Assessment of model chemistries for hydrofluoropolyethers: A DFT/M08‐HX benchmark study

In this work, we report the first detailed theoretical comparative conformational investigation between two different classes of hydrofluoropolyethers: dihydro‐ and dimethoxyfluoropolyethers. The main objective was to determine a cost‐effective computational methodology that could accurately reproduce the energetic rankings and thermal weight factors of the simplest examples of those two classes calculated with M08‐HX/triple‐ζ//M08‐HX/double‐ζ benchmark model chemistries. Between the tested methodologies, M08‐HX/aug‐pcseg‐2//M08‐HX/pcseg‐1 was found to be the most appropriate, exhibiting a good accuracy and considerable reduction in computational cost with respect to the benchmark, being more than three times faster than M08‐HX/aug‐pcseg‐2//M08‐HX/aug‐pcseg‐1. This cost‐effective approach will be essential in future work when studying larger hydrofluoropolyethers, where the computational complexity associated with increasing number of conformers will require such approximations.     

Temperature‐shuffled parallel cascade selection molecular dynamics accelerates the structural transitions of proteins

Parallel cascade selection molecular dynamics (PaCS‐MD) is an enhanced conformational sampling method for searching structural transition pathways from a given reactant to a product. Recently, a temperature‐aided PaCS‐MD (Vinod et al., Eur. Biophys. J. 2016, 45, 463) has been proposed as its extension, in which the temperatures were introduced as additional parameters in conformational resampling, whereas the temperature is fixed in the original PaCS‐MD. In the present study, temperature‐shuffled PaCS‐MD is proposed as a further extension of temperature‐aided PaCS‐MD in which the temperatures are shuffled among different replicas at the beginning of each cycle of conformational resampling. To evaluate their conformational sampling efficiencies, the original, temperature‐aided, and temperature‐shuffled PaCS‐MD were applied to a protein‐folding process of Trp‐cage, and their minimum computational costs to identify the native state were addressed. Through the evaluation, it was confirmed that temperature‐shuffled PaCS‐MD remarkably accelerated the protein‐folding process of Trp‐cage compared with the other methods. © 2017 Wiley Periodicals, Inc.     

Adaptive‐numerical‐bias metadynamics

A metadynamics scheme is presented in which the free energy surface is filled with progressively adding adaptive biasing potentials, obtained from the accumulated probability distribution of the collective variables. Instead of adding Gaussians with assigned height and width in conventional metadynamics method, here we add a more realistic adaptive biasing potential to the Hamiltonian of the system. The shape of the adaptive biasing potential is adjusted on the fly by sampling over the visited states. As the top of the barrier is approached, the biasing potentials become wider. This decreases the problem of trapping the system in the niches, introduced by the addition of Gaussians of fixed height in metadynamics. Our results for the free energy profiles of three test systems show that this method is more accurate and converges more quickly than the conventional metadynamics, and is quite comparable (in accuracy and convergence rate) with the well‐tempered metadynamics method. © 2017 Wiley Periodicals, Inc.     

Structural dissimilarity sampling with dynamically self‐guiding selection

Structural dissimilarity sampling (SDS) has been proposed as an enhanced conformational sampling method for reproducing the structural transitions of a given protein. SDS consists of cycles of two steps: (1) Selections of initial structures with structural dissimilarities by referring to a measure. (2) Conformational resampling by restarting short‐time molecular dynamics (MD) simulations from the initial structures. In the present study, an efficient measure is proposed as a dynamically self‐guiding selection to accelerate the structural transitions from a reactant state to a product state as an extension to the original SDS. In the extended SDS, the inner product (IP ) between the reactant and the snapshots generated by short‐time MD simulations are evaluated and ranked according to the IP s at every cycle. Then, the snapshots with low IP s are selected as initial structures for the short‐time MD simulations. This scheme enables one to choose dissimilar and distant initial structures from the reactant, and thus the initial structures dynamically head towards the product, promoting structural transitions from the reactant. To confirm the conformational sampling efficiency, the extended SDS was applied to maltodextrin binding protein (MBP), and we successfully reproduced the structural transition from the open to closed states with submicrosecond‐order simulation times. However, a conventional long‐time MD simulation failed to reproduce the same structural transition. We also compared the performance with that obtained by the ordinary SDS and other sampling techniques that have been developed by us to characterize the possible utility of the extended SDS for actual applications. © 2017 Wiley Periodicals, Inc.     

Determination of selected trace elements in marine biota samples with the application of fast temperature programs and solid sampling continuous source high resolution atomic absorption spectroscopy: method validation

Analytical procedure for the determination of As, Cd, Cu, Ni, Co and Cr in marine biota samples using solid sampling high-resolution continuum source atomic absorption spectrometry (HR CS AAS) and accelerated fast temperature programmes has been developed. Calibration technique based on the use of solid certified reference materials similar to the nature of the analysed sample and statistics of regression analysis were applied. A validation approach in line with the requirements of ISO 17025 standard and Eurachem guidelines was followed. Accordingly, blanks, selectivity, calibration, linearity, working range, trueness, repeatability and reproducibility, limits of detection and quantification and expanded uncertainty for all investigated elements were assessed. The major contributors to the combined uncertainty of the analyte mass fractions were found to be the homogeneity of the samples and the microbalance precision. Traceability to the SI system of units of the obtained with the proposed analytical procedure results was also demonstrated. The potential of the proposed analytical procedure based on solid sampling HR CS AAS technique was demonstrated by direct analysis of marine reference biota samples. Overall, the use of solid sampling HR CS AAS permits obtaining significant advantages for the determination of selected trace elements in marine biota samples, such as straightforward calibration, a high sample throughput, sufficient precision, a suitable limit of detection and reduced risk of analyte loss and contamination.     

