Semenov Institute of Chemical Physics

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTActivation of C−H Bonds by Metal ComplexesAlexander E. Shilov and Georgiy B. Shul'pinView Author Information N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow, Russia Cite this: Chem. Rev. 1997, 97, 8, 2879–2932Publication Date (Web):December 18, 1997Publication History Received12 August 1996Revised8 July 1997Published online18 December 1997Published inissue 1 December 1997https://pubs.acs.org/doi/10.1021/cr9411886https://doi.org/10.1021/cr9411886research-articleACS PublicationsCopyright © 1997 American Chemical SocietyRequest reuse permissionsArticle Views65526Altmetric-Citations2615LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Alkyls,Aromatic compounds,Hydrocarbons,Metals,Oxidation Get e-Alerts

ATSAS is a comprehensive software suite for the analysis of small-angle scattering data from dilute solutions of biological macromolecules or nanoparticles. It contains applications for primary data processing and assessment, ab initio bead modelling, and model validation, as well as methods for the analysis of flexibility and mixtures. In addition, approaches are supported that utilize information from X-ray crystallography, nuclear magnetic resonance spectroscopy or atomistic homology modelling to construct hybrid models based on the scattering data. This article summarizes the progress made during the 2.5–2.8 ATSAS release series and highlights the latest developments. These include AMBIMETER , an assessment of the reconstruction ambiguity of experimental data; DATCLASS , a multiclass shape classification based on experimental data; SASRES , for estimating the resolution of ab initio model reconstructions; CHROMIXS , a convenient interface to analyse in-line size exclusion chromatography data; SHANUM , to evaluate the useful angular range in measured data; SREFLEX , to refine available high-resolution models using normal mode analysis; SUPALM for a rapid superposition of low- and high-resolution models; and SASPy , the ATSAS plugin for interactive modelling in PyMOL . All these features and other improvements are included in the ATSAS release 2.8, freely available for academic users from https://www.embl-hamburg.de/biosaxs/software.html.

The aim of this review article on recent developments of mechanochemistry (nowadays established as a part of chemistry) is to provide a comprehensive overview of advances achieved in the field of atomistic processes, phase transformations, simple and multicomponent nanosystems and peculiarities of mechanochemical reactions. Industrial aspects with successful penetration into fields like materials engineering, heterogeneous catalysis and extractive metallurgy are also reviewed. The hallmarks of mechanochemistry include influencing reactivity of solids by the presence of solid-state defects, interphases and relaxation phenomena, enabling processes to take place under non-equilibrium conditions, creating a well-crystallized core of nanoparticles with disordered near-surface shell regions and performing simple dry time-convenient one-step syntheses. Underlying these hallmarks are technological consequences like preparing new nanomaterials with the desired properties or producing these materials in a reproducible way with high yield and under simple and easy operating conditions. The last but not least hallmark is enabling work under environmentally friendly and essentially waste-free conditions (822 references).

We study energy pumping in an impulsively excited, two-degrees-of-freedom damped system with essential (nonlinearizable) nonlinearities by means of two analytical techniques. First, we transform the equations of motion using the action-angle variables of the underlying Hamiltonian system and bring them into the form where two-frequency averaging can be applied. We then show that energy pumping is due to resonance capture in the 1:1 resonance manifold of the system, and perform a perturbation analysis in an Oε neighborhood of this manifold in order to study the attracting region responsible for the resonance capture. The second method is based on the assumption of 1:1 internal resonance in the fast dynamics of the system, and utilizes complexification and averaging to develop analytical approximations to the nonlinear transient responses of the system in the energy pumping regime. The results compare favorably to numerical simulations. The practical implications of the energy pumping phenomenon are discussed.

The systems considered in this work are composed of weakly coupled, linear and essentially nonlinear (nonlinearizable) components. In Part I of this work we present numerical evidence of energy pumping in coupled nonlinear mechanical oscillators, i.e., of one-way (irreversible) “channeling” of externally imparted energy from the linear to the nonlinear part of the system, provided that the energy is above a critical level. Clearly, no such phenomenon is possible in the linear system. To obtain a better understanding of the energy pumping phenomenon we first analyze the dynamics of the underlying Hamiltonian system (corresponding to zero damping). First we reduce the equations of motion on an isoenergetic manifold of the dynamical flow, and then compute subharmonic orbits by employing nonsmooth transformation of coordinates which lead to nonlinear boundary value problems. It is conjectured that a 1:1 stable subharmonic orbit of the underlying Hamiltonian system is mainly responsible for the energy pumping phenomenon. This orbit cannot be excited at sufficiently low energies. In Part II of this work the energy pumping phenomenon is further analyzed, and it is shown that it is caused by transient resonance capture on a 1:1 resonance manifold of the system.

