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Assessing Radiology Practice Patterns for Obtaining MRI in Pediatric Patients with MR-Conditional Tracheostomy Tubes. 评估放射科为使用磁共振条件下气管造口插管的儿科患者获取磁共振成像的实践模式。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-08-01 Epub Date: 2022-10-19 DOI: 10.1177/01455613221132388
Ellen M Cahill, Michael Chee, Kelvin Kwong
{"title":"Assessing Radiology Practice Patterns for Obtaining MRI in Pediatric Patients with MR-Conditional Tracheostomy Tubes.","authors":"Ellen M Cahill, Michael Chee, Kelvin Kwong","doi":"10.1177/01455613221132388","DOIUrl":"10.1177/01455613221132388","url":null,"abstract":"<p><strong>Objectives: </strong>Silicone tracheostomy tubes are a popular choice for pediatric patients with chronic tracheostomies due to their pliability and increased comfort. However, the presence of wire reinforcement causes them to be labeled \"MR-conditional.\" The objective of this study was to understand practice patterns across radiology departments for obtaining MRI in children with MR-conditional tracheostomy tubes.</p><p><strong>Methods: </strong>A survey consisting of 7 questions aimed at determining a facility's protocol for obtaining MRI in children with tracheostomy tubes was developed and administered via telephone to MRI technologists at US children's hospitals.</p><p><strong>Results: </strong>182 children's hospitals were identified and 59 responses were obtained across 30 states (32.4%). 19 sites (32%) were excluded as they were unable to perform MRI. All 40 facilities reported that they have a standard questionnaire for medical implants, however only 20 reported that tracheostomy tubes are included on that questionnaire (50%). 6 (15%) reported all MR-conditional tubes are changed to MR-safe ones. Of the remaining 34, protocols were as follows: 1 (2.9%) scans patients with conditional tubes for a maximum of 15 minutes, 5 (14.7%) only use a 1.5T magnet, and 28 (82.3%) reported following the manufacturer conditions. In terms of artifact, 3 sites change MR-conditional tubes to MR-safe if scanning the head, neck, chest, or abdomen (8.8%), 6 (17.6%) change the tube if scanning the head or neck, 15 (44.1%) change the tube only if scanning the neck, and 10 (29.4%) were not aware of issues with artifact.</p><p><strong>Conclusion: </strong>Based on this survey of MRI technologists at US children's hospitals, there is no unified protocol for obtaining MRI in pediatric patients with MR-conditional tracheostomy tubes. A lack of standardized protocols may be contributing to unnecessary tracheostomy changes. Future research includes clearly defining the anatomical regions affected by wire-related artifact and developing a standardized MRI protocol for these patients.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"508-512"},"PeriodicalIF":16.4,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40341962","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}
引用次数: 0
Discovery of Stable Extra-large Pore Zeolites Based on Rational Design of Structure-directing Agents. 基于结构导向剂合理设计的稳定超大孔径沸石的发现。
IF 18.3 1区 化学
Accounts of Chemical Research Pub Date : 2025-07-25 DOI: 10.1021/acs.accounts.5c00223
Fei-Jian Chen,Jihong Yu
{"title":"Discovery of Stable Extra-large Pore Zeolites Based on Rational Design of Structure-directing Agents.","authors":"Fei-Jian Chen,Jihong Yu","doi":"10.1021/acs.accounts.5c00223","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00223","url":null,"abstract":"ConspectusAluminosilicate zeolites possess ordered pore structures and tunable acidities as well as remarkable thermal/hydrothermal stabilities, which render them highly suitable for industrial applications in petroleum refining, in organic chemical synthesis, as catalysts, and in gas separation technologies as adsorbents. Computational predictions indicate that millions of theoretical zeolite framework types may be realizable; however, the International Zeolite Association (IZA) has authenticated only 260 zeolite framework types to date. Among these, approximately 20 types have found industrial applications, and their pore systems are generally confined to not exceeding the 12-membered ring (MR). There is an intense demand in industry to develop novel, stable, three-dimensional (3D) zeolites with extra-large pores, which are essential for heavy oil conversion and macromolecular catalysis.Over the past 30 years, more than 30 extra-large pore zeolites have been synthesized by using bulky organic structure-directing agents (SDAs) as templates. Nevertheless, their utilization has been restricted by various factors, like inferior thermal and hydrothermal stability, unexpected interrupted frameworks, and limitation of 3D connectivity. Research on the exploration of stable 3D extra-large pore zeolites has advanced sluggishly, and there has been a persistent inability to achieve breakthroughs along this direction. Recently, we reported the ZEO series of 3D stable silica-based extra-large pore zeolites, which represents a synthetic breakthrough in this area. This Account focuses on the timeline and comprehensively introduces our decade-long efforts in developing novel 3D stable