Topics in Current Chemistry最新文献

To analyze chemical reaction dynamics based on a reaction path network, we have developed the “Reaction Space Projector” (ReSPer) method with the aid of the dimensionality reduction method. This program has two functions: the construction of a reduced-dimensionality reaction space from a molecular structure dataset, and the projection of dynamic trajectories into the low-dimensional reaction space. In this paper, we apply ReSPer to isomerization and bifurcation reactions of the Au₅ cluster and succeed in analyzing dynamic reaction routes involved in multiple elementary reaction processes, constructing complicated networks (called “closed islands”) of nuclear permutation-inversion (NPI) isomerization reactions, and elucidating dynamic behaviors in bifurcation reactions with reference to bundles of trajectories. Interestingly, in the second application, we find a correspondence between the contribution ratios in the ability to visualize and the symmetry of the morphology of closed islands. In addition, the third application suggests the existence of boundaries that determine the selectivity in bifurcation reactions, which was discussed in the phase space. The ReSPer program is a versatile and robust tool to clarify dynamic reaction mechanisms based on the reduced-dimensionality reaction space without prior knowledge of target reactions.

Domesticating solar energy by exploiting photovoltaic technology has become a quintessential strategy for future global energy production. Since 2015, non-fullerene organic solar cells (NF-OSC) have attracted a great deal of attention owing to the marvellous properties of non-fullerene acceptors (NFA) such as structural versability, broad absorption, suitable energy levels, tunable charge transport and morphology, leading to remarkable accomplishments in power conversion efficiency (PCE) from 1% to nearly 20%. One class of materials is provided by the fused ring aromatic indacenodithiophene (IDT) and its derivatives, which are emerging continuously as promising next-generation building blocks to construct high performance photovoltaic materials. Encouraging PCEs of more than 15% have been achieved in their binary NF-OSCs, while careful device engineering and proper amalgamation of a third component have led to PCEs of almost 18% in ternary devices. This review surveys recent developments in the area of IDT-based materials for photovoltaic applications. Different strategies to develop efficient IDT-based NFA and factors influencing the bandgaps, molecular energy levels, charge transport properties, and film morphologies, as well as the photovoltaic performance of these materials, are discussed.

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In this review, we highlight the role played by metal nanoparticles (NPs) in photocatalytic oxidation with titania as a support. This is presented in two parts, namely, partial photo-oxidation in which an organic sacrificial agent is oxidised in anaerobic conditions to produce hydrogen (photo-reforming), and photo-oxidative mineralisation of organics in aerobic conditions. We present some rules for such reactions that dictate which organic molecules can react readily, and which metals are likely to be useful for such reactions. Generally, the presence of metal NPs enhances enormously the ability of titania to yield hydrogen from photo-reforming, and a wide range of molecules can be used, including biomass. The metal NPs most used are those that are easily reduced, that is, the precious metals. The large enhancement in rate seen with metal for hydrogen production is not so extreme for the oxidation reactions, but is still significant. An important factor in all of this catalysis is the nature of the interaction between the metal NPs, which can play a multiplicity of chemical and electronic roles, and the photoactive support. A sharp dependency of rate on loading of metal is found, with maximum rates at ~0.5–2 wt% loading, depending on the metal used. The source of this dependency is the bifunctional nature of the system, in which the intimacy of both materials is crucial to performance. This rate variation is linked to the interface between the two, which is then linked to the size of the metal NPs. In fact, the rate is proportional to an area adjacent to the metal particles that we call the expanding photocatalytic area and overlap (EPAO) kinetic model. This model describes the dependence well. Rising rates with increasing coverage of particles is associated with increase in this total area but, at the maximum, these areas overlap and at higher loadings the available active area diminishes, reproducing the observed behaviour well.

RNA plays critical roles in a wide range of physiological processes. For example, it is well known that RNA plays an important role in regulating gene expression, cell proliferation, and differentiation, and many other chemical and biological processes. However, the research community still suffers from limited approaches that can be applied to readily visualize a specific RNA-of-interest (ROI). Several methods can be used to track RNAs; these rely mainly on biological properties, namely, hybridization, aptamer, reporter protein, and protein binding. With respect to covalent approaches, very few cases have been reported. Happily, several new methods for efficient labeling studies of ROIs have been demonstrated successfully in recent years. Additionally, methods employed for the detection of ROIs by RNA modifying enzymes have also proved feasible. Several approaches, namely, phosphoramidite chemistry, in vitro transcription reactions, co-transcription reactions, chemical post-modification, RNA modifying enzymes, ligation, and other methods targeted at RNA labeling have been revealed in the past decades. To illustrate the most recent achievements, this review aims to summarize the most recent research in the field of synthesis of RNAs-of-interest bearing a variety of unnatural nucleosides, the subsequent RNA labeling research via biocompatible ligation, and beyond.

We present a nonadiabatic statistical theory (NAST) package for predicting kinetics of spin-dependent processes, such as intersystem crossings, spin-forbidden unimolecular reactions, and spin crossovers. The NAST package can calculate the probabilities and rates of transitions between the electronic states of different spin multiplicities. Both the microcanonical (energy-dependent) and canonical (temperature-dependent) rate constants can be obtained. Quantum effects, including tunneling, zero-point vibrational energy, and reaction path interference, can be accounted for. In the limit of an adiabatic unimolecular reaction proceeding on a single electronic state, NAST reduces to the traditional transition state theory. Because NAST requires molecular properties at only a few points on potential energy surfaces, it can be applied to large molecular systems, used with accurate high-level electronic structure methods, and employed to study slow nonadiabatic processes. The essential NAST input data include the nuclear Hessian at the reactant minimum, as well as the nuclear Hessians, energy gradients, and spin–orbit coupling at the minimum energy crossing point (MECP) between two states. The additional computational tools included in the NAST package can be used to extract the required input data from the output files of electronic structure packages, calculate the effective Hessian at the MECP, and fit the reaction coordinate for more advanced NAST calculations. We describe the theory, its implementation, and three examples of application to different molecular systems.