In this review we consider the effects of endogenous and pharmacological levels of nitrite under conditions of hypoxia. In humans, the nitrite anion has long been considered as metastable intermediate in the oxidation of nitric oxide radicals to the stable metabolite nitrate. This oxidation cascade was thought to be irreversible under physiological conditions. However, a growing body of experimental observations attests that the presence of endogenous nitrite regulates a number of signaling events along the physiological and pathophysiological oxygen gradient. Hypoxic signaling events include vasodilation, modulation of mitochondrial respiration, and cytoprotection following ischemic insult. These phenomena are attributed to the reduction of nitrite anions to nitric oxide if local oxygen levels in tissues decrease. Recent research identified a growing list of enzymatic and nonenzymatic pathways for this endogenous reduction of nitrite. Additional direct signaling events not involving free nitric oxide are proposed. We here discuss the mechanisms and properties of these various pathways and the role played by the local concentration of free oxygen in the affected tissue.

In the last decade, the use of multivariate statistical techniques developed for analytical chemistry has been adopted widely in food science and technology. Usually, chemometrics is applied when there is a large and complex dataset, in terms of sample numbers, types, and responses. The results are used for authentication of geographical origin, farming systems, or even to trace adulteration of high value-added commodities. In this article, we provide an extensive practical and pragmatic overview on the use of the main chemometrics tools in food science studies, focusing on the effects of process variables on chemical composition and on the authentication of foods based on chemical markers. Pattern recognition methods, such as principal component analysis and cluster analysis, have been used to associate the level of bioactive components with in vitro functional properties, although supervised multivariate statistical methods have been used for authentication purposes. Overall, chemometrics is a useful aid when extensive, multiple, and complex real-life problems need to be addressed in a multifactorial and holistic context. Undoubtedly, chemometrics should be used by governmental bodies and industries that need to monitor the quality of foods, raw materials, and processes when high-dimensional data are available. We have focused on practical examples and listed the pros and cons of the most used chemometric tools to help the user choose the most appropriate statistical approach for analysis of complex and multivariate data.

The skin is the largest organ of the body, which meets the environment most directly. Thus, the skin is vulnerable to various damages, particularly burn injury. Skin wound healing is a serious interaction between cell types, cytokines, mediators, the neurovascular system, and matrix remodeling. Tissue regeneration technology remarkably enhances skin repair via re-epidermalization, epidermal-stromal cell interactions, angiogenesis, and inhabitation of hypertrophic scars and keloids. The success rates of skin healing for burn injuries have significantly increased with the use of various skin substitutes. In this review, we discuss skin replacement with cells, growth factors, scaffolds, or cell-seeded scaffolds for skin tissue reconstruction and also compare the high efficacy and cost-effectiveness of each therapy. We describe the essentials, achievements, and challenges of cell-based therapy in reducing scar formation and improving burn injury treatment.

Transcranial magnetic stimulation (TMS) is an effective method used to diagnose and treat many neurological disorders. Although repetitive TMS (rTMS) has been used to treat a variety of serious pathological conditions including stroke, depression, Parkinson's disease, epilepsy, pain, and migraines, the pathophysiological mechanisms underlying the effects of long-term TMS remain unclear. In the present review, the effects of rTMS on neurotransmitters and synaptic plasticity are described, including the classic interpretations of TMS effects on synaptic plasticity via long-term potentiation and long-term depression. We also discuss the effects of rTMS on the genetic apparatus of neurons, glial cells, and the prevention of neuronal death. The neurotrophic effects of rTMS on dendritic growth and sprouting and neurotrophic factors are described, including change in brain-derived neurotrophic factor concentration under the influence of rTMS. Also, non-classical effects of TMS related to biophysical effects of magnetic fields are described, including the quantum effects, the magnetic spin effects, genetic magnetoreception, the macromolecular effects of TMS, and the electromagnetic theory of consciousness. Finally, we discuss possible interpretations of TMS effects according to dynamical systems theory. Evidence suggests that a rTMS-induced magnetic field should be considered a separate physical factor that can be impactful at the subatomic level and that rTMS is capable of significantly altering the reactivity of molecules (radicals). It is thought that these factors underlie the therapeutic benefits of therapy with TMS. Future research on these mechanisms will be instrumental to the development of more powerful and reliable TMS treatment protocols.

