation from the physical to the computational plane is at least third-order accurate in space, which has been demonstrated with numerical experiments. It efficiently captures both transient and steady-state solutions of the N–S equations with Dirichlet as well as Neumann boundary conditions. The proposed scheme is likely to be very useful for the computation of transient viscous flows involving free and wall bounded shear layers which invariably contain spatial scale variation. Numerical results are presented and compared with analytical as well as established numerical data. Excellent comparison is obtained in all the cases.     

Rapid and accurate estimation of protein–ligand relative binding affinities using site-identification by ligand competitive saturation

Predicting relative protein–ligand binding affinities is a central pillar of lead optimization efforts in structure-based drug design. The site identification by ligand competitive saturation (SILCS) methodology is based on functional group affinity patterns in the form of free energy maps that may be used to compute protein–ligand binding poses and affinities. Presented are results obtained from the SILCS methodology for a set of eight target proteins as reported originally in Wang et al. (J. Am. Chem. Soc., 2015, 137, 2695–2703) using free energy perturbation (FEP) methods in conjunction with enhanced sampling and cycle closure corrections. These eight targets have been subsequently studied by many other authors to compare the efficacy of their method while comparing with the outcomes of Wang et al. In this work, we present results for a total of 407 ligands on the eight targets and include specific analysis on the subset of 199 ligands considered previously. Using the SILCS methodology we can achieve an average accuracy of up to 77% and 74% when considering the eight targets with their 199 and 407 ligands, respectively, for rank-ordering ligand affinities as calculated by the percent correct metric. This accuracy increases to 82% and 80%, respectively, when the SILCS atomic free energy contributions are optimized using a Bayesian Markov-chain Monte Carlo approach. We also report other metrics including Pearson''s correlation coefficient, Pearlman''s predictive index, mean unsigned error, and root mean square error for both sets of ligands. The results obtained for the 199 ligands are compared with the outcomes of Wang et al. and other published works. Overall, the SILCS methodology yields similar or better-quality predictions without a priori need for known ligand orientations in terms of the different metrics when compared to current FEP approaches with significant computational savings while additionally offering quantitative estimates of individual atomic contributions to binding free energies. These results further validate the SILCS methodology as an accurate, computationally efficient tool to support lead optimization and drug discovery.

Predicting relative protein–ligand binding affinities is a central pillar of lead optimization efforts in structure-based drug design.     

Nanoengineering of methylene blue loaded silica encapsulated magnetite nanospheres and nanocapsules for photodynamic therapy

Core–shell nanostructures have emerged as an important class of functional materials with potential applications in diverse fields, especially in health sciences. In this article, nanoengineering of novel magnetic colloidal dispersion containing surface modifiable silica with a core of single domain magnetite nanoparticles loaded with photosensitizer (PS) drug “Methylene blue” (MB) has been described. Magnetite core is produced by the well-established chemical coprecipitation technique and silica shell is formed over it by the modified hydrolysis and condensation of TEOS (tetraethyl orthosilicate). Conditions for reaction kinetics have been established to tailor the core–shell structures in the form of nanospheres and nanocapsules. MB is loaded into the nanostructures by demethylation reaction. The major conclusion drawn from this study is that the synthesis route yields stable, non-aggregated MB loaded superparamagnetic magnetite-silica nanostructures with tailored morphology, tunable loading, and excellent magnetic properties.     

Theoretical and Experimental Study of Long-Period Grating Refractive Index Sensor

Abstract

This article presents the theoretical and experimental investigation of the response of long-period gratings as a refractive index sensor. Cladding modes are calculated, and results are compared with Optigrating 4.2.2 (Optiwave Systems Inc., Ottawa, Canada). The response has been checked for refractive indices ranging from 1 to 1.458. Theoretically simulated results are in accordance with the experimental results. It was found that the software package calculated values correctly up to the seventh decimal point. The ambient refractive index response of a long-period grating over a much wider index range has been modeled for values both less and more than the cladding refractive index.     

SH-waves in viscoelastic heterogeneous layer over half-space with self-weight

The effect of gravity, heterogeneity and internal friction on propagation of SH-waves (horizontally polarised shear waves) in viscoelastic layer over a half-space has been studied. Using the method of separation of variables, dispersion equation has been obtained and used to recover the damped velocity of SH-waves. Both the real and imaginary parts of dispersion equation are in well agreement with the classical Love wave equation. It has been observed that heterogeneity of the medium affects the velocity profile of SH-wave significantly. Some other peculiarities have been observed and discussed in our study.     

Mesoscopic spin-dependent reflection experiments on InSb- and InAs-based heterostructures

Spin–orbit interaction in two-dimensional electron systems can lead to a spin-dependent reflection of carriers off a lithographic barrier. Scattering of a spin-unpolarized beam from the barrier leads to the creation of two fully spin-polarized side beams in addition to an unpolarized specularly reflected beam. We experimentally demonstrate a method to create spin-polarized beams of ballistic electrons in mesoscopic samples fabricated on InSb/InAlSb and InAs/AlGaSb heterostructures. We describe two geometries, one open and one closed, in which the spin-dependent reflection and spin-dependent semiclassical trajectories were observed.     

Radiation grafting of acrylonitrile on ethylene-propylene diene terpolymer rubber: Optimization of grafting parameters and oil resistance properties

Radiation induced grafting of acrylonitrile (ACN) on ethylene-propene diene terpolymer (EPDM) rubber film was investigated by mutual radiation grafting technique. Effect of experimental variables viz. radiation dose, dose rate, type of solvent and monomer content on extent of grafting was studied. From the kinetic studies a mathematical relation R _g α[M]^0.7 D ^0.68 showing non-linear relationship for rate of grafting with monomer concentration and dose was deduced. The grafted samples showed increased hardness and oil resistance.