extra-large pore zeolites, especially for the progressive innovation of designing SDAs. Starting with the semirigid imidazole salts as SDAs, we successfully synthesized NUD-1/2/3, a series of new large and extra-large pore germanosilicate zeolites; later efforts were extended to highly rigid benzimidazole-based SDAs, which led to the successful synthesis of high silica and pure silica extra-large pore zeolites NUD-5/6. Although imidazole salts were found to be much more efficient, their lower stability under alkaline and high temperature conditions limited their application. At the same time, most of the as-synthesized zeolites have only 1D extra-large pores due to the strong molecular interactions between the SDAs caused by their aromatic rings. To address this issue, bulky and stable SDAs derived from cycloalkyl phosphines were subsequently developed. With tricyclohexylmethylphosphonium (TCyMP) as the SDA, we synthesized the first 3D stable extra-large pore aluminosilicate zeolite, ZEO-1, which is a breakthrough in zeolite synthesis. Furthermore, a new 1D to 3D topotactic condensation mechanism stemming from a novel 1D chain silicate, ZEO-2, was discovered, by which the 3D stable extra-large pore zeolites ZEO-3 and ZEO-5 were synthesized, continuously expanding the pore size lim","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"121 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144701109","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}
引用次数: 0
Generating Surprisingly Powerful Pharmacology from Chemically Induced Protein Interactions. 从化学诱导的蛋白质相互作用中产生惊人的强大药理学。
IF 18.3 1区 化学
Accounts of Chemical Research Pub Date : 2025-07-24 DOI: 10.1021/acs.accounts.5c00225
Stephen M Hinshaw,Steven M Banik,Nathanael S Gray
{"title":"Generating Surprisingly Powerful Pharmacology from Chemically Induced Protein Interactions.","authors":"Stephen M Hinshaw,Steven M Banik,Nathanael S Gray","doi":"10.1021/acs.accounts.5c00225","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00225","url":null,"abstract":"ConspectusSmall molecules that induce proximity between proteins have transformed our ability to manipulate and study cellular processes. Beyond this, proximity-inducing small molecules and biologics are now a clinical reality with increasing reach over different targets and disease indications, benefiting from our rapidly expanding abilities to exploit diverse biochemical mechanisms and being powered by emerging design principles. Targeted protein degradation has become a predominant proximity-dependent therapeutic mechanism. We contend that there are many yet-unexplored pharmacologically useful mechanisms that can be triggered by chemically induced protein interactions. We discuss the general principles of proximity pharmacology and highlight two areas we believe are ripe for innovation.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"105 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144693248","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}
引用次数: 0
Design and Engineering of Semiconductor-Organic Interfaces: Multilayer Synthesis on the Si(001) Surface Based on Cyclooctyne Chemistry. 半导体-有机界面的设计与工程:基于环辛基化学的Si(001)表面多层合成。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-07-23 DOI: 10.1021/acs.accounts.5c00316
Michael Dürr, Ulrich Höfer, Ulrich Koert, Ralf Tonner-Zech
{"title":"Design and Engineering of Semiconductor-Organic Interfaces: Multilayer Synthesis on the Si(001) Surface Based on Cyclooctyne Chemistry.","authors":"Michael Dürr, Ulrich Höfer, Ulrich Koert, Ralf Tonner-Zech","doi":"10.1021/acs.accounts.5c00316","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00316","url":null,"abstract":"<p><p>ConspectusIn this Account, we will focus on how chemoselective strategies were employed for the controlled synthesis of organic multilayers on silicon, thus forming well-defined semiconductor-organic interfaces. We will start with the chemoselective [2 + 2] cycloaddition of functionalized cyclooctynes to Si-Si dimers which was used as the key step for the surface-orthogonal first layer attachment of bifunctional organic molecules to the Si(001) surface. It results in well-ordered monolayers of bifunctional molecules on the highly reactive Si(001) surface, which serve as a starting point for the further layer-by-layer growth.Various strategies for the covalent attachment of further molecular layers are then developed; they include, among others, a combination of UHV- and solution-based chemistry for the application of selective and orthogonal reaction schemes in solution as well as a carefully tuned enolether/tetrazine cycloaddition for click chemistry under UHV conditions.In particular, well-ordered multilayers of organic molecules were realized on prefunctionalized Si(001) via a two-step reaction cycle in solution. Alternating the application of two selective, orthogonal reaction steps based on asymmetric building blocks led to a well-controlled layer-by-layer growth of organic molecular layers on Si(001).Further exploitation of these strategies, e.g., in the framework of on-surface synthesis, will be discussed; our approach for the selective growth of covalently bound layers perpendicular to the surface might be further combined with lateral structuring of the surface for the synthesis of organic architectures with control in all three dimensions.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144697059","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}
