Evaluation of basis sets and theoretical methods for estimating rate constants of mercury oxidation reactions involving chlorine

The occurrence of elemental mercury in flue gases from coal combustion is a problem of current environmental concern. Oxidized mercury species can be effectively removed from the flue gases by chemical scrubbers. However, the detailed mechanism by which oxidation occurs remains unclear. Theoretical rate constants are calculated for mercury oxidation by atomic chlorine. The potential energy surface is determined using standard quantum chemical methods with relativistic effects included via the use of an effective core potential (ECP). Experimental thermodynamic and kinetic data are employed to assess the accuracy of these calculations. Results show that the QCISD method with the 1992 basis set of Stevens et al. gives good agreement with experiment, suggesting that this combination may be useful for other mercury–chlorine chemical systems.     

Mixed Quantum/Classical Molecular Dynamics Simulations of Chemical Reactions in Clusters and in Solids

An overview is given of a recent method for dynamical simulations of many-atom systems, which incorporates also important quantum effects. The method treats a few pertinent degrees of freedom (e.g., a light atom) by time-dependent wavepackets and all the other coordinates by classical trajectories. The classical and quantum subsystems are coupled in this approach by a hybrid quantum/classical Time-Dependent Self-Consistent Field (TDSCF) approximation. The properties, validity, range, and limitations of this method are discussed, and numerical tests of its accuracy are presented for simple model systems. The method is illustrated by applications to photodissociation of HI molecules in solid Xe and in Xe clusters of different sizes. The scope of potential applications, open problems, and possible directions of extending the method are discussed.     

Quantum Computing for Molecular Biology**

Molecular biology and biochemistry interpret microscopic processes in the living world in terms of molecular structures and their interactions, which are quantum mechanical by their very nature. Whereas the theoretical foundations of these interactions are well established, the computational solution of the relevant quantum mechanical equations is very hard. However, much of molecular function in biology can be understood in terms of classical mechanics, where the interactions of electrons and nuclei have been mapped onto effective classical surrogate potentials that model the interaction of atoms or even larger entities. The simple mathematical structure of these potentials offers huge computational advantages; however, this comes at the cost that all quantum correlations and the rigorous many-particle nature of the interactions are omitted. In this work, we discuss how quantum computation may advance the practical usefulness of the quantum foundations of molecular biology by offering computational advantages for simulations of biomolecules. We not only discuss typical quantum mechanical problems of the electronic structure of biomolecules in this context, but also consider the dominating classical problems (such as protein folding and drug design) as well as data-driven approaches of bioinformatics and the degree to which they might become amenable to quantum simulation and quantum computation.     

Electron transfer rates in the levich and dogonadze theory of redox reactions

The Levich and Dogonadze theory of redox reactions in solutions is regarded as a suitable model to discuss the nature of quantum effects in electron transfer. In Section I the quantum mechanical framework—first order perturbation theory and the Born—Oppenheimer approximation—is reviewed; an inaccuracy in the corresponding treatment by Levich is corrected. In Section II the electron transfer rate is calculated. The result differs from the formula given by Levich; the difference becomes especially important at intermediate and at low temperatures. As a consequence quantum effects should already be observable at ordinary temperatures. It is shown that the high temperature approximation can also be obtained by a semiclassical calculation. These results are compared with the activated complex theory.     

Valence Bond-Based Hybrid Quantum Mechanics Molecular Mechanics Approaches and Proper Inclusion of the Effect of the Surroundings

The pioneering development of multiscale models for complex chemical systems by Karplus, Levitt, and Warshel, including the hybrid quantum mechanics molecular mechanics (QM/MM) approach and its application to enzymes, established a new field in chemistry that allows the modeling of reactivity within complex chemical systems. Inspired by the potential of such methods, many groups developed different QM/MM variants. Valence bond (VB) theory, which always was and still is an important conceptual tool for chemists, is well suited to deal with problems of chemical reactivity. Hence, here we review VB-based QM/MM methods, including the early semi-empirical methods that utilize VB concepts and more recent ab initio VB-based QM/MM methods. Special emphasis is given to the different ways to include effects of the surroundings on the solute. It is shown that within the VB framework, simple mechanical embedding for each diabatic state, followed by mixing of the states, accounts for most of these effects.     

