Chemical Reviews最新文献

This review chronicles rapid advances in computational approaches in high-energy-density materials (HEDMs), which display a tradeoff between performance and safety that poses challenges from molecular to system levels. We illustrate the transformative fusion of predictive theory and modern experimentation─which is driving the transition of HEDM science from empirical discovery to data-driven rational design. The analysis begins with the physics-based foundation of the field, illustrating how quantum chemistry and multiscale dynamics provide insight into stability and emergent behavior from an energetic perspective. At the heart of our analysis lies the iterative feedback loop between simulation and experimental validation, a core element of this emerging paradigm. The review ultimately frames the critical questions and opportunities that will define the future of the field, as we move toward a new generation of HEDMs that are potentially safer, more sustainable, and higher-performing energetic materials.

Vicinal amino alcohols, also called 1,2- or β-amino alcohols, are an important class of chemical modalities that may serve as chiral ligands for metal-based catalysts or as catalysts themselves and are found within numerous pharmaceutically active compounds. As such, a multitude of strategies have been adopted for their preparation, with traditional approaches leveraging diastereoselective synthesis of this scaffold based upon existing stereochemistry within a substrate. Many times, naturally occurring chiral variants or syntheses of the moiety from chiral natural sources have been utilized. Given their prominence, there have been myriad strategies developed for the catalytic enantioselective synthesis of β-amino alcohols; however, these have largely focused on the formation of secondary alcohols. In this Review, we detail the existing methods in the significantly less explored area of the catalytic enantioselective preparation of 1,2-amino tertiary alcohols and their analogues.

Stretchable ionic conductors (SICs) have been the focus of recent research due to their potential in soft electronics, bioelectronics, and flexible energy devices. A key challenge in this field is achieving a good balance between ionic conductivity and mechanical robustness, particularly in solvent-free systems where durability and long-term stability are critical. Recent progress in elastomer-based SICs has demonstrated innovative strategies to enhance performance, including the use of dynamic cross-linking, supramolecular interactions, and phase-separated networks. Materials such as poly(ionic liquid)-based elastomers (PILs), polymerizable deep eutectic solvents (PDESs), and dual-network ionogels have emerged as promising candidates, offering high stretchability, tunable conductivity, and improved mechanical strength. This review provides an overview of the design strategies and key properties of SICs, focusing on the interplay between mechanical performance and ion-transport. By analyzing recent advances in material architecture, cross-linking chemistry, and ion transport mechanisms, we highlight promising approaches for optimizing SICs for the next generation of stretchable devices.

Reversible chemistry strategies in cancer treatment and diagnosis have attracted significant attention due to their unique ability to dynamically respond to both exogenous (e.g., light, ultrasound, and magnetic fields) and endogenous (e.g., pH, redox potential, and hypoxia-normoxia) stimuli, thereby modulating the functional characteristics of materials. Reversible cancer therapy offers distinct advantages over irreversible cancer therapy including sustainable cyclic function, shape-specific function, tumor-site-specific function, tumor-specific targeting, on-demand control, deep tumor penetration, and long-term circulation and drug retention. This review comprehensively explores reversible chemistry strategies for cancer therapy and imaging, providing a comprehensive overview of utilizing multiscale (molecular-scale, nanoscale, microscale, and macroscale) materials for various reversible control mechanisms, such as electronic transitions, molecular isomerization, valence state changes, material morphology changes, and mechanical motion. Furthermore, we present various applications, advantages, and challenges of reversible chemistry in cancer therapy and imaging along with the potential for clinical applications and associated challenges. In conclusion, reversible therapeutic and diagnostic approaches offer promising avenues for precise cancer treatment and early diagnosis.

Soft materials are polymer networks that can be easily deformed by external forces. Incorporating dynamic bonds into these networks imparts various functionalities─such as self-healing, recyclability, and 3D printability─by enabling fast and reversible bond formation. However, the relatively short lifetimes of dynamic bonds compared with permanent covalent bonds can compromise the mechanical robustness of the material. This review highlights design strategies that harness dynamic bonds effectively to achieve both functionality and mechanical robustness in soft materials. We first survey the types of dynamic bonds and their characteristic lifetimes, followed by introducing analytical methods to quantify the network dynamicity. Since the required degree of dynamicity varies depending on the target functionality, we further discuss how to incorporate appropriate dynamic bonds for functionality. Through this, we aim to provide design guidelines for soft materials that combine functionalities with mechanical toughness for reliable use in advanced applications.