引用次数: 0
N-Arylene Ethynylene Foldamers: Structures and Functions. n -芳烯-乙炔文件夹:结构和功能。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-07-22 DOI: 10.1021/acs.accounts.5c00358
Seungwon Lee, Geunmoo Song, Kyu-Sung Jeong
{"title":"<i>N</i>-Arylene Ethynylene Foldamers: Structures and Functions.","authors":"Seungwon Lee, Geunmoo Song, Kyu-Sung Jeong","doi":"10.1021/acs.accounts.5c00358","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00358","url":null,"abstract":"<p><p>ConspectusThe construction of synthetic counterparts that mimic the structures and functions of proteins and nucleic acids has become a central focus of research in supramolecular chemistry. Aromatic foldamers are capable of folding into secondary or higher-order structures that resemble those of biomacromolecules. Over the past two decades, a variety of aromatic foldamers have been developed, including <i>N</i>-arylene ethynylene foldamers summarized in this Account. <i>N</i>-Arylene ethynylene foldamers consist of N- and NH-containing aryl heterocycles alternately linked through ethynyl bonds. These foldamers adopt stable helical structures with internal tubular cavities, driven by dipole-dipole and π-stacking interactions. Indolocarbazole-pyridine (IP) foldamers have demonstrated how folding stability and helical handedness can be modulated, with applications in anion recognition and sensing. Moreover, an indolocarbazole-naphthyridine (IN) foldamer with a larger internal cavity enables the binding of simple monosaccharides such as glucose and galactose. Utilizing dynamic covalent bonds and guest-directed synthesis, homochiral foldamers with covalently fixed, one-handed helical cavities have been quantitatively synthesized. These foldamers selectively bind the chiral guests used in their syntheses over enantiomeric or analogous guests. Furthermore, the quantitative assembly of imine-linked foldamers can be achieved from short precursors in the presence of appropriate guests. Interestingly, an imine-linked foldamer forms 2:2 complexes with both methyl β-d-glucopyranoside and methyl β-d-galactopyranoside, with temperature changes inducing complete switching of interacting guests. Each complex contains two identical cavities generated through guest-adaptive folding in a domain-swapping manner, enabling strong and selective binding. Finally, nonclassical helical duplexes are described, exhibiting duplex-to-duplex transformations in response to external stimuli. Future studies in aromatic foldamer chemistry may focus on the development of smart materials, enzyme-like catalysts, and bioapplicable foldamers.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144688289","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}
引用次数: 0
Structural Descriptor Bridging the Microstructural Feature and Catalytic Reactivity for Rational Design of Metal Catalysts. 结构描述子桥接微观结构特征和催化反应性为金属催化剂的合理设计。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-07-21 DOI: 10.1021/acs.accounts.5c00219
Haoxiang Xu, Jiayi Wang, Jin Liu, Daojian Cheng
{"title":"Structural Descriptor Bridging the Microstructural Feature and Catalytic Reactivity for Rational Design of Metal Catalysts.","authors":"Haoxiang Xu, Jiayi Wang, Jin Liu, Daojian Cheng","doi":"10.1021/acs.accounts.5c00219","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00219","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusMetal heterogeneous catalysis is the workhorse of the chemical industry, driving the conversion of reactants to desirable products. Traditional design approaches for metal catalysts rely on trial-and-error tests and take a lot of time to identify promising catalytic active species from the large candidate space. Over the decades, much focus has been placed on identifying the factors affecting the active sites, which, in turn, guides the design and preparation of more active, selective, and stable catalysts. In the context of theoretical design method for catalysts, the concept of the energy descriptor strategy provides correlations between the adsorption energy of key intermediates and catalytic reactivity. Such energy descriptors for catalytic reactivity can be used to predict the activity of candidate catalysts and understand trends among different catalysts.However, a more efficient descriptor strategy is still attractive and needed that avoids density functional theory calculation on the adsorption energy of each candidate and possesses the guidance power for the rational design of microstructural characteristics of catalytic active species. In this regard, bridging the gap between the electronic/atomic-level descriptions of the microscopic properties of the catalytic active species and the macroscopic catalytic performance of the desirable reaction, that is, the microscopic-to-macroscopic relationship, remains intriguing yet challenging, toward