{"title":"Programmed photocontrol of polymer materials with multiple stimuli for fabrication and degradation","authors":"Hiroshi Masai","doi":"10.1039/d6cs01019a","DOIUrl":"https://doi.org/10.1039/d6cs01019a","url":null,"abstract":"Light-induced synthesis, degradation, and processing of polymer materials are powerful technologies in materials science that exploit the exceptional spatiotemporal resolution of light to achieve precise material control. Recently, the integration of precision synthetic chemistry with polymer materials science has led to the emergence of a new generation of photocontrol technologies. Such systems go beyond conventional, simple light-triggered approaches by employing multiple wavelengths of light, integrating light with multiple other stimuli that act independently, and implementing cooperative systems in which light and additional stimuli act in concert. Through such sophisticated designs, both bond formation and cleavage within polymer backbones can be precisely regulated, enabling unprecedented manipulation of polymer materials. These advances have unlocked diverse applications, ranging from functional materials for on-demand control of material degradation and adhesion to high-resolution microfabrication technologies, such as photolithography and photoprinting, as well as biotechnological fields, including drug delivery and control of cellular behavior. This Review highlights recent progress in polymer materials endowed with “programmed” photocontrol, focusing on emerging methodologies that enable polymers to be fabricated and degraded at desired locations and times. These advances offer an overarching perspective on the design and application of multi-stimuli photocontrol for creating next-generation polymer systems with advanced and programmable functionalities.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":"53 1","pages":""},"PeriodicalIF":46.2,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173219","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Metal–organic frameworks based on macrocycles: from design to function","authors":"Junyu Ren,Joshua Phipps,Shengqian Ma,Jian Tian","doi":"10.1039/d6cs00546b","DOIUrl":"https://doi.org/10.1039/d6cs00546b","url":null,"abstract":"Metal–organic frameworks (MOFs) built from macrocyclic building blocks stand at the intersection of two Nobel-Prize-recognized traditions. Within such lattices, the framework amplifies individual molecular events into bulk material properties through periodic replication and geometric control allowing for recognition, gating, or catalytic specificity that conventional linkers struggle to bestow. The solid-state host–guest behaviour of these hybrid materials diverges from their homogeneous counterparts in solution. The lattice locks cavity conformations to sharpen selectivity, fixes orientations to enable cooperative multisite binding, and combines discrete recognition events with collective responses in conductivity, luminescence, or mass transport. This interplay has already led to macrocyclic MOFs whose performance surpasses that of both parent components. Despite rapid progress, the field still lacks a systematic way of relating macrocyclic properties to material function. Conceptualizing and realizing the full potential of these materials therefore demands a coherent understanding of how macrocycle characteristics dictate reticular compatibility, how synthetic mechanisms govern cavity accessibility, and how these aspects jointly determine function. This review develops that integrated understanding in stages: the physicochemical attributes that matter for the material's reticular nature, the synthetic logic that weaves macrocycles into periodic frameworks, and the emergent performance these architectures deliver. It concludes by outlining the frontiers where macrocyclic MOFs may transition from laboratory proof-of-concept to engineered technology.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":"27 1","pages":""},"PeriodicalIF":46.2,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Annah J. Wilson,Ehsan Sadeghi,Niccolò Silvestri,Eleonora Giannotta,Diba Farmanbordar,Giuseppe Maruccio,Teresa Pellegrino
{"title":"Magnetic induction heating: where will the field go next?","authors":"Annah J. Wilson,Ehsan Sadeghi,Niccolò Silvestri,Eleonora Giannotta,Diba Farmanbordar,Giuseppe Maruccio,Teresa Pellegrino","doi":"10.1039/d5cs01155h","DOIUrl":"https://doi.org/10.1039/d5cs01155h","url":null,"abstract":"Under the broader concept of magnetic induction (MI), in which magnetic fields are used to induce a current in conductors, magnetic induction heating (MIH) is known in oncotherapy for tumour ablation in what is called magnetic hyperthermia. However, a multitude of wider applications of MIH are beginning to shape opportunities at the interface of materials fabrication. This includes organic and inorganic synthesis, a comprehensive spectrum of biomedical needs, sensing, diagnostics, industrial processing, sustainable technologies, power generation and locomotion. A comparative analysis of reported MI studies is given grouped by application type, providing insight into the