Molecular dynamics simulations and free energy calculations on the enzyme 4‐hydroxyphenylpyruvate dioxygenase

4‐Hydroxyphenylpyruvate dioxygenase is a relevant target in both pharmaceutical and agricultural research. We report on molecular dynamics simulations and free energy calculations on this enzyme, in complex with 12 inhibitors for which experimental affinities were determined. We applied the thermodynamic integration approach and the more efficient one‐step perturbation. Even though simulations seem well converged and both methods show excellent agreement between them, the correlation with the experimental values remains poor. We investigate the effect of slight modifications on the charge distribution of these highly conjugated systems and find that accurate models can be obtained when using improved force field parameters. This study gives insight into the applicability of free energy methods and current limitations in force field parameterization. © 2011 Wiley Periodicals, Inc. J Comput Chem 2011     

Coupled fluid–solid interaction under shock wave loading

This paper considers the treatment of fluid–solid interaction problems under shock wave loading, where the solid experiences large bulk Lagrangian displacements. This work addresses the issues associated with using a level set as a generalized interface for fluid–solid coupling where the fluid–solid interface is embedded in an unstructured fluid grid. We outline the formulation used for the edge‐based unstructured‐grid Euler solver. The identification of the fluid–solid interface on the unstructured fluid mesh uses a super‐sampled ??² projection technique, which in conjunction with a Lagrangian interface position, permits fast identification of the interface and the concomitant imposition of boundary conditions. The use of a narrow‐band approach for the identification of the wetted interface is presented with the details of the construction of interface conditions. A series of two and three‐dimensional shock‐body computations are presented to demonstrate the validity of the current approach on problems with static and dynamic interfaces, including projectile/shock interaction simulations. Copyright © 2010 John Wiley & Sons, Ltd.     

Heterogeneous polycondensation for composition control of poly(p‐mercaptobenzoyl‐co‐p‐benzamide) by shearing

Composition control of aromatic poly(thioester‐amide) was examined by the reaction‐induced phase separation during polymerization of S‐acetyl‐4‐mercaptobenzoic acid (AMBA) and p‐acetylaminobenzoic acid (AABA) in aromatic solvent. The poly(thioester‐amide)s were obtained as precipitates and their yields became lower at the middle range of the content of AMBA in feed (χ_f). The contents of p‐mercaptobenzoyl (MB) moiety (χ_p) in the precipitates prepared without shearing were in good agreement with the χ_f values. In contrast to this, the χ_p values of the precipitates prepared at χ_f of 50–70 mol % under shearing were much lower than the χ_f values. The reaction rate of AMBA increased with shearing, whereas that of AABA was unchanged by shearing. This shearing effect on the reaction rates accelerated to form the homo‐oligomers. The solubility of MB oligomers enhanced by shearing, whereas that of p‐benzamide oligomers did not enhance owing to the strong interaction through hydrogen bonding. The MB oligomers were inhibited to be precipitated, resulting in the lower χ_p values than the χ_f values. The composition could be controlled by the application of the shearing to the heterogeneous polymerization. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4301–4308     

变系数模型变窗宽和一步局部M-估计

用变窗宽和一步局部M-估计对变系数模型的系数参数进行估计,得到了估计的渐近正态性.     

Poly(arylene sulfide)s by nucleophilic aromatic substitution polymerization of 2,7‐difluorothianthrene

Poly(thianthrene phenylene sulfide) and poly(thianthrene sulfide) have been prepared by nucleophilic aromatic substitution polymerization of the activated monomer 2,7‐difluorothianthrene with bis thiophenoxide and sulfide nucleophiles, respectively. The resulting polymers are thermally stable, amorphous materials that have been characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), gel permeation chromatography (GPC), matrix‐assisted laser desorption/ionization‐time‐of‐flight (MALDI‐TOF) mass spectrometry, UV‐Vis spectroscopy, refractometry, and intrinsic viscosity (IV) measurements. The polymers produced exhibit 5% weight loss values approaching 500 °C in inert and air atmospheres and glass transition temperatures that range from 149 to 210 °C. Poly(thianthrene phenylene sulfide) with a number average molecular weight of 22,100 g/mol has been synthesized with an IV in DMPU of 0.62 dL/g at 30 °C. Creasable films of this polymer have been prepared by solvent casting and melt pressing at 250 °C. Films of poly(thianthrene phenylene sulfide) exhibit transparencies greater than 50% at wavelengths exceeding 400 nm and a high refractive index value of 1.692 at a wavelength of 633 nm, making the polymer interesting for optical applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2453–2461, 2009     

The onset of mixed-mode intralaminar cracking in a cross-ply composite laminate

The intralaminar fracture toughness of a unidirectionally reinforced glass/epoxy composite is determined experimentally at several mode I and mode II loading ratios. The crack propagation criterion, expressed as a quadratic form in terms of single-mode stress intensity factors (alternatively, linear in terms of energy release rates), approximates the test results reasonably well. The mixed-mode cracking criterion obtained is used to predict the intralaminar crack on set in a cross-ply glass/epoxy composite under off-axis tensile loading. Translated from Mekhanika Kompozitnykh Materialov, Vol. 44, No. 6, pp. 785–794, November–December, 2008.     

氧化物表面的侧表面原子成象——Ⅰ.Eu_2O_2晶体由位错滑移形成表面台阶的动态原位观察

通过高分辨电子显微术获得了Eu_2O_3晶体分子清洁的表面侧面原子成象,观察到了由表面附近位错滑移出表面而形成表面原子台阶的动态变化过程,同时还观察到了此种表面台阶的形核生长。     

Identification of temperature‐dependent thermophysical properties in a partial differential equation subject to extra final measurement data

We consider an inverse problem for estimating the two coefficient functions c and k in a parabolic type partial differential equation c(u)u_t = ?[k(u)u_x]/?x with the aid of the measurements of u at two different times. The first‐ and second‐order one‐step group preserving schemes are developed. Solving the resultant algebraic equations with a closed‐form, we can estimate the unknown temperature‐dependent thermal conductivity and heat capacity. The new methods possess threefold advantages: they do not require any a priori information on the functional forms of thermal conductivity and heat capacity; no initial guesses are required; and no iterations are required. Numerical examples are examined to show that the new approaches have high accuracy and efficiency, even there are rare measured data. When the measured temperatures are polluted by uniform or normal random noise, the estimated results are also good. © 2007 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2007     

端头带有质量块的悬臂梁在冲击载荷下的两种剪切失效模型

剪切失效是强动载荷作用下结构失效的重要模式。本文给出了计及梁的转动惯量时端头带有质量块的悬臂梁结构受到冲击载荷作用后发生剪切失效的无量纲判据。分析表明，在初始速度间断面上是否发生剪切失效取决于质量块初始动能和质量块尺寸与梁厚之比，而与梁的长度无关。梁的转动惯量对于剪切失效具有不可忽略的影响。     

秩协方差分析及应用

吴占鹏．秩协方差分析及应用．数理统计与管理，１９９８，１７（３），７～１０．在随机区组试验中，区组内往往存在土壤梯度差异，使试验误差增大。为此，本文提出秩协方差分析方法，即把土壤差异εｉｊ分解成Δ·ｘｉｊ和δｉｊ两个成份，从中剔除土壤梯度差异Δ·ｘｉｊ对试验精度的影响，以提高试验结果的可靠性