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Phase engineering of polyoxometalate assembled superstructures 聚氧化铝组装超结构的相工程学
Nature synthesis Pub Date : 2024-06-25 DOI: 10.1038/s44160-024-00569-7
Fenghua Zhang, Haoyang Li, Zhong Li, Qingda Liu, Xun Wang
{"title":"Phase engineering of polyoxometalate assembled superstructures","authors":"Fenghua Zhang, Haoyang Li, Zhong Li, Qingda Liu, Xun Wang","doi":"10.1038/s44160-024-00569-7","DOIUrl":"10.1038/s44160-024-00569-7","url":null,"abstract":"Superstructures of cluster assemblies have extraordinary properties compared with individual clusters, however, their precise synthesis and phase engineering remain challenging. Here the modular synthesis of a library of clusters based on anisotropic polyoxometalate clusters (CTA)2(TBA)2[PW11MO39] (PW11M) is reported. Different phases of superstructures including nanoribbons, spiral nanosheets, tetragonal nanosheets, polyhedral frameworks and nanotubes are prepared by the tuning of interactions between and inside the polyoxometalate building blocks. This synthetic strategy can be applied to six kinds of PW11M cluster building block. A phase diagram based on these results, which can be used to adjustably assemble polyoxometalate clusters, is presented. The direct bonding of clusters and electron delocalization among nanoribbons results in improved conductivity and reduced energy barrier for redox reactions. The nanoribbons exhibit enhanced activity for photoresponse and catalytic olefin epoxidation compared with unassembled clusters. The phase engineering of cluster-assembled superstructures with atomic precision models may help understand the structure–property relationship at the sub-nanometre scale. A library of clusters based on anisotropic polyoxometalate clusters is synthesized. Different phases of superstructures are prepared by tuning interactions between and inside the polyoxometalate building blocks, which adds to our understanding of structure–property relationships at sub-nanometre scale.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 8","pages":"1039-1048"},"PeriodicalIF":0.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Electrocatalytic C–N bond formation 电催化 C-N 键形成
Nature synthesis Pub Date : 2024-06-25 DOI: 10.1038/s44160-024-00594-6
Alexandra Groves
{"title":"Electrocatalytic C–N bond formation","authors":"Alexandra Groves","doi":"10.1038/s44160-024-00594-6","DOIUrl":"10.1038/s44160-024-00594-6","url":null,"abstract":"Marta Costa Figueiredo, an Assistant Professor of electrochemistry at Eindhoven University of Technology, talks to Nature Synthesis about electrocatalysis and the electrochemical formation of C–N bonds.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 7","pages":"797-798"},"PeriodicalIF":0.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Photoinduced double hydrogen-atom transfer for polymerization and 3D printing of conductive polymer 光诱导双氢原子转移用于导电聚合物的聚合和三维打印
Nature synthesis Pub Date : 2024-06-21 DOI: 10.1038/s44160-024-00582-w
Xin Zhou, Shangwen Fang, Yangnan Hu, Xin Du, Haibo Ding, Renjie Chai, Jie Han, Jin Xie, Zhongze Gu
{"title":"Photoinduced double hydrogen-atom transfer for polymerization and 3D printing of conductive polymer","authors":"Xin Zhou, Shangwen Fang, Yangnan Hu, Xin Du, Haibo Ding, Renjie Chai, Jie Han, Jin Xie, Zhongze Gu","doi":"10.1038/s44160-024-00582-w","DOIUrl":"10.1038/s44160-024-00582-w","url":null,"abstract":"The photoinduced polymerization of electron-rich heteroaromatic pentacycles (ERHPs), such as thiophene derivatives and pyrrole derivatives, is challenging owing to the inherent stability of their aromatic structure. The resultant polymers are organic semiconductor materials that are widely used in both organic electronic and bioelectronic devices. Here we report an efficient hydrogen-atom transfer (HAT) photocatalyst, which is the dimerization product (1,2-bis(4-(2-hydroxyethoxy)phenyl)ethane-1,2-dione) of an acyl radical generated by the photolysis of Irgacure 2959, and its use for the dehydrogenation of coupled ERHPs formed in an acidic environment. The dehydrogenation occurs via a double HAT process, enabling the photopolymerization of ERHPs. This reaction also allows us to fabricate three-dimensional (3D) conductive pathways in hydrogels. The hydrogel can be printed to form free-standing 3D conductive structures of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate with a precision of 220 nm, markedly surpassing structures built using previous methods (>10 µm). The approach introduces opportunities for precision engineering of 3D electrodes with the possibility of expanding applications in organic electronics and bioelectronics. A photopolymerization strategy for electron-rich heteroaromatic pentacycles, suitable for two-photon printing, is reported. A dimerized product of an acyl radical, formed by photolysis of Irgacure 2959, catalyses the dehydrogenation of coupled heteroaromatic pentacycles synthesized in acidic conditions via double hydrogen-atom transfer to produce conductive polymers.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 9","pages":"1145-1157"},"PeriodicalIF":0.0,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510626","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Pd-catalysed direct β-C(sp3)–H fluorination of aliphatic carboxylic acids 钯催化脂肪族羧酸的直接 β-C(sp3)-H氟化反应