different materials employed and temperatures achieved. While MIH is predominantly based on magnetic materials that dissipate energy through hysteresis and Néel/Brownian relaxation losses, electrically conductive materials can also generate heat via eddy-current-induced Joule heating, although they remain relatively underexplored in biomedical applications. We examine the field parameters, the set-ups used and experimental configurations to provide a clear overview of the current landscape. In chemistry these applications will interest researchers in areas such as materials synthesis, electrocatalysis and sustainable chemistry. In the biomedical landscape, we explore studies from neuropathology to endometriosis and ocular disease, and even dental applications. Thus, we enable both specialists and researchers from adjacent fields to contribute with fresh perspectives. This review examines MIH through a new lens, highlighting underrepresented and recent developments and identifying promising directions to accelerate progress across different areas of science.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":"293 1","pages":""},"PeriodicalIF":46.2,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172441","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Large-scale first-principles electronic structure methods","authors":"Weiqing Zhou,Zhichang Fu,Shengjun Yuan","doi":"10.1039/d6cs00665e","DOIUrl":"https://doi.org/10.1039/d6cs00665e","url":null,"abstract":"First-principles electronic structure methods provide a quantum-mechanically grounded route to describing microscopic matter, but their application to structurally complex and large-scale systems is constrained by global operations whose cost usually scales cubically or worse. Linear-scaling electronic-structure methods seek to overcome this bottleneck by exploiting locality, or nearsightedness, in electronic matter. Their practical performance, however, is not determined by formal scaling alone. It depends on how local representations are reconciled with global fermionic constraints, including orthogonality, idempotency, and electron-number conservation, as well as with numerical prefactors, accuracy control, and implementation details. This review uses this locality-constraint balance as a guiding principle to revisit recent advances in large-scale first-principles methods. Fragment-based schemes, direct expansion and purification approaches, local subspace projection, stochastic representations, and variational optimization methods are discussed in terms of mathematical foundations, favorable regimes, limiting cases, and open challenges. Special attention is given to stochastic methods, which replace part of the deterministic enforcement of global constraints with controlled statistical averaging and thereby provide a complementary route to ultra-large systems. Linear-scaling treatments of long-range Coulomb interactions and exact exchange are also reviewed, together with their implications for hybrid-functional and many-body calculations. The review further examines how exascale computing, artificial intelligence, and quantum computing are broadening the routes to large-scale first-principles simulations. Exascale computing provides a hardware-driven path to larger systems and reshapes the practical implementation of linear-scaling algorithms, whereas artificial intelligence and quantum computing introduce learned or hybrid paradigms that may compete with, complement, or interface with traditional linear-scaling theory. By connecting algorithmic principles, practical applicability, and emerging interfaces, this article provides a framework for assessing the current status and future development of large-scale first-principles simulations.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":"14 1","pages":""},"PeriodicalIF":46.2,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Surface area determination of porous materials: the BET approach, its limitations, and alternatives","authors":"Jui Tu,Szu-Chia Chien,Li-Chiang Lin","doi":"10.1039/d6cs00693k","DOIUrl":"https://doi.org/10.1039/d6cs00693k","url":null,"abstract":"Surface area is a key property in the characterization of porous materials, and it strongly influences their performance in a variety of applications such as gas storage and separation. To quantify such a textural property, the Brunauer–Emmett–Teller (BET) method has been the most widely used approach, based on gaseous adsorption isotherms of non-reactive gases such as N2 at 77 K and Ar at 87 K. Despite its widespread use, the physical validity and reliability of the BET method for porous materials remain subjects of active debate. These include the selection of the linear region used to compute the BET surface area, violations of its fundamental assumptions (e.g., pore filling in porous materials), and sensitivity to the choice of adsorbates as probe molecules (e.g., N2vs. Ar). By integrating insights from both experimental and computational developments over the past decades, this review comprehensively evaluates the applicability and limitations of the BET method across diverse porous materials. Specifically, current understanding of surface-area determination in porous materials is summarized, including how pore structure, adsorption mechanisms, adsorbate choice, and analysis protocols influence the BET-derived surface area, thereby offering best practices for the BET approach. In addition, this review synthesizes insights into conditions under which the BET analysis may become fundamentally unreliable. A variety of alternative approaches that have been developed to enable more consistent, comparable, and physically meaningful surface-area characterizations are also highlighted. Finally, this review outlines key future directions toward achieving more accurate surface-area characterizations.