Environmental effects on fibre reinforced polymeric composites: Evolving reasons and remarks on interfacial strength and stability

The interface between fibre and matrix of fibrous polymeric composites is most critical and decisive in maintaining sustainability, durability and also reliability of this potential material, but unfortunately a comprehensive conclusion is yet to meet the label of confidence for the engineering viability. Fiber reinforced polymer (FRP) composites are being accepted and also utilized as better and reliable alternative materials for repairing and/or replacing conventional materials, starting from tiny objects to mega structure in various engineering applications. The promise and potential of these materials are sometimes threatened in speedy replacement of conventional materials because of their inhomogeneities and inherent susceptibility to degradation due to moist and thermal environments. Environmental conditioning is traditionally believed to be a physical phenomenon but present literature has revealed that the interdiffusion between fiber and polymer matrix resin comprises of physical, chemical, mechanical, physico-chemical and mechano-chemical phenomena. The failure and fracture behavior at ambient conditions itself is a complex phenomenon till at present. The service conditions which are mostly hygrothermal in nature, along with a variation of applied loads make the mechanical behavior nearly unpredictable, far off from conclusions in evaluating the short term as well as long term durability and reliability of FRPs. It is essential to accurately simulate the initial and subsequent evolution process of this kind of damage phenomena, in order to explore the full potential of the mechanical properties of composite laminates. The present review has emphasized the need of complying scattered as well as limited literature on this front, and has focused on creating the urgency to highlight the importance of judicious uses of these materials with minimum safety factors with an aim to achieving lighter weight in enhancing specific properties.     

Tutorial review on validation of liquid chromatography–mass spectrometry methods: Part I

This is the part I of a tutorial review intending to give an overview of the state of the art of method validation in liquid chromatography mass spectrometry (LC–MS) and discuss specific issues that arise with MS (and MS/MS) detection in LC (as opposed to the “conventional” detectors). The Part I briefly introduces the principles of operation of LC–MS (emphasizing the aspects important from the validation point of view, in particular the ionization process and ionization suppression/enhancement); reviews the main validation guideline documents and discusses in detail the following performance parameters: selectivity/specificity/identity, ruggedness/robustness, limit of detection, limit of quantification, decision limit and detection capability. With every method performance characteristic its essence and terminology are addressed, the current status of treating it is reviewed and recommendations are given, how to determine it, specifically in the case of LC–MS methods.     

High‐temperature superconductivity and long‐range order in strongly correlated electronic systems

A selective review of the question of how repulsive electron correlations might give rise to off‐diagonal long‐range order (ODLRO) in high‐temperature superconductors is presented. The article makes detailed explanations of the relevance to superconductivity of reduced electronic density matrices and how these can be used to understand whether ODLRO might arise from Coulombic repulsions in strongly correlated electronic systems. Time‐reversed electron pairs on alternant Cuprate and the iron‐based pnictide and chalcogenide lattices may have a weak long‐range attractive tail and much stronger short‐range repulsive Coulomb interaction. The long‐range attractive tail may find its origin in one of the many suggested proposals for high‐T_c superconductivity and thus has an uncertain origin. A phenomenological Hamiltonian is invoked whose model parameters are obtained by fitting to experimental data. A detailed summary is given of the arguments that such interacting electrons can cooperate to produce a superconducting state in which time‐reversed pairs of electrons effectively avoid the repulsive hard‐core of the Coulomb interaction but reside on average in the attractive well of the long‐range potential. Thus, the pairing of electrons itself provides an enhanced screening mechanism. The alternant lattice structure is the key to achieving robust high‐temperature superconductivity with dx²‐y² or sign alternating s‐wave or s± condensate symmetries in cuprates and iron‐based compounds. Some attention is also given to the question first raised by Leggett as to where the Coulombic energy is saved in the superconducting transition in cuprates. A mean‐field‐type model in which the condensate density serves as an order parameter is discussed. Many of the observed trends in the thermal properties of cuprate superconductors are reproduced giving strong support for the proposed model for high‐temperature superconductivity in such strongly correlated electronic systems. © 2015 Wiley Periodicals, Inc.     

Application of Löwdin's canonical orthogonalization method to the Slater‐type orbital configuration‐interaction basis set

We apply Löwdin's canonical orthogonalization method to investigate the linearly dependent problem arising from the variational calculation of atomic systems using Slater‐type orbital configuration‐interaction (STO‐CI) basis functions. With a specific arithmetic precision used in numerical computations, the nonorthogonal STO‐CI basis is easily linearly dependent when the number of basis functions is sufficiently large. We show that Löwdin's canonical orthogonalization method can successfully overcome such problem and simultaneously reduce the dimension of basis set. This is illustrated first through an S‐wave model He atom, and then the real two‐electron atoms in both the ground and excited states. In all of these calculations, the variational bound state energies of the two‐electron systems are obtained in reasonably high accuracy using over‐redundant STO‐CI bases, however, without using extended high‐precision technique. © 2015 Wiley Periodicals, Inc.     