which progress leads to revolutionizing catalyst design.In this Account, we propose a structural descriptor strategy that for the first time maps the quantitative relationship between microstructural features and catalytic performances for metal catalysts, as well as its application in the high-throughput screening and rational design of catalytic active species. We begin with the analysis of the microstructural characteristics of the reaction center and its coordination environment and extract key feature parameters to build a mathematical expression of the structural descriptor. Next, through regression fitting, a mathematical correlation is built between the structural descriptor and the energetics involved with the reaction pathway. Finally, substituting the above statistical correlations into the rate equation derived from microkinetic model offers the structural descriptor-based prediction model for metal catalysts. The use of easily accessible structural descriptors has proven to be a powerful method to advance and accelerate the discovery and design of metal catalysts, including atomically dispersed metal catalysts, metal alloy catalysts, and metal cluster catalysts. Overall, the structural descriptor strategy not only demonstrates much potential to elucidate the quantitative interplay between microstructural features of catalytic active species and intrinsic catalytic reactivity but also provides a new approach in kinetics analysis to rationalize metal catalyst design. We conc","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144681640","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}
引用次数: 0
Alkyne Benzannulations: A Powerful Tool for the Efficient Synthesis of Chiral and Achiral Nanographenes and of Graphene Nanoribbons. 炔苯环:高效合成手性和非手性纳米石墨烯及石墨烯纳米带的有力工具。
IF 18.3 1区 化学
Accounts of Chemical Research Pub Date : 2025-07-21 DOI: 10.1021/acs.accounts.5c00211
Ryan J Malone,Wesley A Chalifoux
{"title":"Alkyne Benzannulations: A Powerful Tool for the Efficient Synthesis of Chiral and Achiral Nanographenes and of Graphene Nanoribbons.","authors":"Ryan J Malone,Wesley A Chalifoux","doi":"10.1021/acs.accounts.5c00211","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00211","url":null,"abstract":"ConspectusPolycyclic aromatic hydrocarbons (PAHs) have become ubiquitous in the design of organic electronics due to their extended π-electron systems that give rise to potentially useful optical and electronic properties. These properties─chiefly absorption, emission, and semiconductivity─can be tuned to suit a particular device application through changes to the size and shape of the molecule's backbone, through incorporation of heteroatoms into the core structure, and through functionalization along the periphery. To that end, synthetic design of PAHs necessitates versatile methodology to rapidly expand the π-electron system without sacrificing the solubility that allows the materials to be processed into devices.Alkyne benzannulation is a powerful tool for the synthesis of such PAHs due to the energetically downhill process of making an aromatic ring from a high-energy triple bond. Furthermore, functionalization of the alkynes can increase not only solubility but also steric strain in the backbone, resulting in highly contorted, even chiral, structures. Because the benzannulation process is so energetically favorable, even these very strained PAHs can be synthesized with relative ease under mild conditions.In this Account, we summarize our work and the development of our methods for utilizing alkyne benzannulation to synthesize contorted, and in many cases chiral, PAHs, as well as highly soluble graphene nanoribbons. Trifluoroacetic acid (TFA) is effective for the benzannulation of alkynes to cata-condensed PAH systems, creating phenanthrene-like moieties. However, we found that to generate peri-condensed systems with pyrene-like moieties, a much stronger Brønsted acid, such as triflic acid (TfOH), is required. Our combination of TFA for clean benzannulation of half of the alkynes under mild conditions, followed by TfOH to complete benzannulation of the remaining alkynes, was used to great effect in the synthesis of 5-armchair graphene nanoribbons and their oligomers, the pyrenacenes. This method was, unfortunately, limited to alkynes bearing electron-rich aromatic substituents. To overcome this obstacle and broaden the scope, we screened Lewis acid catalysts and found that InCl3 is effective for alkynes bearing much less electron-rich aromatics, and even alkynes bearing only alkyl chains, under milder reaction conditions than with the Brønsted acids. With these two methods, we synthesized the first chiral peropyrenes and the first chiral teropyrene, as well as other compounds exhibiting twistacene and helicene chirality. We later found that the Lewis acidity of InCl3 can be increased by the addition of a AgNTf2 cocatalyst to effect more difficult benzannulations while keeping the reaction conditions mild. These methods of alkyne benzannulation allow us a great deal of control over the size and shape of the PAH backbone, thereby giving us control over the optical and electronic properties, to give us a suite of compounds that exhibit absorpti","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"4 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144669531","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}