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":"83 1","pages":""},"PeriodicalIF":46.2,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yizhou Wang, Shuo Li, Dekang Zhu, Ning Chu, Amna Rayan, Noor Albar, Tianchao Guo, Dana Alsulaiman, Husam N Alshareef
{"title":"Inter-flake modulation of MXenes for advanced sensing applications.","authors":"Yizhou Wang, Shuo Li, Dekang Zhu, Ning Chu, Amna Rayan, Noor Albar, Tianchao Guo, Dana Alsulaiman, Husam N Alshareef","doi":"10.1039/d6cs00989a","DOIUrl":"https://doi.org/10.1039/d6cs00989a","url":null,"abstract":"<p><p>MXenes have emerged as highly promising two-dimensional materials for advanced sensing applications owing to their high electrical conductivity, rich surface chemistry, hydrophilicity, mechanical flexibility, and compositional diversity. While many MXene-based sensors have been interpreted primarily from the perspective of surface-mediated interactions on individual flakes, practical sensing devices are typically constructed from assembled architectures, including films, fibers, aerogels, hydrogels, and composite networks. In these systems, inter-flake regions can make important contributions to the generation and transmission of macroscopic sensing signals by influencing charge transport, ion and molecular diffusion, and local interfacial interactions at the device level. This review focuses on inter-flake modulation as a key design principle for MXene-based sensing systems. We begin by briefly outlining the intrinsic material properties that make MXenes attractive for sensing, then discuss the fundamental inter-flake properties of MXene assemblies, including interlayer spacing, flake orientation, structural porosity, and the chemical microenvironment, with emphasis on their characterization, modulation strategies, and impacts on sensing performance. We further summarize representative advances in inter-flake modulation of MXene assemblies for smart sensing scenarios, spanning piezoresistive sensing, chemiresistive sensing, and electrochemical sensing. Finally, we discuss key challenges and opportunities for optimizing inter-flake structures toward future MXene-based sensing systems. We believe this work will provide useful guidance and new perspectives for future advanced MXene materials and devices in smart sensing applications.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" ","pages":""},"PeriodicalIF":48.3,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Guo Tian, Zining Wang, Chenxi Zhang, Bin Dai, Fei Wei
{"title":"Interfacial reaction-network catalysis: steering complex transformations through physical mixing.","authors":"Guo Tian, Zining Wang, Chenxi Zhang, Bin Dai, Fei Wei","doi":"10.1039/d6cs00516k","DOIUrl":"https://doi.org/10.1039/d6cs00516k","url":null,"abstract":"<p><p>Physical mixing is one of the simplest ways to combine catalytic components, yet it has often been treated as an empirical formulation strategy rather than a rational design principle. This Review states that, when distinct solids are arranged to exchange intermediates, products, inhibitors, heat or local chemical potentials, a physical mixture can function as an interfacial reaction network rather than as a simple sum of independent catalysts. We define this concept as interfacial reaction-network catalysis (IRNC), in which complex transformations are spatially partitioned into coupled functional domains and steered through measurable interdomain exchange. After clarifying the boundaries between physical mixing, conventional bifunctional catalysis and chemically integrated architectures, we introduce three network-control modes: intermediate relay, catalytic shunting and thermodynamic cascading. Intermediate relay connects source and receiving domains through relayed intermediates. Catalytic shunting allocates branch-point flux among desired, side, escape and deactivation pathways. Thermodynamic cascading regulates local activities, residence times and deactivation exposure through enrichment, product removal and inhibitor buffering. We then discuss how these functions operate in oxide-zeolite, Fischer-Tropsch-zeolite and multicomponent systems, and how physical separation and chemical integration provide complementary coupling regimes. Finally, we highlight descriptor quantification, <i>operando</i> characterization, multiscale simulation and catalyst-reactor co-design as key requirements for moving IRNC from empirical combination to predictive network programming. This framework establishes physical mixing as a modular and scalable strategy for steering complex catalytic transformations across molecular, particle and reactor scales.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" ","pages":""},"PeriodicalIF":48.3,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134209","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anissa Haim, Cassandra J Henderson, Merve Akdeniz, Timothy Noël, Tom N Grossmann
