Vibrational analysis of the H5O2+ infrared spectrum using molecular and driven molecular dynamics

Standard molecular and driven molecular dynamics are used to analyze prominent spectral features in the H5O2+ infrared spectrum. In the driven method, the molecular Hamiltonian is augmented with a time-dependent term, mu x epsilon(0) sin(omegat), where mu is the dipole moment of H5O2+, epsilon0 is the electric field, and omega is the frequency. The magnitude of the electric field determines whether the driving is mild (the harmonic limit) or strong (anharmonic motion and mode coupling). We analyze the spectrum in the wavenumber range from 600 to 1900 cm(-1), where recent experimental measurements are available for H5O2+. On the basis of the simulations, we have assigned the broad feature around 1000 cm(-1) to the proton transfer coupled with the torsion motion. Intense absorption near 1780 cm(-1) is assigned to the H2O monomer bend coupled with proton transfer.     

A Comprehensive Kinetic Model of Free‐Radical‐Mediated Interfacial Polymerization

A mathematical model describing interfacial radical polymerization‐based film formation on hydrogels is elucidated. A glucose oxidase‐mediated multistage initiation reaction is used to accomplish interfacial film formation. A polymer concentration‐dependent diffusion coefficient is used to reflect the changing mass transport conditions as the film develops. Model predictions of the film thickness as a function of the species concentrations agree well with experiments. The model predicts that the degree of initiation reaction delocalization with the enzyme‐mediated initiation system is significantly higher than an enzyme‐independent system, thus affecting the film growth rate and structure. The mass transport properties of the film and its adhesion to the underlying substrate are also investigated.

     

Gas Chromatographic-mass Spectrometric Analysis Of Methaqualone,Phendimetrazine And Phenmetrazine

Gas chromatographic - mass spectrometric techniques are gaining acceptance as a tool for drug identification. Standard techniques for the analysis of street drugs are still based upon infrared and ultraviolet spetra in conjunction with specific chemical test. These standard methods are adequate for the identification of a majority of confiscated drugs; but due to the increasing diversification of street drugs, these methods are becoming less conclusive.     

On the global attractor of 2D incompressible turbulence with random forcing

This study revisits bounds on the projection of the global attractor in the energy–enstrophy plane for 2D incompressible turbulence [Dascaliuc, Foias, and Jolly, 2005, 2010]. In addition to providing more elegant proofs of some of the required nonlinear identities, the treatment is extended from the case of constant forcing to the more realistic case of random forcing. Numerical simulations in particular often use a stochastic white-noise forcing to achieve a prescribed mean energy injection rate. The analytical bounds are demonstrated numerically for the case of white-noise forcing.     

Convergence of folding free energy landscapes via application of enhanced sampling methods in a distributed computing environment

We have implemented the serial replica exchange method (SREM) and simulated tempering (ST) enhanced sampling algorithms in a global distributed computing environment. Here we examine the helix-coil transition of a 21 residue alpha-helical peptide in explicit solvent. For ST, we demonstrate the efficacy of a new method for determining initial weights allowing the system to perform a random walk in temperature space based on short trial simulations. These weights are updated throughout the production simulation by an adaptive weighting method. We give a detailed comparison of SREM, ST, as well as standard MD and find that SREM and ST give equivalent results in reasonable agreement with experimental data. In addition, we find that both enhanced sampling methods are much more efficient than standard MD simulations. The melting temperature of the Fs peptide with the AMBER99phi potential was calculated to be about 310 K, which is in reasonable agreement with the experimental value of 334 K. We also discuss other temperature dependent properties of the helix-coil transition. Although ST has certain advantages over SREM, both SREM and ST are shown to be powerful methods via distributed computing and will be applied extensively in future studies of complex bimolecular systems.     

Synthesis using aromatic homolytic substitution--recent advances

This critical review aims at presenting recent developments in intramolecular aromatic homolytic substitution which has become one of the common methodologies in modern synthesis. The application of Bu3SnH-mediated cyclisations have proved especially useful. The critical review illustrates the mechanistic considerations required for planning synthetic applications and a wide range of synthetic protocols and natural product syntheses are shown. The latest evidence for the mechanisms involved in aromatic homolytic substitution are presented. (152 references).     

Continued fractions with multiple limits

For integers m2, we study divergent continued fractions whose numerators and denominators in each of the m arithmetic progressions modulo m converge. Special cases give, among other things, an infinite sequence of divergence theorems, the first of which is the classical Stern–Stolz theorem.We give a theorem on a class of Poincaré-type recurrences which shows that they tend to limits when the limits are taken in residue classes and the roots of their characteristic polynomials are distinct roots of unity.We also generalize a curious q-continued fraction of Ramanujan's with three limits to a continued fraction with k distinct limit points, k2. The k limits are evaluated in terms of ratios of certain q-series.Finally, we show how to use Daniel Bernoulli's continued fraction in an elementary way to create analytic continued fractions with m limit points, for any positive integer m2.