Chemical Reviews最新文献

{"title":"Design Approaches That Utilize Ionic Interactions to Control Selectivity in Transition Metal Catalysis","authors":"Hannah K. Adams, Max Kadarauch, Nicholas J. Hodson, Arthur R. Lit, Robert J. Phipps","doi":"10.1021/acs.chemrev.4c00849","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00849","url":null,"abstract":"The attractive force between two oppositely charged ions can constitute a powerful design tool in selective catalysis. Enzymes make extensive use of ionic interactions alongside a variety of other noncovalent interactions; recent years have seen synthetic chemists begin to seriously explore these interactions in catalyst designs that also incorporate a reactive transition metal. In isolation, a single ionic interaction exhibits low directionality, but in many successful systems they exist alongside additional interactions which can provide a high degree of organization at the selectivity-determining transition state. Even in situations with a single key interaction, low directionality is not always detrimental, and can even be advantageous, conferring generality to a single catalyst. This Review explores design approaches that utilize ionic interactions to control selectivity in transition metal catalysis. It is divided into two halves: in the first, the ionic interaction occurs in the outer sphere of the metal complex, using a ligand which is charged or bound to an anion; in the second, the metal bears a formal charge, and the ionic interaction is with an associated counterion.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"4 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526020","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":"Introduction: “Noncanonical Amino Acids”","authors":"Nediljko Budisa*, ","doi":"10.1021/acs.chemrev.5c0006510.1021/acs.chemrev.5c00065","DOIUrl":"https://doi.org/10.1021/acs.chemrev.5c00065https://doi.org/10.1021/acs.chemrev.5c00065","url":null,"abstract":"","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"125 4","pages":"1659–1662 1659–1662"},"PeriodicalIF":51.4,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486915","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":"Chemical Design of Magnetic Nanomaterials for Imaging and Ferroptosis-Based Cancer Therapy.","authors":"Wei Xu, Guoqiang Guan, Renye Yue, Zhe Dong, Lingling Lei, Heemin Kang, Guosheng Song","doi":"10.1021/acs.chemrev.4c00546","DOIUrl":"10.1021/acs.chemrev.4c00546","url":null,"abstract":"<p><p>Ferroptosis, an iron-dependent form of regulatory cell death, has garnered significant interest as a therapeutic target in cancer treatment due to its distinct characteristics, including lipid peroxide generation and redox imbalance. However, its clinical application in oncology is currently limited by issues such as suboptimal efficacy and potential off-target effects. The advent of nanotechnology has provided a new way for overcoming these challenges through the development of activatable magnetic nanoparticles (MNPs). These innovative MNPs are designed to improve the specificity and efficacy of ferroptosis induction. This Review delves into the chemical and biological principles guiding the design of MNPs for ferroptosis-based cancer therapies and imaging-guided therapies. It discusses the regulatory mechanisms and biological attributes of ferroptosis, the chemical composition of MNPs, their mechanism of action as ferroptosis inducers, and their integration with advanced imaging techniques for therapeutic monitoring. Additionally, we examine the convergence of ferroptosis with other therapeutic strategies, including chemodynamic therapy, photothermal therapy, photodynamic therapy, sonodynamic therapy, and immunotherapy, within the context of nanomedicine strategies utilizing MNPs. This Review highlights the potential of these multifunctional MNPs to surpass the limitations of conventional treatments, envisioning a future of drug-resistance-free, precision diagnostics and ferroptosis-based therapies for treating recalcitrant cancers.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":" ","pages":"1897-1961"},"PeriodicalIF":51.4,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143412272","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":"Introduction: “Noncanonical Amino Acids”","authors":"Nediljko Budisa","doi":"10.1021/acs.chemrev.5c00065","DOIUrl":"https://doi.org/10.1021/acs.chemrev.5c00065","url":null,"abstract":"Published as part of &lt;i&gt;Chemical Reviews&lt;/i&gt; special issue “Noncanonical Amino Acids”. Life is a chemically driven process, shaped by Earth’s geology and relying on persistent small molecules for core chemistry, while transient macromolecules control informational, thermodynamic and kinetic functions. Morowitz and Smith (1) have identified 60 universal carbon metabolites, with the central citric acid cycle providing stable intermediates as building blocks for biosynthesis, including proteins. The genetic code has evolved together with metabolism and expanded from a minimal set of amino acids (e.g., the “Alanine World Model” (2) postulates that there were Gly, Pro, Ala and a cationic amino acid) to the extant canonical 20. The special canonical amino acids selenocysteine and pyrrolysine (3) further expand the genetic code in certain life taxa. Wong’s coevolutionary theory (4) states that the code has evolved together with amino acid biosynthesis, starting with prebiotic amino acids and expanding through the reassignment of codons by means of “codon capture” or “ambiguous intermediate” mechanisms. (5) In this special issue on “&lt;i&gt;Noncanonical Amino Acids&lt;/i&gt;”, Tze-Fei Wong builds on his lifelong work on the Co-evolution Theory and presents an excellent article “&lt;i&gt;Triphasic Development of the Genetic Code&lt;/i&gt;” describing three distinct phases in the evolution of the genetic code. Phase 1 is