Chemical Reviews最新文献

Interactions among biomacromolecules, predominantly noncovalent, underpin biological processes. However, recent advancements in biospecific chemistry have enabled the creation of specific covalent bonds between biomolecules, both in vitro and in vivo. This Review traces the evolution of biospecific chemistry in proteins, emphasizing the role of genetically encoded latent bioreactive amino acids. These amino acids react selectively with adjacent natural groups through proximity-enabled bioreactivity, enabling targeted covalent linkages. We explore various latent bioreactive amino acids designed to target different protein residues, ribonucleic acids, and carbohydrates. We then discuss how these novel covalent linkages can drive challenging protein properties and capture transient protein-protein and protein-RNA interactions in vivo. Additionally, we examine the application of covalent peptides as potential therapeutic agents and site-specific conjugates for native antibodies, highlighting their capacity to form stable linkages with target molecules. A significant focus is placed on proximity-enabled reactive therapeutics (PERx), a pioneering technology in covalent protein therapeutics. We detail its wide-ranging applications in immunotherapy, viral neutralization, and targeted radionuclide therapy. Finally, we present a perspective on the existing challenges within biospecific chemistry and discuss the potential avenues for future exploration and advancement in this rapidly evolving field.

Nanomaterial-microorganism hybrid systems (NMHSs), integrating semiconductor nanomaterials with microorganisms, present a promising platform for broadband solar energy harvesting, high-efficiency carbon reduction, and sustainable chemical production. While studies underscore its potential in diverse solar-to-chemical energy conversions, prevailing NMHSs grapple with suboptimal energy conversion efficiency. Such limitations stem predominantly from an insufficient systematic exploration of the mechanisms dictating solar energy flow. This review provides a systematic overview of the notable advancements in this nascent field, with a particular focus on the discussion of three pivotal steps of energy flow: solar energy capture, cross-membrane energy transport, and energy conversion into chemicals. While key challenges faced in each stage are independently identified and discussed, viable solutions are correspondingly postulated. In view of the interplay of the three steps in affecting the overall efficiency of solar-to-chemical energy conversion, subsequent discussions thus take an integrative and systematic viewpoint to comprehend, analyze and improve the solar energy flow in the current NMHSs of different configurations, and highlighting the contemporary techniques that can be employed to investigate various aspects of energy flow within NMHSs. Finally, a concluding section summarizes opportunities for future research, providing a roadmap for the continued development and optimization of NMHSs.

Interest in energy-to-X and X-to-energy (where X represents green hydrogen, carbon-based fuels, or ammonia) technologies has expanded the field of electrochemical conversion and storage. Solid oxide electrochemical cells (SOCs) are among the most promising technologies for these processes. Their unmatched conversion efficiencies result from favorable thermodynamics and kinetics at elevated operating temperatures (400-900 °C). These solid-state electrochemical systems exhibit flexibility in reversible operation between fuel cell and electrolysis modes and can efficiently utilize a variety of fuels. However, electrocatalytic materials at SOC electrodes remain nonoptimal for facilitating reversible operation and fuel flexibility. In this Review, we explore the diverse range of electrocatalytic materials utilized in oxygen-ion-conducting SOCs (O-SOCs) and proton-conducting SOCs (H-SOCs). We examine their electrochemical activity as a function of composition and structure across different electrochemical reactions to highlight characteristics that lead to optimal catalytic performance. Catalyst deactivation mechanisms under different operating conditions are discussed to assess the bottlenecks in performance. We conclude by providing guidelines for evaluating the electrochemical performance of electrode catalysts in SOCs and for designing effective catalysts to achieve flexibility in fuel usage and mode of operation.

Biomolecular condensates, formed through phase separation, are upending our understanding in much of molecular, cell, and developmental biology. There is an urgent need to elucidate the physicochemical foundations of the behaviors and properties of biomolecular condensates. Here we aim to fill this need by writing a comprehensive, critical, and accessible review on the fundamental aspects of phase-separated biomolecular condensates. We introduce the relevant theoretical background, present the theoretical basis for the computation and experimental measurement of condensate properties, and give mechanistic interpretations of condensate behaviors and properties in terms of interactions at the molecular and residue levels.