Vanadium oxides cystallize in a diverse array of structures and compositions arising from the redox versatility of vanadium, variable covalency of V–O bonds, and myriad coordination geometries. Their open frameworks present abundant interstitial sites that enable insertion of guest-ions. In such compounds, V3d electron and spin localization and disorder couple strongly to structural preferences. The rich structural diversity manifests as a “rugged” free energy landscape with multiple interconvertible polymorphs. Such a landscape sets up structural, electronic, and magnetic transitions that underpin the promise of these materials as ion-insertion battery electrodes; compact primitives for brain-inspired computing, and heterogeneous catalysts. Here, we examine the structural and compositional diversity, electronic instabilities, defect dynamics, structure transformations, mechanical properties, and surface structure of vanadium oxides using single crystals as a distinctive lens. Single crystals enable the measurement of structure–function correlations without the ensemble and orientational averaging inevitable in polycrystalline materials. Their well-defined surfaces further enable examination of facet-dependent reactivity toward molecular adsorbates, ion fluxes, and lattice (mis)matched solids. We provide a comprehensive account of vanadium-oxide single-crystal studies, from delineation of common structural motifs to single-crystal growth techniques, topochemical modification strategies, mechanisms underpinning electronic instabilities, and implementation as electrothermal neurons and battery electrode materials.

Monocrystalline solids have been broadly used in many fields, including batteries, electronics, and optics. Monocrystalline cathode materials have regained intensive study in recent years because of their potential to stabilize the cathode-electrolyte interphase at elevated voltages and/or reduce gassing from high capacity nickel-rich cathode materials; thus, more energy can be extracted from the same materials, except that they are converted into grain boundary-free particles, or so-called “single crystals” in the battery field. This work reviews the history, current progress, and future trends of single crystal cathodes for lithium-based batteries with a focus on cost-effective synthesis, scaleup, and manufacturing. Much work is needed to reduce manufacturing costs of single crystal cathodes, from the selection of precursors and synthesis routes to morphology control and equipment design. This review highlights the importance of cost-oriented fundamental research and processing science to accelerate battery materials manufacturing and establish a resilient manufacturing chain for versatile energy storage technologies.

Molecular dynamics simulations hold great promise for providing insight into the microscopic behavior of complex molecular systems. However, their effectiveness is often constrained by long timescales associated with rare events. Enhanced sampling methods have been developed to address these challenges, and recent years have seen a growing integration with machine learning techniques. This Review provides a comprehensive overview of how they are reshaping the field, with a particular focus on the data-driven construction of collective variables. Furthermore, these techniques have also improved biasing schemes and unlocked novel strategies via reinforcement learning and generative approaches. In addition to methodological advances, we highlight applications spanning different areas, such as biomolecular processes, ligand binding, catalytic reactions, and phase transitions. We conclude by outlining future directions aimed at enabling more automated strategies for rare-event sampling.

Carbonylation reactions constitute one of the most powerful and widely utilized strategies for synthesizing carbonyl-containing compounds in organic chemistry. Among the mechanistic pathways explored, two-electron transfer (TET) processes have been extensively developed and industrially applied. However, besides their obvious advantages, their intrinsic limitations, such as reliance on precious metal catalysts and restricted compatibility with alkyl substrates, have prompted increasing interest in single-electron transfer (SET) alternatives. Alternatively, SET-mediated carbonylation bypasses the traditional oxidative addition step, generating highly reactive radical intermediates under milder reaction conditions, thus providing enhanced selectivity and broader substrate compatibility. This review offers a comprehensive overview of SET-mediated carbonylation chemistry from 2000 to July 2025, emphasizing mechanistic insights, catalytic systems, and synthetic applications. The objective is to establish a conceptual foundation for understanding recent advances and inspire further exploration into novel reactivity paradigms based on SET strategies within the realm of carbonylation chemistry.