A Model to Compute Phase Diagrams in Oxides with Empirical or First-Principles Energy Methods and Application to the Solubility Limits in the CaO–MgO System

The CaO–MgO system is used as a prototype system to evaluate the accuracy of several energy and entropy approximations for predicting solid-state phase diagrams in ionic materials. Configurational disorder between the cations is parameterized with the cluster expansion technique. The vibrational contribution to the free energy is incorporated with a harmonic model that accounts for the dependence of the vibrational density of states on the cation configuration. The CaO–MgO phase diagram can be predicted very accurately with quantum mechanical energy methods, without the use of any adjustable parameters. Published empirical potential parameters for the CaO–MgO system reproduce the qualitative features of the phase diagram but significantly underestimate the solubility limits. Parameters that reasonably reproduce the quantum mechanical results are presented.     

Structural and oxidative changes in the kidney of crucian carp induced by silicon-based quantum dots

Silicon-based quantum dots were intraperitoneally injected in Carassius auratus gibelio specimens and, over one week, the effects on renal tissue were investigated by following their distribution and histological effects, as well as antioxidative system modifications. After three and seven days, detached epithelial cells from the basal lamina, dilated tubules and debris in the lumen of tubules were observed. At day 7, nephrogenesis was noticed. The reduced glutathione (GSH) concentration decreased in the first three days and started to rise later on. The superoxide dismutase (SOD) activity increased only after one week, whereas catalase (CAT) was up-regulated in a time-dependent manner. The activities of glutathione reductase (GR) and glutathione peroxidise (GPX) decreased dramatically by approximately 50% compared to control, whereas the glutathione-S-transferase (GST) and glucose-6-phosphate dehydrogenase (G6PDH) increased significantly after 3 and 7 days of treatment. Oxidative modifications of proteins and the time-dependent increase of Hsp70 expression were also registered. Our data suggest that silicon-based quantum dots induced oxidative stress followed by structural damages. However, renal tissue is capable of restoring its integrity by nephron development.     

Effect of rheological parameters on phase morphology of poly blends: A route to computer aided design and development of industrial polyblends

Set of procedures employing melt viscoelasticity functions for selecting components and composition of the binary polyblends and estimating minor phase domain size is introduced and illustrated with examples. The procedures intended for Computer Aided Manufacture of the polyblends (CAMOBLE) are based on shear stress dependent viscoelasticity ratios, and the selection of the composition exploits stress dependent synergism of the viscoelasticity functions. Also used is auxilary procedure for composition selection is based on verified blending laws accounting for interaction and shear effects. Evaluation of the performance characteristics (“mechanical properties”) is illustrated with a modified Kerner model.     

Effects of Beverages on Alcohol Metabolism: Potential Health Benefits and Harmful Impacts

Nonalcoholic beverages are usually consumed accompanying alcoholic drinks, and their effects on alcohol metabolism are unclear in vivo. In this study, the effects of 20 nonalcoholic beverages on alcohol metabolism and liver injury caused by alcohol were evaluated in mice. Kunming mice were orally fed with alcohol (52%, v/v) and beverages. The concentrations of ethanol and acetaldehyde in blood as well as the activities of alcohol dehydrogenase (ADH) and aldehyde dehydrogenase (ALDH) in liver were assessed to indicate alcohol metabolism. The levels of aspartate aminotransferase (AST) and alanine transaminase (ALT) in serum as well as the levels of malonaldehyde (MDA) and superoxide dismutase (SOD) in liver were measured to reflect the alcohol-induced liver injury. The results showed that the treatment of soda water, green tea and honey chrysanthemum tea could accelerate ethanol metabolism and prevent liver injuries caused by alcohol when companied with excessive alcohol drinking. They might be potential dietary supplements for the alleviation of harmful effects from excessive alcohol consumption. On the contrary, some beverages such as fresh orange juice and red bull are not advised to drink when companied with alcohol consumption due to their adverse effects on ethanol induced liver injury.     