Synthesis of cationic plastoquinone derivatives (SkQs) containing positively charged phosphonium or rhodamine moieties connected to plastoquinone by decane or pentane linkers is described. It is shown that SkQs (i) easily penetrate through planar, mitochondrial, and outer cell membranes, (ii) at low (nanomolar) concentrations, posses strong antioxidant activity in aqueous solution, BLM, lipid micelles, liposomes, isolated mitochondria, and cells, (iii) at higher (micromolar) concentrations, show pronounced prooxidant activity, the "window" between anti- and prooxidant concentrations being very much larger than for MitoQ, a cationic ubiquinone derivative showing very much lower antioxidant activity and higher prooxidant activity, (iv) are reduced by the respiratory chain to SkQH2, the rate of oxidation of SkQH2 being lower than the rate of SkQ reduction, and (v) prevent oxidation of mitochondrial cardiolipin by OH*. In HeLa cells and human fibroblasts, SkQs operate as powerful inhibitors of the ROS-induced apoptosis and necrosis. For the two most active SkQs, namely SkQ1 and SkQR1, C(1/2) values for inhibition of the H2O2-induced apoptosis in fibroblasts appear to be as low as 1x10(-11) and 8x10(-13) M, respectively. SkQR1, a fluorescent representative of the SkQ family, specifically stains a single type of organelles in the living cell, i.e. energized mitochondria. Such specificity is explained by the fact that it is the mitochondrial matrix that is the only negatively-charged compartment inside the cell. Assuming that the Deltapsi values on the outer cell and inner mitochondrial membranes are about 60 and 180 mV, respectively, and taking into account distribution coefficient of SkQ1 between lipid and water (about 13,000 : 1), the SkQ1 concentration in the inner leaflet of the inner mitochondrial membrane should be 1.3x10(8) times higher than in the extracellular space. This explains the very high efficiency of such compounds in experiments on cell cultures. It is concluded that SkQs are rechargeable, mitochondria-targeted antioxidants of very high efficiency and specificity. Therefore, they might be used to effectively prevent ROS-induced oxidation of lipids and proteins in the inner mitochondrial membrane in vivo.

A new method is proposed to detect ultrasonic vibration of the samples in the Atomic Force Microscope (AFM) using nonlinearity in the tip-sample interaction force curve F ( z ). Small amplitude ultrasonic vibration less than 0.2 nm is detected as an average displacement of a cantilever. This Ultrasonic Force Mode (UFM) of operation is advantageous in detecting ultrasonic vibration with frequencies up to the GHz range, using an AFM cantilever with a resonant frequency below 100 kHz. It was found that a strong repulsive force is acting after an ultrasonic amplitude threshold of the is crossed, with the amplitude of this threshold depending upon the average force applied to the tip.

We establish the equivalence of 2D contour dynamics to the dispersionless limit of the integrable Toda hierarchy constrained by a string equation. Remarkably, the same hierarchy underlies 2D quantum gravity.

Articular hyaline cartilage is extensively hydrated, but it is neither innervated nor vascularized, and its low cell density allows only extremely limited self-renewal. Most clinical and research efforts currently focus on the restoration of cartilage damaged in connection with osteoarthritis or trauma. Here, we discuss current clinical approaches for repairing cartilage, as well as research approaches which are currently developing, and those under translation into clinical practice. We also describe potential future directions in this area, including tissue engineering based on scaffolding and/or stem cells as well as a combination of gene and cell therapy. Particular focus is placed on cell-based approaches and the potential of recently characterized chondro-progenitors; progress with induced pluripotent stem cells is also discussed. In this context, we also consider the ability of different types of stem cell to restore hyaline cartilage and the importance of mimicking the environment in vivo during cell expansion and differentiation into mature chondrocytes.

The state of the art and the major trends of development of world energy engineering are analyzed. It is concluded that throughout the 21st century the role of alternative sources will remain rather modest. Fossil fuel will still be the major source of energy until the end of the century. Because of depletion of accessible oil resources, the proportion of crude oil in the world energy balance will constantly decline, while the proportion of natural gas will grow. It is shown that energy production from any source, including alternative sources, cannot be environmentally benign if the scale of production is large. In the long term, humanity has no sources other than fusion energy, but transition to this source would not solve the problem of the planet's heat balance.The bibliography includes 70 references.

