Reactions of phenyllithium with lithium aluminum hydride in diethyl ether

Reactions of phenyllithium with LiAlH₄ in diethyl ether have been studied in detail. Lithium hydride, as an insoluble solid, and LiAlPh_n H_4?n (where n = 2 or 3)_in solution, are formed when the PhLi to LiAlH₄ ratio is 2/1and 3/1. However, Li₃AlH₆ is formed when LiAlH₄ is added to an equimolar solution of PhLi in diethyl ether. The integrity of the products have been established by IR, NMR and X-ray powder diffraction pattern.     

Free vibrations of a beam-mass system with elastically restrained ends

The vibration problem of a beam with an arbitrarily placed concentrated mass and elastically restrained against rotation at either end is solved by using Laplace transforms. The effects on eigenfrequencies of the system produced by varying the ratios of the concentrated mass to the mass of the beam, stiffness of the end spring to the stiffness of the beam and position of the mass to the total length of the beam are presented. The effect of neglecting the mass of the beam is considered.     

Polarization studies by the TSC technique on a blend of cellulose acetate and polyvinyl acetate

The thermally stimulated current (TSC) technique has been used to study solvent-cast blends of a cellulose derivative with a vinyl polymer. TSC peaks are observed at 56, 80, and 120°C. Their origin is investigated because the TSC spectra of the blends differ from the spectra of the individual components. Data on blends with components in the weight ratios 25:75, 50:50, and 75:25 indicate that the 50:50 blend shows the greatest polarization. The enhancement of depolarization currents observed on blending is explained on the basis of a Maxwell–Wagner–Sillars polarization due to increased heterogeneity in the structure. Effects of forming conditions (time, temperature, field) on polarization have been investigated. Activation energies and relaxation times are calculated; there is good agreement between the values obtained from the initial-rise and the full-curve methods.     

Evidence for a single electron transfer mechanism in 1he reduction of aromatic nitrogen heterocycles with main group metal hydrides and dihydropyridyl metal complexes.

Direct spectroscopic (EPR) evidence is presented to support a single electron transfer mechanism to describe the reactions of various simple and complex hydrides of the main group elements and dihydropyridyl metal complexes with aromatic nitrogen heterocyclic compounds.     

High strain-rate behavior of ice under uniaxial compression

In the present study, a modified split Hopkinson pressure bar (SHPB) is employed to investigate the dynamic response of ice under uniaxial compression in the range of strain rates from 60 to 1400 s^?1 and at initial test temperatures of ?10 and ?30 °C. The compressive strength of ice shows positive strain-rate sensitivity over the range of strain rates employed; a slight influence of ice microstructure is observed, but it is much less than that reported previously for ice deformation under quasi-static loading conditions [Schulson, E.M., IIiescu, D., Frott, A., 2005. Characterization of ice for return-to-flight of the space shuttle. Part 1 – Hard ice. NASA CR-2005-213643-Part 1]. Specimen thickness, within the range studied, was found to have little or no effect on the peak (failure) strength of ice, while lowering the test temperature from ?10 to ?30 °C had a considerable effect, with ice behaving stronger at the lower test temperature. Moreover, unlike in the case of uniaxial quasi-static compression of ice, the effect of specimen end-constraint during the high rate compression was found to be negligible. One important result of these experiments, which may have important implications in modeling ice impacts, involves the post “peak-stress” behavior of the ice in that the ice samples do not catastrophically lose their load carrying capacity even after the attainment of peak stress during dynamic compression. This residual (tail) strength of the damaged/fragmented ice is sizable, and in some cases is larger than the quasi-static compression strength reported for ice. Moreover, this residual strength is observed to be dependent on sample thickness and the strain rate, being higher for thinner samples and at higher strain-rates during dynamic compression.     

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.     

A novel system for the synthesis of nitriles from aldehydes using aqueous ammonia and sodium dichloroiodate

A simple and mild method for the conversion of varieties of aldehydes to the corresponding nitriles using aqueous ammonia and aqueous sodium dichloroiodate reagent at room temperature is discussed. Advantages of this system are short reaction time, easy work-up and moderate to good yields.     

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.     

A highly effective synthesis of 2-alkynyl-7-azaindoles: Pd/C-mediated alkynylation of heteroaryl halides in water

The reaction of 4-chloro-2-iodo-7-azaindole with terminal alkynes was investigated using 10% Pd/C-PPh₃-CuI as a catalyst system in water. This study afforded a new, mild and selective process for the preparation of 2-alkynyl-4-chloro-7-azaindole in good yields via C-C bond forming reaction. The resulting chloro derivative can be functionalized further via another Pd-mediated C-C bond forming reaction with arylboronic acid.