the initial development of the amino acid repertoire in the RNA world. Phase 2 marks the emergence of cells with core metabolic pathways capable of delivering stable intermediates that served as precursors for most canonical amino acids in the extant genetic code. With an eye to the future, Wong anticipates Phase 3, in which the genetic code will expand its amino acid repertoire through anthropogenic intervention (incorporation of noncanonical amino acids (ncAAs)), paving the way for synthetic life forms with brand new genetic codes. The 20 α-L-canonical amino acids encoded by the universal genetic code are translated by ribosomal machinery, including tRNA, aminoacyl-tRNA synthetases (aaRSs), ribosomes, and associated factors. Protein translation decodes amino acid structures from nucleic acid sequences and recodes them into proteins, enabling programmable peptide and protein production. Expansion of the genetic code to incorporate ncAAs presents a significant biochemical challenge and offers insights into information flow, evolutionary innovation, and the possibilities for creating an “orthogonal central dogma” (6) (see Scheme 1) and synthetic cells with alternative life chemistry. (7) This approach enables new therapeutic proteins, biocatalysts for synthetic chemistry, and biological containment strategies. Although the technology has immense academic and industrial potential, much of it still remains untapped. &lt;span&gt;&lt;sup&gt;a&lt;/sup&gt;&lt;/span&gt;This framework comprises two main approaches: designing alternative nucleic acids (Xeno-Nucleic Acids, XNAs) as information po","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"66 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143496053","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":"Electrostatics, Hydration, and Chemical Equilibria at Charged Monolayers on Water.","authors":"Kenneth D Judd, Sean W Parsons, Tirthick Majumder, Jahan M Dawlaty","doi":"10.1021/acs.chemrev.4c00676","DOIUrl":"10.1021/acs.chemrev.4c00676","url":null,"abstract":"<p><p>The chemistry and physics of soft matter interfaces, especially aqueous-organic interfaces, are centrally important to many areas of science and technology. Often, the thermodynamics, kinetics, and selectivity of reactions are modified at interfaces. Here, we review the electrostatics and hydration at charged monolayers on water and their influence on interfacial chemical equilibria. First, we provide an understanding of interfaces as a conceptual continuation of the solvation shell of small molecules, along with recent relevant experimental work. Then, we provide a summary of models for describing the electrostatics of aqueous interfaces. While we will discuss a range of new developments, our focus will be on systems where the electrostatics of the surface is controllable by the choice of relatively simple insoluble surfactants. New insights into the molecular structure of the double layer, with particular attention on the knowledge gained from spectroscopy will be reviewed. Our approach is to familiarize the reader with simple models, followed by discussion of models with further complexity for explaining interfacial phenomena. Experiments that test the limits of such models will also be discussed. Finally, we will provide an outlook on engineering the interfacial environment for tailored reactivity, along with the anticipated experimental advancements and potentials impacts.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":" ","pages":"2440-2473"},"PeriodicalIF":51.4,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143397511","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":"Strategies to Expand the Genetic Code of Mammalian Cells.","authors":"Arianna O Osgood, Zeyi Huang, Kaitlyn H Szalay, Abhishek Chatterjee","doi":"10.1021/acs.chemrev.4c00730","DOIUrl":"10.1021/acs.chemrev.4c00730","url":null,"abstract":"<p><p>Genetic code expansion (GCE) in mammalian cells has emerged as a powerful technology for investigating and engineering protein function. This method allows for the precise incorporation of a rapidly growing toolbox of noncanonical amino acids (ncAAs) into predefined sites of target proteins expressed in living cells. Due to the minimal size of these genetically encoded ncAAs, the wide range of functionalities they provide, and the ability to introduce them freely at virtually any site of any protein by simple mutagenesis, this technology holds immense potential for probing the complex biology of mammalian cells and engineering next-generation biotherapeutics. In this review, we provide an overview of the underlying machinery that enables ncAA mutagenesis in mammalian cells and how these are developed. We have also compiled an updated list of ncAAs that have been successfully incorporated into proteins in mammalian cells. Finally, we provide our perspectives on the current challenges that need to be addressed to fully harness the potential of this technology.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":" ","pages":"2474-2501"},"PeriodicalIF":51.4,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143404898","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":"Principles and Design of Molecular Tools for Sensing and Perturbing Cell Surface Receptor Activity","authors":"Jennifer Sescil, Steven M. Havens, Wenjing Wang","doi":"10.1021/acs.chemrev.4c00582","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00582","url":null,"abstract":"Cell-surface receptors are vital for controlling numerous cellular processes with their dysregulation being linked to disease states. Therefore, it is necessary to develop tools to study receptors and the signaling pathways they control. This Review broadly describes molecular approaches that enable 1) the visualization of receptors to determine their localization and distribution; 2) sensing receptor activation with permanent readouts as well as readouts in real time; and 3) perturbing receptor activity and mimicking receptor-controlled processes to learn more about these processes. Together, these tools have provided valuable insight into fundamental receptor biology and helped to characterize therapeutics that target receptors.