引用次数: 0
Genetically Encoded Photocatalysis for Spatiotemporally Resolved Mapping of Biomolecules in Living Cells and Animals. 遗传编码光催化用于活细胞和动物生物分子的时空分辨定位。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-07-21 DOI: 10.1021/acs.accounts.5c00390
Yuxin Fang, Peng Zou
{"title":"Genetically Encoded Photocatalysis for Spatiotemporally Resolved Mapping of Biomolecules in Living Cells and Animals.","authors":"Yuxin Fang, Peng Zou","doi":"10.1021/acs.accounts.5c00390","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00390","url":null,"abstract":"<p><p>ConspectusEngineered photosensitizer proteins, such as miniSOG, KillerRed, and SuperNova, have long been used for light-triggered protein inhibition and cell ablation. Compared to synthetic organic dyes, these genetically encoded tags provide superior spatial precision for subcellular targeting. More recently, the photochemistry of miniSOG has been repurposed for subcellular omics studies. Upon light activation, miniSOG generates reactive oxygen species (ROS) that oxidize nearby nucleic acids or proteins. These oxidized biomolecules can then react with exogenously supplied nucleophilic probes, which introduce bio-orthogonal handles for downstream enrichment and analysis.This labeling strategy, known as photocatalytic proximity labeling (PPL), has emerged as a powerful approach for profiling the molecular architecture of subcellular compartments and identifying RNA or protein interactors of specific targets. The use of light provides exceptional temporal control, enabling labeling windows as short as 1 s. Moreover, PPL readily supports pulse-chase experiments through simple light on/off switching, an advantage not easily achievable with conventional platforms such as APEX or TurboID.In this account, we highlight our recent developments and applications of genetically encoded PPL tools. These include CAP-seq for RNA/DNA labeling, RinID for protein labeling, and LAP-seq/MS/CELL for bioluminescence-activated multi-omic profiling. Together, these tools enable detailed mapping of the cellular biomolecular landscape. For example, CAP-seq revealed enrichment of transcripts encoding secretory and mitochondrial proteins near the endoplasmic reticulum membrane and outer mitochondrial membrane, supporting models of localized translation. Additionally, pulse-chase labeling using RinID in the ER lumen uncovered distinct decay kinetics of secretory proteins.Looking forward, future efforts may focus on developing low-toxicity and low-background chemical probes, engineering red-shifted photosensitizers for deep-tissue and <i>in vivo</i> applications, and integrating multiple proximity labeling (PL) platforms to study organelle contact sites and interorganelle molecular trafficking.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144681639","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}
引用次数: 0
Stereoselective Nondirected α-C(sp3)-H Functionalization of Oxygen Heterocycles. 氧杂环的立体选择性非定向α-C(sp3)-H功能化。
IF 18.3 1区 化学
Accounts of Chemical Research Pub Date : 2025-07-18 DOI: 10.1021/acs.accounts.5c00355
Yuanyuan Ping,Sheng Xu,Wangqing Kong
{"title":"Stereoselective Nondirected α-C(sp3)-H Functionalization of Oxygen Heterocycles.","authors":"Yuanyuan Ping,Sheng Xu,Wangqing Kong","doi":"10.1021/acs.accounts.5c00355","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00355","url":null,"abstract":"ConspectusOxygen-containing heterocycles are increasingly recognized for their biological significance, especially in the field of drug discovery. Therefore, the enantioselective synthesis of oxygen-containing heterocycles has attracted great attention in the past few decades, and many ingenious synthetic strategies have been developed. Despite remarkable progress, they are often limited in terms of the diversity of target scaffolds, accessibility of starting materials, substrate scope, and stereoselectivity. Simple saturated heterocycles are easily accessible, making them ideal starting points for further transformations. Therefore, approaches to functionalize the existing C(sp3)-H bonds in these readily available saturated heterocycles appear to be of great potential, opening up new avenues for the design and development of chiral heterocyclic drug candidates. However, saturated oxygen-containing heterocycles have similar steric hindrance and no additional sites for the installation of directing groups, making the catalytic enantiofacial differentiation of oxygen-containing heterocycles extremely challenging. To date, stereoselective C(sp3)-H functionalization of saturated oxygen heterocycles remains an unsolved problem in contemporary organic synthesis.In this Account, we summarize the recent progress made in our laboratory in stereoselective functionalization of nondirected oxygen-containing heterocycles via hydrogen atom transfer (HAT)/nickel dual catalysis. First, we discuss the construction of high-value chiral