Chemical Reviews最新文献

CO₂ reduction using renewable H₂ represents an emerging approach for minimizing dependency on fossil fuels and reducing the carbon footprint while providing chemicals and fuels. In this context, CO₂ hydrogenation using Fe-based oxide, which exhibits outstanding capabilities in both reverse water gas shift (RWGS) and Fischer–Tropsch synthesis (FTS) reactions, integrated with zeolite has been a promising method for heavy hydrocarbon (C₅₊) production. This review investigates the critical roles of promoter, zeolite topology and acidity, and synthesis methods in optimizing product distribution and their contributions to active site proximity. It has been found that the catalyst integration manner and the interaction between the basic sites of Fe-based oxide and the acidic sites of zeolites significantly influence catalytic performance. In addition, the proximity of active sites, a crucial factor in tandem catalysis, can be controlled via different catalyst synthesis methods, dispersion on mesoporous supports, or using encapsulated structures that can provide the confinement effect while guiding the reaction sequence. Furthermore, the choice of alkali promoters (Na vs K) is very important since each can alter electronic properties, reduction behavior, and hydrocarbon distribution due to different electronegativity and ionic radii. While Na could hamper all reduction steps and diffuses into bulk iron oxide, K remains mainly on the surface, increasing electron density and facilitating iron carbide formation. Besides, integrating spectroscopic imaging techniques with proximity metrics will enhance the understanding of active site spatial distribution. To bridge the gap between lab-scale results and industrial applications, advanced computational methods coupled with artificial intelligence (AI) and machine learning (ML) techniques are required to monitor and analyze catalyst behavior and optimize large-scale production. The findings of this study provide a comprehensive understanding of catalyst design principles with emphasis on the importance of the proximity of active sites, offering insights for the next generation of efficient CO₂ hydrogenation catalysts for industrial-scale fuel production.

The active sites at the unliganded forms of many of Nature’s most proficient catalysts of metabolic reactions do not show a good fit for the enzymatic transition state; this fit is created by utilization of substrate binding energy to drive protein conformational changes that move side chains to positions that provide optimal transition-state stabilization. Static protein X-ray crystal structures of enzyme Michaelis complexes provide a critical starting point for determination of the roles of these side chains in stabilizing the enzymatic transition state but provide little insight into the catalytic role of the substrate-driven protein conformational change. Important elements of the mechanism of action of nature’s most proficient enzyme catalysts are therefore only revealed after examination of the structure for unliganded enzyme active sites and their substrate-driven transformations to structured forms that are complementary to reaction transition states. There have been few studies to determine the effect on enzyme activity of site-directed substitution of protein side chains that participate in substrate-driven enzyme conformational changes. The fascinating effects of these substitutions were probed by site-directed substitution of amino acid side chains that take part in conformational changes during catalysis by triosephosphate isomerase, glycerol phosphate dehydrogenase, and orotidine 5′-monophosphate decarboxylase.

Circularly polarized luminescence (CPL)─the emission of circularly polarized light from luminescent chiral nonracemic matter─has garnered unprecedented attention in the past decade. Once a niche technique used for the characterization of excited states, CPL has evolved to a powerful and widespread tool for developing functional materials with multiple applications. The development of novel CPL emitters is costly and time-consuming because the key CPL quantities (dissymmetry factor, g_lum, and CPL brightness, B_CPL) often elude simple structure-to-property relationships based on existing knowledge. Today, research in the field is aided by quantum chemistry calculations which offer insight into CPL properties and serve as a predictive tool for the rational design of efficient CPL-active materials. The present review is divided into three sections: (1) a comprehensive presentation of the theoretical foundation of CPL calculations, electronic structure description, environment effects, vibronic modulation, band shape broadening, and aggregate simulation; (2) an extensive literature survey, organized according to a structural criterion; and (3) a critical reassessment of literature data, accompanied by a statistical analysis, aimed at offering the best practices for accurate CPL calculations and identifying the key structural and electronic features that enable the simulation-guided design of novel CPL emitters.