In the present era of the industrial revolution, we all are familiar with ever-increasing environmental pollution released from various chemical processes. Chemical production has had a severe impact on the environment and human health. For the betterment of our environment, the chemical community has turned their interest to developing green, harmless and sustainable synthetic processes. To accomplish these goals of green chemistry, the extraordinary properties of sonication play an important role. It is well known that sonochemistry can make decisive contributions to creating high pressures of almost 1000 atm and very high temperatures in the range of 4500–5000 °C. The implementation of ultrasound in chemical transformations somehow fulfils the measures of green chemistry, as it reduces energy consumption, enhances product selectivity, and uses lesser amounts of hazardous chemicals and solvents. Furthermore, heterocyclic synthesis under ultrasonication offers several environmental and process-related advantages compared with conventional methods. The remarkable contribution of ultrasonics to the development of green and sustainable synthetic routes inspired us to write this article. Herein, we have discussed only some of the various synthetic methodologies developed for the construction of heterocyclic cores under ultrasonic irradiation, accompanied by mechanistic insights. In some cases, a comparison between sonochemical conditions and conventional conditions has also been investigated. We emphasized principally ‘up to date’ developments on various sono-accelerated chemical transformations comprising aza-Michael, aldol reactions, C–C couplings, oxidation, cycloadditions, multi-component reactions, etc. for the synthesis of heterocycles.

Captivating achievements in developing advanced hybrid biostructures through integrating natural biopolymers with inorganic materials (e.g., metals and metalloids) have paved the way towards the application of bioactive organometallic scaffolds (OMSs) in tissue engineering and regenerative medicine (TERM). Of various biopolymers, chitosan (CS) has been used widely for the development of bioactive OMSs, in large part due to its unique characteristics (e.g., biocompatibility, biodegradability, surface chemistry, and functionalization potential). In integration with inorganic elements, CS has been used to engineer advanced biomimetic matrices to accommodate both embedded cells and drug molecules and serve as scaffolds in TERM. The use of the CS-based OMSs is envisioned to provide a new pragmatic potential in TERM and even in precision medicine. In this review, we aim to elaborate on recent achievements in a variety of CS/metal, CS/metalloid hybrid scaffolds, and discuss their applications in TERM. We also provide comprehensive insights into the formulation, surface modification, characterization, biocompatibility, and cytotoxicity of different types of CS-based OMSs.

The present review article strives to compile the latest synthetic approaches for the synthesis of triazolothiadiazine and its derivatives, along with their diverse pharmacological activities, viz. anticancer, antimicrobial, analgesic and anti-inflammatory, antioxidant, antiviral, enzyme inhibitors (carbonic anhydrase inhibitors, cholinesterase inhibitors, alkaline phosphatase inhibitors, anti-lipase activity, and aromatase inhibitors) and antitubercular agents. The review focuses particularly on the structure–activity relationship of biologically important 1,2,4-triazolo[3,4-b][1,3,4]thiadiazines, which have profound importance in drug design, discovery and development. In silico pharmacokinetic and molecular modeling studies have also been summarized. It is hoped that this review article will be of help to researchers engaged in the development of new biologically active entities for the rational design and development of new target-oriented 1,2,4-triazolo[3,4-b][1,3,4]thiadiazine-based drugs for the treatment of multifunctional diseases.

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We present mixed quantum-classical approaches based on the exact factorization framework. The electron–nuclear correlation term in the exact factorization enables us to deal with quantum coherences by accounting for electronic and nuclear nonadiabatic couplings effectively within classical nuclei approximation. We compare coupled- and independent-trajectory approximations with each other to understand algorithms in description of the bifurcation of nuclear wave packets and the correct spatial distribution of electronic wave functions along with nuclear trajectories. Finally, we show numerical results for comparisons of coupled- and independent-trajectory approaches for the photoisomerization of a protonated Schiff base from excited state molecular dynamics (ESMD) simulations with the recently developed Python-based ESMD code, namely, the PyUNIxMD program.

The demand for lowering interfacial tension (IFT) in different processes has persuaded researchers to use stable and resistant surfactants with low environmental impact. For this purpose, surface-active ionic liquids (SAILs) have attracted much attention owing to their good amphiphilic nature and prominent properties like recyclability and high performance under harsh conditions. This review initially explains how the IFT and critical micelle concentration of different systems vary in the presence of different SAILs with a variety of alkyl chain lengths, head groups, and counter anions. Towards this aim, some physicochemical properties of SAILs as well as the corresponding theoretical aspects of adsorption are considered. Then, recent advances in utilizing SAILs for reducing IFT of different chemical systems are surveyed. Relevantly, the role of important operating parameters of temperature, pH, presence of electrolytes, and the chemical nature of involved phases are adequately discussed. Further, an overview of different SAILs applications in stabilization, separation, and in petroleum industries is scrutinized. To allow better judgment, precise comparisons between different types of SAILs and conventional surfactants are provided. Finally, challenges and possible directions of future research on SAILs are highlighted.