Test methods for characterizing concrete properties at elevated temperature

Fire resistance of structural members is dependent on the thermal and mechanical properties of constituent materials and these properties vary as a function of temperature. Currently, there are limited standardized test procedures for evaluating thermal and mechanical properties of construction materials at elevated temperatures. This paper provides a review and assessment of test methods and procedures for evaluating high temperature thermal and mechanical properties of concrete. The drawbacks and variations in currently available test procedures and methods in standards are discussed. Recommendations on the most suitable methods and procedures for measuring thermal and mechanical properties at elevated temperature is presented. In addition, applicability of the proposed high temperature test methods and procedures is illustrated through a case study on conventional concrete specimens. Further, the need for developing standards by organizations such as American Society for Testing and Materials (ASTM), with standardized specifications and test procedures for measuring high temperature properties of construction materials, is laid out.     

An interpenetrating network biohydrogel of gelatin and gellan gum by using a combination of enzymatic and ionic crosslinking approaches

Gelatin is a popular substrate for cell culture applications due to its biocompatibility and biodegradability. However, the mechanical property of gelatin is not satisfactory in certain tissue engineering areas where tunable and higher mechanical strengths are required. To achieve this purpose without exposure of materials to cytotoxic chemicals or procedures, a new biohydrogel of gelatin and gellan gum with an interpenetrating network (IPN) structure was prepared using a combination of enzymatic and ionic crosslinking approaches. The gelation procedure and thermal stability of the IPN structure were demonstrated in detail by a rheological study. The resulting IPN biohydrogel exhibited significantly increased and tunable mechanical strength, decreased swelling ratios and lower degradation rate compared with pure gelatin gel. The composite biohydrogels supported the attachment and proliferation of L929 fibroblasts as shown in vitro. These results indicate that this mechanically robust biohydrogel has the promising potential for serving as a cell support in the field of tissue engineering. © 2013 Society of Chemical Industry     

Enhanced photoluminescence of porous silicon nanoparticles coated by bioresorbable polymers

A significant enhancement of the photoluminescence (PL) efficiency is observed for aqueous suspensions of porous silicon nanoparticles (PSiNPs) coated by bioresorbable polymers, i.e., polylactic-co-glycolic acid (PLGA) and polyvinyl alcohol (PVA). PSiNPs with average size about 100 nm prepared by mechanical grinding of electrochemically etched porous silicon were dispersed in water to prepare the stable suspension. The inner hydrophobic PLGA layer prevents the PSiNPs from the dissolution in water, while the outer PVA layer makes the PSiNPs hydrophilic. The PL quantum yield of PLGA/PVA-coated PSiNPs was found to increase by three times for 2 weeks of the storage in water. The observed effect is explained by taking into account both suppression of the dissolution of PSiNPs in water and a process of the passivation of nonradiative defects in PSiNPs. The obtained results are interesting in view of the potential applications of PSiNPs in bioimaging.     

Behavioural analysis of adhesive-bonded structural joints in space vehicles

In space structures, the design of adhesive-bonded joints generally involves a very low safety ratio as opposed to a high one, indicating reliability. This requires careful choice of the criteria applied to account for external factors (mechanical, static and dynamic, and thermal effects). The situation is complicated by the behaviour of the materials involved, particularly composites, which undergo large distortions and whose fracture criteria depend on load cycles. In addition, polymerization effects in joints between different material,, such as metals and composites, must also be taken into account. In this paper a calculation tool is presented for bonded structures, and procedures for the accurate determination of the mechanical properties of adhesive materials are given.     

Non-Born-Oppenheimer molecular dynamics

Electronically nonadiabatic or non-Born-Oppenheimer (non-BO) chemical processes (photodissociation, charge-transfer, etc.) involve a nonradiative change in the electronic state of the system. Molecular dynamics simulations typically treat nuclei as moving classically on a single adiabatic potential energy surface, and these techniques are not immediately generalizable to non-BO systems due to the inherently quantum mechanical nature of electronic transitions. Here we generalize the concept of a single-surface molecular dynamics trajectory to that of a coupled-surface non-BO trajectory that evolves "semiclassically" under the influence of two or more electronic states and their couplings. Five non-BO trajectory methods are discussed. Next, we summarize the results of a series of systematic studies using a database of accurate quantum mechanical reaction probabilities and internal energy distributions for several six-dimensional model bimolecular scattering collisions. The test set includes three kinds of prototypical nonadiabatic interactions: conical intersections, avoided crossings, and regions of weak coupling. We show that the coherent switching with decay of mixing (CSDM) non-BO trajectory method provides a robust and accurate way to extend molecular dynamics to treat electronically nonadiabatic chemistry for all three kinds of nonadiabatic interactions, and we recommend it for molecular dynamics simulations involving nonradiative electronic state changes.     

