An Efficient Low‐Temperature Stille–Migita Cross‐Coupling Reaction for Heteroaromatic Compounds by Pd–PEPPSI–IPent

The reactivity of Pd–PEPPSI (Pyridine, Enhanced, Precatalyst, Preparation, Stabilization, and Initiation) precatalysts in the Stille–Migita cross‐coupling reaction between heteroaryl stannanes and aryl or heteroaryl halides was evaluated. In general, Pd–PEPPSI–IPent (IPent=diisopentylphenylimidazolium derivative) demonstrated high efficiency over a variety of challenging aryl or heteroaryl halides with thiophene‐, furan‐, pyrrole‐, and thiazole‐based organostannanes when compared with Pd–PEPPSI–IPr (IPr=diisopropylphenylimidazolium derivative). The transformations proceeded at appreciably lower temperatures (30–80 °C) than triarylphosphine‐based Pd catalysts, improving the scope of this useful carbon–carbon bond‐forming process.     

Dislocation structure and microhardness of L-arginine perchlorate single crystal

This paper presents the chemical etching and microhardness studies carried out on L-arginine perchlorate (LAPCl), a non-linear optical crystal (NLO) with a view to characterize the dislocation structure and mechanical strength of the grown crystals. LAPCl crystals employed in this investigation were grown from aqueous solution by solvent evaporation method. Optical microscopic studies of as grown habit faces revealed formation of macrosteps and valley on (100) habit face. Chemical etching of (100) face with impurity added organic solvents played an important role in the formation of etch pits. Selective etching of matched pairs on opposite faces of the same plane confirms that the pits are formed at the dislocation sites. Microhardness measurement by indentation method shows decrease of microhardness with increasing load. Nature of hardness profile is explained with the help of Meyer’s law. The work hardening index value indicates that LAPCl belongs to hard crystal category.     

Improvement of damping characteristics of structural members with high damping elastic inserts

The major objective of this work is to investigate theoretically the possibility of improving the damping capacities of structural members with the help of inserts of special high damping materials. The inserts have been considered to be both welded and press-fit to the members. It has been observed that the effectiveness of the press-fit inserts is much more than that of the welded inserts. In case of the welded inserts there exists an optimum size whereas for shrink-fit inserts best results are expected when the inserts are solid. It has been found that with such a method the damping capacity of a member can be considerably increased with no significant loss in static rigidity.     

Methoxy-mercuration of methacrylic and cinnamic esters and cinnamaldehyde

The methoxymercuration of methyl and ethyl methacrylates, ethyl cinnamate and cinnamaldehyde has been kinetecally studied in the temperature range 35°–50°. Second-order kinetics has been observed for the over-all reaction. In all the cases, the reaction is appreciably accelerated by acetic acid and strongly retarded by sodium acetated and nitrogen bases. The results indicate an ionic mechanism involving a reactive carbonium ion as an intermediate formed by interaction between the unsaturated compound and undissociated mercuric acetate.     

Transport of excitation energy in a three-dimensional doped molecular crystal. IV. Fourth-order propagation,exciton clothing,and exciton diffusion

The problem of excitons in interaction with phonons in a molecular crystal has been reinvestigated as a continuation of our earlier work. The exciton-phonon interaction has been taken to be linear in lattice displacements. The external medium, the phonon assembly, has been considered to be in thermal equilibrium. Following Simons, we have incorporated the effects of the medium on the exciton dynamics into a time-dependent effective potential that contains the equilibrium average exciton-phonon interaction as well as terms arising from the fluctuations in the medium's coordinates about their equilibrium values. A correlation function that represents the probability of exciton transfer has been given in the interaction picture. The time evolution of this correlation function has been determined by following Kubo's technique of cumulant expansion. The zeroth-, second-, and fourth-order contributions to the correlation function have been calculated in this way. The second- and fourth-order contributions have been diagrammatically represented. The second-order contribution has been explicitly calculated in different physical limits, namely, the slow exciton and the slow phonon limits at high and low temperatures and for very large and very small time. A few simple formulas for the transfer probability of a bare exciton in a molecular crystal of cubic symmetry have been derived from the Debye approximation for the dispersion of phonons. It has been specifically shown that the sum over phonon modes in the large time dynamics leads to a fully destructive interference in second order at a very low temperature and gives rise to a diffusive transport at a high enough temperature. A natural way of clothing the excitons has been considered and the clothed exciton has been represented diagrammatically. The dressing requires the correlation function to be redefined in terms of the clothed states and the clothed operators. The clothed exciton correlation function that represents the probability of transfer of excitons fully clothed by the phonons in thermal equilibrium turns out to be identical with the bare exciton correlation function. This attaches a novel interpretation to the correlation function which was originally defined by Simons. Transfer probabilities for a clothed exciton in a cubic crystal has been explicitly worked out for different physical limits under the Debye model of phonon dispersion. From these results a few expressions for the macroscopic diffusion coefficient of the clothed exciton have been obtained. A few critical comments have been incorporated. © 1996 John Wiley & Sons, Inc.     