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"14 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143496052","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":"Methods for Theoretical Treatment of Local Fields in Proteins and Enzymes","authors":"Mark E. Eberhart, Anastassia N. Alexandrova, Pujan Ajmera, Daniel Bím, Shobhit S. Chaturvedi, Santiago Vargas, Timothy R. Wilson","doi":"10.1021/acs.chemrev.4c00471","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00471","url":null,"abstract":"Electric fields generated by protein scaffolds are crucial in enzymatic catalysis. This review surveys theoretical approaches for detecting, analyzing, and comparing electric fields, electrostatic potentials, and their effects on the charge density within enzyme active sites. Pioneering methods like the empirical valence bond approach rely on evaluating ionic and covalent resonance forms influenced by the field. Strategies employing polarizable force fields also facilitate field detection. The vibrational Stark effect connects computational simulations to experimental Stark spectroscopy, enabling direct comparisons. We highlight how protein dynamics induce fluctuations in local fields, influencing enzyme activity. Recent techniques assess electric fields throughout the active site volume rather than only at specific bonds, and machine learning helps relate these global fields to reactivity. Quantum theory of atoms in molecules captures the entire electron density landscape, providing a chemically intuitive perspective on field-driven catalysis. Overall, these methodologies show protein-generated fields are highly dynamic and heterogeneous, and understanding both aspects is critical for elucidating enzyme mechanisms. This holistic view empowers rational enzyme engineering by tuning electric fields, promising new avenues in drug design, biocatalysis, and industrial applications. Future directions include incorporating electric fields as explicit design targets to enhance catalytic performance and biochemical functionalities.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"7 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486400","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":"Organic Artificial Nerves: Neuromorphic Robotics and Bioelectronics","authors":"Min-Jun Sung, Kwan-Nyeong Kim, Chunghee Kim, Hyun-Haeng Lee, Seung-Woo Lee, Somin Kim, Dae-Gyo Seo, Huanyu Zhou, Tae-Woo Lee","doi":"10.1021/acs.chemrev.4c00571","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00571","url":null,"abstract":"Neuromorphic electronics are inspired by the human brain’s compact, energy-efficient nature and its parallel-processing capabilities. Beyond the brain, the entire human nervous system, with its hierarchical structure, efficiently preprocesses complex sensory information to support high-level neural functions such as perception and memory. Emulating these biological processes, artificial nerve electronics have been developed to replicate the energy-efficient preprocessing observed in human nerves. These systems integrate sensors, artificial neurons, artificial synapses, and actuators to mimic sensory and motor functions, surpassing conventional circuits in sensor-integrated electronics. Organic synaptic transistors (OSTs) are key components in constructing artificial nerves, offering tunable synaptic plasticity for complex sensory processing and the mechanical flexibility required for applications in soft robotics and bioelectronics. Compared to traditional sensor-integrated electronics, early implementations of organic artificial nerves (OANs) incorporating OSTs have demonstrated a higher signal-to-noise ratio, lower power consumption, and simpler circuit designs along with on-device processing capabilities and precise control of actuators and biological limbs, driving progress in neuromorphic robotics and bioelectronics. This paper reviews the materials, device engineering, and system integration of the OAN design, highlights recent advancements in neuromorphic robotics and bioelectronics utilizing the OANs, and discusses current challenges and future research directions.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"29 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143471062","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":"The Cation−π Interaction in Chemistry and Biology","authors":"Dennis A. Dougherty","doi":"10.1021/acs.chemrev.4c00707","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00707","url":null,"abstract":"The cation−π interaction is an important noncovalent binding force that impacts all areas of chemistry and biology. Extensive computational and gas phase experimental studies have established the potential strength and the essential nature of the interaction. Previous reviews have emphasized studies of model systems and a variety of biological examples. This work includes discussion of those areas but emphasizes other areas that are perhaps less well appreciated. These include the novel cation−π binding ability of alkali metals in water; the application of the cation−π interaction to organic synthesis and chemical biology; cooperative behaviors of multiple cation−π interactions, including adhesive proteins from mussels and similar organisms and the formation and modulation of biomolecular condensates (phase separation); and cation−π interactions involved in recognizing DNA/RNA.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"2 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462160","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}