Compendium of photovoltaic degradation rates

Published data on photovoltaic (PV) degradation measurements were aggregated and re‐examined. The subject has seen an increased interest in recent years resulting in more than 11 000 degradation rates in almost 200 studies from 40 different countries. As studies have grown in number and size, we found an impact from sampling bias attributable to size and accuracy. Because of the correlational nature of this study we examined the data in several ways to minimize this bias. We found median degradation for x‐Si technologies in the 0.5–0.6%/year range with the mean in the 0.8–0.9%/year range. Hetero‐interface technology (HIT) and microcrystalline silicon (µc‐Si) technologies, although not as plentiful, exhibit degradation around 1%/year and resemble thin‐film products more closely than x‐Si. Several studies showing low degradation for copper indium gallium selenide (CIGS) have emerged. Higher degradation for cadmium telluride (CdTe) has been reported, but these findings could reflect a convolution of less accurate studies and longer stabilization periods for some products. Significant deviations for beginning‐of‐life measurements with respect to nameplate rating have been documented over the last 35 years. Therefore, degradation rates that use nameplate rating as reference may be significantly impacted. Studies that used nameplate rating as reference but used solar simulators showed less variation than similar studies using outdoor measurements, even when accounting for different climates. This could be associated with confounding effects of measurement uncertainty and soiling that take place outdoors. Hotter climates and mounting configurations that lead to sustained higher temperatures may lead to higher degradation in some, but not all, products. Wear‐out non‐linearities for the worst performing modules have been documented in a few select studies that took multiple measurements of an ensemble of modules during the lifetime of the system. However, the majority of these modules exhibit a fairly linear decline. Modeling these non‐linearities, whether they occur at the beginning‐of‐life or end‐of‐life in the PV life cycle, has an important impact on the levelized cost of energy. Copyright © 2016 John Wiley & Sons, Ltd.     

A rigorous assessment of the benefits of miniaturization in the Kolsky bar system

A rigorous experimental and numerical assessment is made of the benefits and limits of miniaturization in the Kolsky bar system. The primary issues that arise in very high strain rate testing (stress equilibration, inertial effects, wave dispersion, friction, and controllability of deformations) are addressed through experiments coupled with explicit finite element analyses. A miniaturized Kolsky bar system that includes the input bar is developed, together with the use of the laser occlusive radius detector to obtain local measurements of specimen strain during the very high rate deformations. It is demonstrated that this miniaturized Kolsky bar system can be used to provide fully validated results, including the explicit determination of equilibration, over a very wide range of strain rates (1×10³ to 5×10⁴ s⁻¹). The desired high strain rate can be achieved even at low accumulated strains, and the total strain developed can be controlled very effectively. Specific conditions are developed for determining the range of utility of the technique for a given material. The technique is applied to the characterization of 6061-T651 aluminum, and the results are compared with the results obtained using a conventional Kolsky bar.     

2003—2007年中国儿童铅中毒率的分析研究——发铅检测结果

通过计算机检索收集了2003—2007年间公开发表的、关于儿童发铅水平和铅中毒率的中文文献,对涉及8省16万人作了调查分析。结果表明,近5年内中国儿童的平均发铅水平为7.5μg/g,铅中毒率平均为27.5%,与同一时期血铅检测结果一致。     

基于DCSBM模型的受访者驱动抽样调查估计量改进

大数据背景下,将受访者驱动抽样(RDS)用于网络抽样调查,解决了传统抽样调查难以获得可用抽样框、难以接触被调查者以及难以获得回答等问题,也使得网络调查可以实现概率抽样,得到一定误差范围内的总体参数估计.然而,在实际抽样过程中,同质性问题(即样本单元在推荐同伴时倾向于推荐那些与自己有相同属性的同伴)会导致RDS估计量的方...     

Accurate free energy calculation along optimized paths

The path‐based methods of free energy calculation, such as thermodynamic integration and free energy perturbation, are simple in theory, but difficult in practice because in most cases smooth paths do not exist, especially for large molecules. In this article, we present a novel method to build the transition path of a peptide. We use harmonic potentials to restrain its nonhydrogen atom dihedrals in the initial state and set the equilibrium angles of the potentials as those in the final state. Through a series of steps of geometrical optimization, we can construct a smooth and short path from the initial state to the final state. This path can be used to calculate free energy difference. To validate this method, we apply it to a small 10‐ALA peptide and find that the calculated free energy changes in helix‐helix and helix‐hairpin transitions are both self‐convergent and cross‐convergent. We also calculate the free energy differences between different stable states of β‐hairpin trpzip2, and the results show that this method is more efficient than the conventional molecular dynamics method in accurate free energy calculation. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010