Transfer of excitation energy in a three-dimensional-doped molecular crystal. V. Self-consistency of the temporal processes involved in energy transfer in photosynthetic units

Numerical experiments were carried out to determine the timewise self-consistency of different physical processes involved in the energy transfer in green plant photosynthetic units. A 6 × 6 × 6 array of chlorophyll-a with cubic lattice constants a = b = c = 20 Å was chosen as a model of the thylakoid disc. Another model aggregate was obtained by substituting chlorophyll-b molecules for some of the chlorophyll-a molecules. In both models, a reaction center occupied a central site in the last xy plane. Two extreme arrangements were considered for the orientation of molecules. In one, the transition moments of all molecules were directed along the y-axis. The other had chlorophyll molecules randomly oriented. The four resulting model systems were used in our investigation on exciton generation, transport, decay by fluorescence, and trapping. All excitons were assumed to be generated by a 20 ms exposure to sunlight at high altitudes. The general trends noticed from these computations are as follows: The number of excitons generated is influenced by lattice disorders. Disorders also increase the time for the establishment of an equilibrium distribution. The decay of excitons by fluorescence is always a monotonic function of time. The energy transfer is adversely affected by a lower degree of orientation in the crystal: The trapping time increases with disorder. The number of trappings decreases with the onset of fluorescence of the host molecules and the trap. From these investigations, we also made three specific observations: (1) The efficiency of exciton utilization varies from 12% for a completely random arrangement of transition dipoles to 46% for a perfectly ordered arrangement. This agrees with the experimental efficiency, about 20%. (2) The number of excitons trapped varies from one to six. This tallies with the time scale of electron transfer along the Z-scheme that requires at least two excitons trapped in about 20 ms. Thus, the photon density and the exciton transfer rate are consistent with the rates of electron transfers. (3) The trapping rate also indicates that the thylakoid disc must resemble a considerably ordered system. © 1996 John Wiley & Sons, Inc.     

The Synthesis of Warfarin Using a Reconfigurable-Reactor Platform Integrated to a Multiple-Variable Optimization Tool

Optimization of the asymmetric synthesis of warfarin, an important anticoagulant, has been evaluated using a reconfigurable reaction platform capable of performing batch, continuous flow, and plug-flow synthesis. Further, this platform has been integrated with a novel, multidimensional, multiple variable analysis tool that can evaluate multiple critical quality attributes (CQA), percent conversion and enantiomeric excess in this case, from a single injection that is repeatedly recycled in a closed loop of chromatography columns, a detector and a heart-cut valve. Further, the new, integrated analysis system also facilitates validation of each QA, providing a high-level of confidence in analytical measurements, which are obtained without operator intervention.     

Preparation of high‐selective HPLC packing materials based on alternating copolymer‐grafted silica

Three alternating copolymer‐grafted silica stationary phases for use in high‐selective RP‐HPLC were prepared from two vinyl monomers selected from styrene, N‐methylmaleimide, N‐octadecylmaleimide, and octadecyl acrylate; they were characterized by elemental analyses, thermogravimetric analysis, diffuse reflectance infrared Fourier transform spectroscopy, and ¹³C cross‐polarization magic‐angle spinning NMR spectroscopy. Aspects of molecular‐shape selectivity were evaluated for three different columns using Standard Reference Material 869b, Column Selectivity Test Mixture for Liquid Chromatography. The best selectivity for isomer separations was obtained for the stationary phase prepared with a copolymer of octadecyl acrylate and N‐octadecylmaleimide, which was able to separate 16 polycyclic aromatic hydrocarbons (Standard Reference Material 1647e) in an isocratic elution. In this paper, the effectiveness of this phase is also demonstrated by separation of tocopherol isomers.