Ab initio SCF calculations on [V10O28]6−: A benchmark for the classical calculation and processing of molecular integrals on large Gaussian basis sets

A vector efficient implementation of the McMurchie and Davidson algorithm for the calculation of one- and two-electron molecular integrals is presented, as available in the Cray version of the ASTERIX program system. The implementation and performance of a vector-oriented strategy for the generation and processing of the P supermatrix is also discussed. This program system has been applied to the ab initio SCF computation of the ground-state wave function for the [V₁₀O₂₈]^6? ion, with a basis set of triple-zeta quality for the valence shell of oxygen generating 1404 GTOS and 574 CGTOS for the complete system. The performance and the bottlenecks of the integral calculation are discussed as a function of the integral classes. Two-dimensional maps of the electrostatic potential are presented for this molecule and compared to experimental information about proton fixation.     

Monte Carlo vs molecular dynamics for all-atom polypeptide folding simulations

An efficient Monte Carlo (MC) algorithm including concerted rotations is directly compared to molecular dynamics (MD) in all-atom statistical mechanics folding simulations of small polypeptides. The previously reported algorithm "concerted rotations with flexible bond angles" (CRA) has been shown to successfully locate the native state of small polypeptides. In this study, the folding of three small polypeptides (trpzip2/H1/Trp-cage) is investigated using MC and MD, for a combined sampling time of approximately 10(11) MC configurations and 8 micros, respectively. Both methods successfully locate the experimentally determined native states of the three systems, but they do so at different speed, with 2-2.5 times faster folding of the MC runs. The comparison reveals that thermodynamic and dynamic properties can reliably be obtained by both and that results from folding simulations do not depend on the algorithm used. Similar to previous comparisons of MC and MD, it is found that one MD integration step of 2 fs corresponds to one MC scan, revealing the good sampling of MC. The simplicity and efficiency of the MC method will enable its future use in folding studies involving larger systems and the combination with replica exchange algorithms.     

Combined wavelet transform-artificial neural network use in tablet active content determination by near-infrared spectroscopy

The pharmaceutical industry faces increasing regulatory pressure to optimize quality control. Content uniformity is a basic release test for solid dosage forms. To accelerate test throughput and comply with the Food and Drug Administration's process analytical technology initiative, attention is increasingly turning to nondestructive spectroscopic techniques, notably near-infrared (NIR) spectroscopy (NIRS). However, validation of NIRS using requisite linearity and standard error of prediction (SEP) criteria remains a challenge. This study applied wavelet transformation of the NIR spectra of a commercial tablet to build a model using conventional partial least squares (PLS) regression and an artificial neural network (ANN). Wavelet coefficients in the PLS and ANN models reduced SEP by up to 60% compared to PLS models using mathematical spectra pretreatment. ANN modeling yielded high-linearity calibration and a correlation coefficient exceeding 0.996.     

CONTROLLING THE 3D NANOSCALE ORGANIZATION OF BULK HETEROJUNCTION POLYMER SOLAR CELLS

In this study,the three dimensional nanoscale organization in the photoactive layers of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM) is revealed by transmission electron tomography.After annealing treatment,either at elevated temperature or during slow solvent evaporation,nanoscale interpenetrating networks are formed with high crystalline order and favorable concentration gradients of both components through the thickness of the photoactive layer.Such a tailored morphology acco...     

Polypeptide folding using Monte Carlo sampling, concerted rotation, and continuum solvation

An efficient concerted rotation algorithm for use in Monte Carlo statistical mechanics simulations is applied to fold three polypeptides, U(1-17)T9D, alpha(1), and trpzip2, which exhibit native beta-hairpin and alpha-helix folds. The method includes flexible bond and dihedral angles, and a Gaussian bias is applied with driver bond and dihedral angles to optimize the sampling efficiency. Solvation in water is implemented with the generalized Born (GBSA) model. The computed lowest-energy manifolds for the folded structures of the two beta-hairpins agree closely with the corresponding NMR structures. In the case of the alpha(1) peptide, the folded alpha-helical state, which is observed as oligomers in concentrated solution and crystals, is not stable in isolation. The computed preference for random coil structures is in agreement with NMR experiments at low concentration. The fact that native states can be located on high dimensional energy surfaces starting from extended conformations shows that the present methodology samples all relevant parts of the conformational space. The OPLS-AA force field with the GBSA solvent model was also found to perform well in leading to clear energetic separation of the correctly folded structures from misfolded structures for the two peptides that form beta-turns.     

Near-infrared determination of active substance content in intact low-dosage tablets

Near-infrared (NIR) spectroscopy can be applied to determine the active substance content of tablets. Its great advantage lies in the minimal sample preparation required, which helps to reduce the potential for error. The aim of this study is to show the feasibility of this method on low-dosage tablets. The influence of various spectral pretreatments [standard normal variate (SNV), multiplicative scatter correction (MSC), second derivative (D2), orthogonal signal correction (OSC), separately and combined] and regression methods on prediction error are compared. Partial least square (PLS) regression provided better prediction than principal component regression (PCR). SNV was applied to the first data set and SNV and a second derivative to the second set to maximise model accuracy for quantifying the active substance of intact pharmaceutical products using diffuse reflectance NIR. The models yielded standard errors of prediction (SEP) of 0.1768 and 0.0682 mg for the two products. The experiments were conducted with two low-dosage pharmaceutical forms and results of NIR predictions were comparable to currently approved methods. Diffuse reflectance NIR has the potential to become a reliable and robust quality control method for determining active tablet content.     

Models for capacitated lot-sizing problem with backlogging,setup carryover and crossover

Setup operations are significant in some production environments. It is mandatory that their production plans consider some features, as setup state conservation across periods through setup carryover and crossover. The modelling of setup crossover allows more flexible decisions and is essential for problems with long setup times. This paper proposes two models for the capacitated lot-sizing problem with backlogging and setup carryover and crossover. The first is in line with other models from the literature, whereas the second considers a disaggregated setup variable, which tracks the starting and completion times of the setup operation. This innovative approach permits a more compact formulation. Computational results show that the proposed models have outperformed other state-of-the-art formulation.     

Preparation, structural analysis and dielectric properties of Bi x La1−x FeO3 perovskite

Rare earth element substituted bismuth ferrites (BiFeO₃) are of enormous importance as magnetoelectric materials. The polycrystalline samples of Bi _x La_1−x FeO₃ (x=0, 0.2, 0.4, 0.6, 0.8) were prepared by solid-state reaction using standard ceramic method. The single-phase formation of these compounds was confirmed by X-ray diffraction (XRD) studies. The samples with x=0, 0.2, 0.4, 0.6 are found to be orthorhombic while the sample with x=0.8 is triclinic. The dielectric constant (ε′) and dissipation factor (tan δ) were measured in the frequency range 100 Hz to 1 MHz at room temperature and as a function of temperature at certain fixed frequencies (1 kHz, 10 kHz, 100 kHz, 1 MHz). All the samples showed dielectric dispersion. The dielectric constant with temperature shows a broad peak; the peak temperature shifts with frequency which reflects the relaxor-type behavior. The peak above 600 K in the measured temperature range corresponds to antiferromagnetic ordering temperature (Néel temperature). The broadness of the peak changes with composition. The ac conductivity as well as ε′ are found to be maximum for the sample x=0.2 at room temperature.