Organic reactions in water or biphasic aqueous systems under sonochemical conditions. A review on catalytic effects

Catalysis in aqueous systems under sonochemical conditions has become an irreplaceable method in green synthetic chemistry after more than two decades of studies in this domain. The present review has the aim of describing the state-of-the-art with a comprehensive view of advantages and limitations as well as new potential applications. Catalytic procedures in water assisted by ultrasound and/or hydrodynamic cavitation are environmentally friendly with milder conditions, shorter reaction times and higher yields. Sonochemical processes can reduce the formation of hazardous by-products, the generation of waste and also produce energy savings. Cavitational implosion generates mechanical and chemical effects such as cleaning of catalyst surface and formation of free radicals by sonolysis of water. The present overview of sonochemical reactions in water (oxidation, bromination, aza-Michael, C–C couplings, MCR and aldol reactions) should provide useful models for furthering the progress of organic synthesis using harmless and greener sound energy.     

Electrochemistry of chlorogenic acid: experimental and theoretical studies

Cyclic voltammetry, chronoamperometry and rotating disk electrode voltammetry as well as quantum chemical methods, are used for electrochemical study of chlorogenic acid, as an important biological molecule. The standard formal potential, diffusion coefficient, and heterogeneous electron transfer rate constant of chlorogenic acid in aqueous solution are investigated. Acidic dissociation constant of chlorogenic acid is also obtained. Quantum mechanical calculations on oxidation of chlorogenic acid in aqueous solution, using density functional theory are presented. The change of Gibbs free energy and entropy of oxidation of chlorogenic acid are calculated using thermochemistry calculations. The calculations in aqueous solution are carried out with the use of polarizable continuum solvation method. Theoretical standard electrode potential of chlorogenic acid is achieved to be 0.580 V versus standard calomel electrode (SCE) which is in agreement with the experimental value of 0.617 V obtained experimentally in this work. The difference is consistent with the values we previously reported for other quinone derivatives.     

Laser-induced desorption of small molecules from oxide surfaces: A first-principles study

Recent efforts in the theoretical simulation of laser-induced desorption of small molecules from surfaces are summarized. As a representative example, photodesorption of CO molecules from a Cr₂O₃(0001) surface is investigated since detailed quantum state resolved experimental results are available for this system. In particular, vectorial properties such as the alignment of the desorbing species are considered. Furthermore, the influence of surface temperature as a control parameter is investigated, and lateral velocity distributions are calculated and compared with experimental results. All simulations presented in the present study are based on ab initio potential energy surfaces (PESs) for the electronic ground state as well as electronically excited states involved in the desorption process. These PESs provide the prerequisite for extensive high-dimensional quantum mechanical simulations of the dynamics of nuclear motion based on a stochastic wave packet scheme. These wave packet calculations allow for a detailed microscopic understanding of experimental results and provide a perspective for future experiments.     

Quantum Dots for Hybrid Energy Harvesting: From Integration to Piezo‐Phototronics

Energy harvesting, which converts wasted environmental energy into electricity by utilizing various physical effects, hasattracted tremendous research interests as is one of the key technologies to realize advanced electronics in the future. In this review, we introduce recent progress in the field of hybrid energy harvesting technology. In particular, we focus on a quantum dots (QD)‐based hybrid energy harvesting device. Attributed to fascinating material properties that QD possess, employment of QDs into hybrid energy harvesting has shown great potential for independent and sustainable energy supply.First, an integration of a QD solar cell into a mechanical energy harvester is discussed to harness different types of environmental energy sources simultaneously. Second, a comprehensive explanation of a piezotronic and piezo‐phototronic effect is provided, which is followed by QD‐based piezo‐phototronic applications. Finally, we summarize recent progress that has been made in energy harvesting technology involving a photovoltaic and piezo/triboelectric effect