Understanding the crystallization of cement-binding phases, from basic units to macroscopic structures, can enhance cement performance, reduce clinker use, and lower CO₂ emissions in the construction sector. This review examines the crystallization pathways of C–S–H (the main phase in PC cement) and other alternative binding phases, particularly as cement formulations evolve toward increasing SCMs and alternative binders as clinker replacements. We adopt a nonclassical crystallization perspective, which recognizes the existence of critical intermediate steps between ions in solution and the final crystalline phases, such as solute ion associates, dense liquid phases, amorphous intermediates, and nanoparticles. These multistep pathways uncover innovative strategies for controlling the crystallization of binding phases through additive use, potentially leading to highly optimized cement matrices. An outstanding example of additive-controlled crystallization in cementitious materials is the synthetically produced mesocrystalline C–S–H, renowned for its remarkable flexural strength. This highly ordered microstructure, which intercalates soft matter between inorganic and brittle C–S–H, was obtained by controlling the assembly of individual C–S–H subunits. While large-scale production of cementitious materials by a bottom-up self-assembly method is not yet feasible, the fundamental insights into the crystallization mechanism of cement binding phases presented here provide a foundation for developing advanced cement-based materials.

The aryl O-carbamate (ArOAm) group is among the strongest of the directed metalation groups (DMGs) in directed ortho metalation (DoM) chemistry, especially in the form Ar-OCONEt₂. Since the last comprehensive review of metalation chemistry involving ArOAms (published more than 30 years ago), the field has expanded significantly. For example, it now encompasses new substrates, solvent systems, and metalating agents, while conditions have been developed enabling metalation of ArOAm to be conducted in a green and sustainable manner. The ArOAm group has also proven to be effective in the anionic ortho-Fries (AoF) rearrangement, Directed remote metalation (DreM), iterative DoM sequences, and DoM-halogen dance (HalD) synthetic strategies and has been transformed into a diverse range of functionalities and coupled with various groups through a range of cross-coupling (CC) strategies. Of ultimate value, the ArOAm group has demonstrated utility in the synthesis of a diverse range of bioactive and polycyclic aromatic compounds for various applications.

The development of microelectronics and large-scale intelligence nowadays promotes the integration, miniaturization, and multifunctionality of electronic and devices but also leads to the increment of signal transmission delays, crosstalk, and energy consumption. The exploitation of materials with low permittivity (low-k) is crucial for realizing innovations in microelectronics. However, due to the high permittivity of conventional interlayer dielectric material (k ∼ 4.0), it is difficult to meet the demands of current microelectronic technology development (k < 3.0). Organic dielectric materials have attracted much attention because of their relatively low permittivity owing to their low material density and low single bond polarization. Polyimide (PI) exhibits better application potential based on its well permittivity tunability (k = 1.1–3.2), high thermal stability (>500 °C), and mechanical property (modulus of elasticity up to 3.0–4.0 GPa). In this review, based on the synergistic relationship of dielectric parameters of materials, the development of nearly 20 years on low-k PI is thoroughly summarized. Moreover, process strategies for modifying low-k PI at the molecular level, multiphase recombination, and interface engineering are discussed exhaustively. The industrial application, technological challenges, and future development of low-k PI are also analyzed, which will provide meaningful guidance for the design and practical application of multifunctional low-k materials.

This roadmap reviews the new, highly interdisciplinary research field studying the behavior of condensed matter systems exposed to radiation. The Review highlights several recent advances in the field and provides a roadmap for the development of the field over the next decade. Condensed matter systems exposed to radiation can be inorganic, organic, or biological, finite or infinite, composed of different molecular species or materials, exist in different phases, and operate under different thermodynamic conditions. Many of the key phenomena related to the behavior of irradiated systems are very similar and can be understood based on the same fundamental theoretical principles and computational approaches. The multiscale nature of such phenomena requires the quantitative description of the radiation-induced effects occurring at different spatial and temporal scales, ranging from the atomic to the macroscopic, and the interlinks between such descriptions. The multiscale nature of the effects and the similarity of their manifestation in systems of different origins necessarily bring together different disciplines, such as physics, chemistry, biology, materials science, nanoscience, and biomedical research, demonstrating the numerous interlinks and commonalities between them. This research field is highly relevant to many novel and emerging technologies and medical applications.

Plasmon refers to the coherent oscillation of all conduction-band electrons in a nanostructure made of a metal or a heavily doped semiconductor. Upon excitation, the plasmon can decay through different channels, including nonradiative Landau damping for the generation of plasmon-induced energetic carriers, the so-called hot electrons and holes. The energetic carriers can be collected by transferring to a functional material situated next to the plasmonic component in a hybrid configuration to facilitate a range of photochemical processes for energy or chemical conversion. This article centers on the recent advancement in generating and utilizing plasmon-induced hot electrons in a rich variety of hybrid nanostructures. After a brief introduction to the fundamentals of hot-electron generation and decay in plasmonic nanocrystals, we extensively discuss how to collect the hot electrons with various types of functional materials. With a focus on plasmonic nanocrystals made of metals, we also briefly examine those based upon heavily doped semiconductors. Finally, we illustrate how site-selected growth can be leveraged for the rational fabrication of different types of hybrid nanostructures, with an emphasis on the parameters that can be experimentally controlled to tailor the properties for various applications.