This brief review describes recent findings by the author and his co-workers in the field of catalytic systems for the oxidation of saturated and aromatic hydrocarbons with molecular oxygen (from air), hydrogen peroxide and some other compounds. These systems are based on metal complexes as catalysts and often include obligatory co-catalysts, such as amino acids, nitrogen-containing bases or weak carboxylic acids. Some of these reactions can be considered as biomimetic models of corresponding oxidation processes occurring in living cells. In some cases, aerobic oxidations considered here occur in some cases under the action of light. Some features of these reactions and their mechanisms are presented and discussed.

Molecular transformation (chemical reaction) as an electron−nuclear rearrangement of the reactants into the products is the heart of chemistry, the central event which all chemistry circulates about. It is selective to the nuclei, both in mass and spin. Nuclear mass selectivity of reactions results in classical isotope effect (CIE), the remarkable phenomenon which continues to play a unique role and has served served for many years as a powerful and reliable tool of mechanistic chemistry and biochemistry. Another breakthrough of similar scale and importance is the discovery of nuclear spin selectivity of chemical reactions, which is the dependence of the reaction rates on the nuclear spin and nuclear magnetic moment of the reactants. In contrast to CIE, which is governed by chemical energy of the starting and transition states of reactant molecules, this new isotope effect is controlled by magnetic interactions, so it was christened the magnetic isotope effect (MIE). The general principles of tuning of the reactions to MIE are discussed, particularly by microwaves, tunable on frequency and amplitude, to selectively modify and control chemical reactivity.

We demonstrate that p-adic analysis is a natural basis for the construction of a wide variety of the ultrametric diffusion models constrained by hierarchical energy landscapes. A general analytical description in terms of p-adic analysis is given for a class of models. Two exactly solvable examples, i.e. the ultrametric diffusion constraned by the linear energy landscape and the ultrametric diffusion with reaction sink, are considered. We show that such models can be applied to both the relaxation in complex systems and the rate processes coupled to rearrangenment of the complex surrounding.

The process of heat conduction in a chain with a periodic potential of nearest-neighbor interaction is investigated by means of molecular dynamics simulation. It is demonstrated that the periodic potential of nearest-neighbor interaction allows one to obtain normal heat conductivity in an isolated one-dimensional chain with conserved momentum. The system exhibits a transition from infinite to normal heat conductivity with the growth of its temperature. The physical reason for normal heat conductivity is the excitation of high-frequency stationary localized rotational modes. These modes absorb the momentum and facilitate locking of the heat flux.

The present paper deals with important differences in the distribution of free volume in high and low free volume polymers as indicated by a joint investigation utilizing molecular modeling and positron annihilation lifetime studies. The main focus of this paper is on the molecular modeling approach. The polymers in question are the ultrahigh free volume polymer poly(1-(trimethylsilyl)-1-propyne) (PTMSP) and two polystyrene derivatives containing Si and F. Extended equilibration procedures were necessary to obtain reasonable packing models for the polymers. The transition state Gusev−Suter Monte Carlo method was utilized to prove a reasonable agreement between simulated and measured diffusivity and solubility values for the model structures. The free volume distribution was analyzed for the validated packing models and compared with respective positron annihilation data. In both cases, a bimodal distribution of free volume was observed for PTMSP while the polystyrene derivatives as other conventional glassy polymers showed a more or less monomodal behavior. Good qualitative agreement is demonstrated between size distributions of free volume elements in these polymers obtained via molecular computer modeling and experiments using positron annihilation technique.

The regularities of the reaction of aminopolysaccharide chitosan with glutaraldehyde (GA) have been considered. The equilibrium forms of GA in water have been thoroughly studied by NMR spectroscopy. It has been established that at pH 5.6, the exchange of the protons of O=CHCH2 groups for deuterium occurs, indicating the presence of an anion, a product of the first stage of the aldol reaction; at pH > 7.2, the formation of the products of an aldol reaction and aldol condensation takes place. The kinetics of the reaction between the amino groups of chitosan and GA, the kinetics of gel formation in chitosan solutions in the presence of GA, and the kinetics of changes in the rigidity of gels formed have been studied by UV spectroscopy. IR spectra of cross-linked chitosan have been obtained. It has been shown that chitosan catalyzes the polymerization of GA to form irregular products; in this process, the length of oligomeric chains in modified or cross-linked chitosan and the concentration of conjugated bonds increase with the GA concentration and pH of the reaction medium.