{"title":"Chemical reactions for the ligand-directed modification of native proteins.","authors":"Anissa Haim, Cassandra J Henderson, Merve Akdeniz, Timothy Noël, Tom N Grossmann","doi":"10.1039/d6cs00702c","DOIUrl":"10.1039/d6cs00702c","url":null,"abstract":"<p><p>Selective modifications of native proteins provide powerful opportunities to study and manipulate biological systems, yet achieving site-selective functionalization remains challenging due to the surfeit of competing amino acids, often addressed by genetic engineering of target proteins. Ligand-directed protein modification addresses these limitations by exploiting reversible molecular recognition to position reactive groups in proximity to a defined protein site, thereby enabling selective covalent modification of native proteins under physiological conditions. Importantly, ligand-directed protein modification is evolving from a specialized labeling methodology into a versatile platform for the selective manipulation of protein function in native biological environments. In this review, we discuss recent advances in ligand-directed strategies that employ synthetically accessible small molecules and peptides as recognition elements. Current approaches are categorized into (i) ligation reactions, in which the ligand remains attached to the protein, (ii) transfer reactions, which install a functional moiety while releasing the ligand, and (iii) ligand-directed catalysis, where ligand-tethered catalysts promote protein-substrate reactions with catalytic turnover. For each strategy, employed chemical reactions, amino acid selectivities, and applications in chemical biology and biotechnology are described. We further compare the strengths and limitations of these approaches considering the balance between reactivity, selectivity, and biocompatibility.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" ","pages":""},"PeriodicalIF":48.3,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13647452/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134235","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Unraveling complexity: advances in metal-catalyzed sequential double hydrofunctionalization of alkynes.","authors":"Zhaoyang Cheng, Minghua Li, Yufeng Sun, Zhan Lu","doi":"10.1039/d6cs00306k","DOIUrl":"https://doi.org/10.1039/d6cs00306k","url":null,"abstract":"<p><p>Sequential double hydrofunctionalization of alkynes (SDHFA) represents an atom- and pot-economical strategy to access geminal- and vicinal-difunctionalized compounds, which are widespread in drug molecules, bioactive natural products, and functional polymers and materials. However, the multiple-step nature of SDHFA brings more challenges associated with chemo-, regio- and stereoselective control; meanwhile, the one-pot setting may introduce incompatibility between the two steps. Metal catalysis has played an important role in modern organic chemistry, and various catalytic systems have been applied to solve the above-mentioned challenges. Over the past decades, considerable advances have been made in metal-catalyzed SDHFA. This review provides a comprehensive summary of this field, covering the addition reactions of O-H, N-H, C-H, P-H, S-H, B-H, and Si-H bonds, and highlights representative mechanisms and synthetic applications with the aim of providing useful insight into this area and promoting its further development.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" ","pages":""},"PeriodicalIF":48.3,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Henrik Gotfredsen, Jorge Labella, Yifan Bo, Dominik Thiel, Tomás Torres, Dirk M Guldi, Rik R Tykwinski
{"title":"Porphyrinoids for up- and down-conversion.","authors":"Henrik Gotfredsen, Jorge Labella, Yifan Bo, Dominik Thiel, Tomás Torres, Dirk M Guldi, Rik R Tykwinski","doi":"10.1039/d6cs00775a","DOIUrl":"https://doi.org/10.1039/d6cs00775a","url":null,"abstract":"<p><p>Chemistry is deeply connected to nearly every aspect of our lives and will therefore play a key role in addressing global challenges related to health, materials, and energy. In this context, the design and synthesis of new molecular materials remains at the forefront of research aimed at delivering transformative advances. A leading example for such shifts in existing scientific paradigms is surpassing the \"thermodynamic limit for single-junction solar cells\", which limits the maximum solar conversion efficiency achievable by a single p-n junction solar cell to just over 30%.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" ","pages":""},"PeriodicalIF":48.3,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149126095","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}