Crystallization-driven self-assembly (CDSA) offers precise control over the size, shape, and hierarchical organization of polymeric nanostructures by harnessing the crystallization of a core-forming block. Unlike conventional self-assembly, CDSA favors the formation of low-curvature morphologies, such as fibers and platelets, with exceptional uniformity. This review highlights key CDSA strategies, including seeded growth, self-seeding, and polymerization-induced CDSA, along with factors influencing assembly, such as polymer composition, solvent, temperature, and additives. We summarize advanced characterization techniques─spanning light scattering, microscopy, spectroscopy and fluorescence imaging─and computational approaches, including Monte Carlo and Brownian dynamics simulations, for understanding assembly mechanisms and predicting morphologies. Finally, we discuss emerging applications in biomedicine, catalysis, optoelectronics, and functional materials, and outline future challenges in precision control, multitechnique characterization, and scalable synthesis. By integrating mechanistic insights, advanced characterization, and application-driven design, this review establishes a comprehensive foundation for future development of CDSA-based functional materials.

RNA splicing is orchestrated by a complex and exceptionally dynamic RNA–protein machine, called the spliceosome. Stepwise, large-scale structural and compositional remodeling of the spliceosome enables splicing and ensures its fidelity. While cryogenic electron microscopy provided structural information on numerous splicing cycle intermediates, allowing large-scale rearrangements to be inferred on a comparative basis, all-atom simulations complement and enrich structural studies by capturing the dynamic nature of the spliceosome on a finer but equally important scale. Here, we review the current understanding of the spliceosome’s function attained by enriching experimental insights with computation. We focus on splicing factors mediating the spliceosome’s dynamic behavior, key for splicing cycle progression, and discuss computational challenges on the path toward more accurate large-scale simulations that could further bridge the gap between computational and experimental data. A synergistic interplay between experiment and computation is vital for obtaining high-accuracy structural ensembles of the spliceosome and its components and for addressing unresolved mechanistic and biological questions related to splicing. Such integrative approaches also hold promise for advancing the design of splicing-targeted therapeutics and gene modulation technologies for treating diseases linked to splicing dysregulation.

The piezoelectric effect enables the conversion between electrical and mechanical energy, making it essential across various fields. While synthetic piezoelectric ceramics and polymers are extensively utilized in electronics and biomedicine, their inherent rigidity, fragility, processing challenges, toxicity, and nondegradability limit their potential. In contrast, piezoelectric biomaterials offer a promising alternative for biomedical fields because of their natural biocompatibility, biodegradability, and environmental friendliness. However, weak piezoelectricity and challenges in large-scale fabrication hinder their applications. This paper critically reviews recent advances in piezoelectric biomaterials, focusing primarily on design strategies and manufacturing methods. We first summarize the principles, advantages, and categories of a variety of piezoelectric biomaterials. Next, we explore computational studies, highlight emerging approaches in molecular engineering and manufacturing, and examine their cutting-edge applications in bioelectronics and biomedicine. Additionally, we evaluate the effectiveness of various design and manufacturing approaches in enhancing piezoelectric performance, outlining their respective advantages and limitations. Finally, we discuss key challenges and provide insights into computational modeling, fabrication techniques, characterization methods, and biomedical applications to guide future research.

The growing demand for ever-higher-energy-density Li-ion batteries has accelerated the development of Ni-rich transition metal (TM) oxide cathodes. Despite their potential, unsolved degradation mechanisms continue to limit their practical capacity and cycle life. Single-crystalline morphologies have emerged as a promising solution, offering superior mechanical and structural stability compared to polycrystalline cathodes. Nevertheless, degradation still occurs, driven by atomic-scale instabilities, interfacial side reactions, and particle-level mechanical strain. To address these challenges, this review systematically examines cathode development from the atomic to cell level and provides critical insight into how different material design strategies can enhance long-term performance.

Sodium/potassium-ion storage devices have ushered in a turning point in development, becoming a new trend in energy storage devices after lithium-ion batteries (LIBs). Carbonaceous material, as a very promising negative electrode for sodium- and potassium-ion storage electrodes, has been widely studied and applied. Clarifying the energy storage mechanism of carbonaceous materials to guide the controllable synthesis of carbon is a key issue in carbon science. Electrochemical behavior is usually the most intuitive representation of the understanding of the mechanism and structural changes of material energy storage. Obtaining the regularity information on carbonaceous materials from electrochemical characteristic curves is a valuable consideration. In order to comprehensively and profoundly understand the structural properties of carbonaceous materials and the electrochemical reaction regularity characteristics brought about by carbon structure changes, this review starts with modeling electrochemical curves, systematically summarizes the structural characteristics of carbonaceous materials corresponding to each model and analyzes the transformation regulation among models, providing comprehensive insights and guidance for mastering the sodium/potassium-ion storage characteristics of carbonaceous materials. The preparation, modification, and large-scale application of carbonaceous materials have been systematically summarized. In addition, our perspectives on the future development of carbonaceous materials for energy storage applications are provided.