oxygen heterocycles from simple and readily available oxacycles via enantioselective C(sp3)-H arylation and alkenylation reactions, focusing on the effects of the ring, ligands, and photocatalysts on C(sp3)-C(sp2) bond formation and their respective roles. Experimental and density functional theory calculation studies further elucidate the mechanism of the asymmetric C(sp3)-H functionalization reactions and the origin of the enantioselectivity. Second, we describe a novel catalytic system that we designed for the enantioselective C(sp3)-H alkylation of saturated heterocycles, providing an efficient strategy for the stereoselective construction of C(sp3)-C(sp3) bonds. Finally, we disclose a facile and versatile method to synthesize a wide range of C-glycosides from readily accessible and bench-stable 1-deoxyglycosides. We further develop a catalyst-controlled, site-divergent carbohydrate functionalization approach that can be used to synthesize various unexplored carbohydrates containing arylated quaternary stereocenters. The synthetic applicability of our developed method has been demonstrated in the stereoselective synthesis of natural products, blockbuster drugs, and versatile synthetic building blocks.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"1 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144661903","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}
引用次数: 0
Perovskitoids as Functional Materials. 钙钛矿类功能材料。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-07-15 Epub Date: 2025-06-27 DOI: 10.1021/acs.accounts.5c00240
Isaiah W Gilley, Taylor E Wiggins, Edward H Sargent, Mercouri G Kanatzidis
{"title":"Perovskitoids as Functional Materials.","authors":"Isaiah W Gilley, Taylor E Wiggins, Edward H Sargent, Mercouri G Kanatzidis","doi":"10.1021/acs.accounts.5c00240","DOIUrl":"10.1021/acs.accounts.5c00240","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusFollowing the development of perovskite solar cells, the synthesis of hybrid Pb, Sn, and Ge halides exploded in popularity, with more than 3000 such crystal structures uploaded to the Cambridge Structural Database since the start of 2015. This synthetic interest has been accompanied by demonstrations of the materials' efficacy, such as solar cells, light-emitting diodes, and detectors. Though perovskites are the dominant focus for these optoelectronics applications, they comprise just over half of the 3000 structures mentioned. The nearly 1400 remaining nonperovskite materials include face- and edge-sharing structures like δ-FAPbI&lt;sub&gt;3&lt;/sub&gt; and δ-CsPbI&lt;sub&gt;3&lt;/sub&gt;, often seen as undesirable products of failed perovskite syntheses. Indeed, all-face- and all-edge-sharing structures have had little success as optoelectronics, but a subset of these nonperovskites has demonstrated some success as functional materials. We call this subset perovskitoids, a class of materials defined, like perovskites, by their structural connectivity. While both perovskites and perovskitoids have corner-sharing octahedra in their crystal structures, perovskitoids can also contain face- or edge-sharing octahedra. This mixed sharing lends perovskitoids a much greater degree of structural diversity than is present in materials with a single sharing type, and the resulting materials combine properties of their respective connectivities.As corner-, edge-, and face-sharing octahedral connections require different M-X-M bond angles, the degree of orbital overlap between consecutive octahedra varies with the sharing type, resulting in a strong dependence of perovskitoids' bandgaps on their specific connectivities. This dependence enables bandgap modulation by varying fractions of corner-, edge, and face-sharing within perovskitoids, accessing bandgaps that, for perovskites, would require halide mixing or dimensional reduction. The added edge- and face-sharing connections in perovskitoids also lend the materials greater air, water, and thermal stability than their perovskite counterparts by virtue of the added redundancy of the octahedral connections.In this Account, we give an overview of the structures, properties, and applications of perovskitoids, focusing on the ways in which they resemble and differ from perovskites. Specifically, examples of common types of perovskitoids are presented along with a summary of the relative effects of corner-, edge-, and face-sharing connectivity on their bandgaps, luminescence, and stability. Following is a discussion of applications of perovskitoids, highlighting our groups' previous work on perovskitoid phosphors, photodetectors, X-ray detectors, γ-ray detectors, capping layers for perovskite solar cells, and wide bandgap solar absorbers. Subsequently, we discuss strategies for improving upon the optoelectronic properties of existing perovskitoids, focusing on the synthesis of perovskitoids with high fractions of corner-","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"2243-2254"},"PeriodicalIF":16.4,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144511239","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}
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