Influence of relative humidity and loading frequency on the PA6.6 thermomechanical cyclic behavior: Part II. Energy aspects

In this study, we investigated the influence of relative humidity (RH) and loading rate on the energy response of PA6.6 matrix specimens. The latter were subjected to oligocyclic tensile-tensile tests at 3 different RH and 2 loading rates. Infrared thermography was used to obtain a direct estimate of heat sources using the heat diffusion equation. Using the mechanical and thermal responses discussed in the first part of this work, complete energy rate balances were drawn up. In particular, the time courses of deformation, and dissipated and stored energy rates are discussed. The strong influence of the loading frequency and RH on the energy storage mechanisms is also highlighted.     

Synthesis and application of mesoporous molecular sieve for miniaturized matrix solid‐phase dispersion extraction of bioactive flavonoids from toothpaste,plant, and saliva

This article describes the use of the mesoporous molecular sieve KIT‐6 as a sorbent in miniaturized matrix solid‐phase dispersion (MSPD) in combination with ultra‐performance LC for the determination of bioactive flavonoids in toothpaste, Scutellariae Radix, and saliva. In this study, for the first time, KIT‐6 was used as a sorbent material for this mode of extraction. Compared with common silica‐based sorbents (C18 and activated silica gel), the proposed KIT‐6 dispersant with a three‐dimensional cubic Ia3d structure and highly ordered arrays of mesoporous channels exhibits excellent adsorption capability of the tested compounds. In addition, several experimental variables, such as the mass ratio of sample to dispersant, grinding time, and elution solvent, were optimized to maximize the extraction efficiency. The proposed analytical method is simple, fast, and entails low consumption of samples, dispersants and elution solvents, thereby meeting “green chemistry” requirements. Under the optimized conditions, the recoveries of three bioactive flavonoids obtained by analyzing the spiked samples were from 89.22 to 101.17%. Also, the LODs and LOQs for determining the analytes were in the range of 0.02–0.04 μg/mL and 0.07–0.13 μg/mL, respectively. Finally, the miniaturized matrix solid‐phase dispersion method was successfully applied to the analysis of target solutes in real samples, and satisfactory results were obtained.     

Revisiting the extrapolation of correlation energies to complete basis set limit

The extrapolation scheme of correlation energy is revisited to evaluate the complete basis set limit from double‐zeta (DZ) and triple‐zeta levels of calculations. The DZ level results are adjusted to the standard asymptotic behavior with respect to the cardinal number, observed at the higher levels of basis sets. Two types of adjusting schemes with effective scaling factors, which recover errors in extrapolations with the DZ level basis set, are examined. The first scheme scales the cardinal number for the DZ level energy, while the second scheme scales the prefactor of the extrapolation function. Systematic assessments on the Gaussian‐3X and Gaussian‐2 test sets reveal that these calibration schemes successfully and drastically reduce errors without additional computational efforts. © 2015 Wiley Periodicals, Inc.     

Mechanism of proteolysis in matrix metalloproteinase‐2 revealed by QM/MM modeling

The mechanism of enzymatic peptide hydrolysis in matrix metalloproteinase‐2 (MMP‐2) was studied at atomic resolution through quantum mechanics/molecular mechanics (QM/MM) simulations. An all‐atom three‐dimensional molecular model was constructed on the basis of a crystal structure from the Protein Data Bank (ID: 1QIB), and the oligopeptide Ace‐Gln‐Gly～Ile‐Ala‐Gly‐Nme was considered as the substrate. Two QM/MM software packages and several computational protocols were employed to calculate QM/MM energy profiles for a four‐step mechanism involving an initial nucleophilic attack followed by hydrogen bond rearrangement, proton transfer, and C? N bond cleavage. These QM/MM calculations consistently yield rather low overall barriers for the chemical steps, in the range of 5–10 kcal/mol, for diverse QM treatments (PBE0, B3LYP, and BB1K density functionals as well as local coupled cluster treatments) and two MM force fields (CHARMM and AMBER). It, thus, seems likely that product release is the rate‐limiting step in MMP‐2 catalysis. This is supported by an exploration of various release channels through QM/MM reaction path calculations and steered molecular dynamics simulations. © 2015 Wiley Periodicals, Inc.     

预裂化理论研究:基质表面酸性位类型及不同类型酸性位接触顺序对裂化过程小分子烯烃收率的影响

在区分氢负离子转移反应与氢转移反应、非选择性氢转移反应与总的氢转移反应的情况下,通过合成物性相近但酸性不同的氧化铝,用以作为裂化催化剂基质材料,在固定床反应器上考察了催化裂化过程,基质酸性位类型及基质表面Lewis及Brönsted酸性位接触顺序对小分子烯烃(丙烯、丁烯)收率的影响。结果表明,催化裂化生成小分子烯烃过程中,分子筛与基质所呈现出的反应特点存在较大的区别,前者活性虽高,但总的氢转移反应活性过强。基质材料裂化活性虽低但其表面以氢负离子转移反应为主,反应路径角度更有利于小分子烯烃收率的提高。另外,基质表面存在Brönsted酸性位,或原料油首先与基质表面Lewis酸性位相接触再与Brönsted酸性位反应的预裂化过程,会在促进裂化反应发生的同时抑制总的氢转移反应,更有利于小分子烯烃收率的提高。