Nature synthesis Pub Date : 2024-06-21 DOI: 10.1038/s44160-024-00578-6
Sourjya Mal, Friedrich Jurk, Kerstin Hiesinger, Manuel van Gemmeren
{"title":"Pd-catalysed direct β-C(sp3)–H fluorination of aliphatic carboxylic acids","authors":"Sourjya Mal, Friedrich Jurk, Kerstin Hiesinger, Manuel van Gemmeren","doi":"10.1038/s44160-024-00578-6","DOIUrl":"10.1038/s44160-024-00578-6","url":null,"abstract":"The ever-increasing demand for fluorinated molecules due to their widespread applications has raised substantial interest in the development of new synthetic methodologies that selectively introduce fluorine into molecular scaffolds. While transition-metal-catalysed fluorination reactions in principle provide a direct means to convert inert C–H bonds into C–F bonds, fundamental challenges such as the high energetic barriers associated with the formation of C–F bonds by reductive elimination, among others, remain to be systematically addressed. Carboxylic acids, owing to their versatile synthetic utility in organic synthesis, serve as ideal model substrates in this context. Here we report a protocol that enables the β-C(sp3)–H fluorination of free carboxylic acids, giving access to a wide range of fluorinated carboxylic acids. The rational design of the oxidizing reagent proved to be crucial in establishing the protocol and introduces an additional design dimension to the field of C–H activation. C–F bond formation using transition-metal catalysis is a challenge owing to the high energy barrier associated with reductive elimination. Now the direct β-C(sp3)–H fluorination of aliphatic carboxylic acids with a broad substrate scope is reported, using rational oxidant design to facilitate the reductive elimination step.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 10","pages":"1292-1298"},"PeriodicalIF":0.0,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s44160-024-00578-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510625","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Cyclolignan synthesis streamlined by enantioselective hydrogenation of tetrasubstituted olefins 通过四取代烯烃的对映选择性氢化简化环木质素的合成
Nature synthesis Pub Date : 2024-06-20 DOI: 10.1038/s44160-024-00564-y
Wen-Xiu Xu, Zhuo Peng, Qing-Xiu Gu, Yao Zhu, Li-Han Zhao, Fucheng Leng, Hai-Hua Lu
{"title":"Cyclolignan synthesis streamlined by enantioselective hydrogenation of tetrasubstituted olefins","authors":"Wen-Xiu Xu, Zhuo Peng, Qing-Xiu Gu, Yao Zhu, Li-Han Zhao, Fucheng Leng, Hai-Hua Lu","doi":"10.1038/s44160-024-00564-y","DOIUrl":"10.1038/s44160-024-00564-y","url":null,"abstract":"Natural products have long been valuable sources of inspiration for drug discovery. Unfortunately, the inherent limitations of direct semisynthetic derivatizations have become clear, and the need to overcome these limitations is now particularly urgent because the most valuable natural products tend to be isolated in minute amounts; de novo synthesis with ideal modularity and diversity is therefore a critical goal in drug discovery research. Herein we report a powerful, general platform for cyclolignan synthesis that involves challenging rhodium-catalysed enantioselective hydrogenation of tetrasubstituted 1,2-dihydronaphthalene esters (>40 examples; up to 99% yield, >99% e.e.). This unique platform allows ready access to various types of cyclolignans, as exemplified by the expedient and mostly protecting-group-free synthesis of over thirty cyclolignans, including many that have not previously been synthesized, such as 6-methoxy podophyllotoxin, cleistantoxin, picrobursenin, austrobailignan-4, (+)-lirionol, (+)-gaultherin C, ovafolinin D, fimbricalyxoid A, and aglacins D, F–H (with three revised structures). We expect this work to inspire modular, de novo syntheses of other important classes of natural products and thus to rejuvenate the role of natural products in drug discovery and development. Semisynthetic derivatization approaches to synthesize cyclolignans are limited to using natural sources with inflexible structural features. Now, a powerful, general platform for the synthesis of various types of optically active cyclolignans is achieved through the strategic application of the asymmetric hydrogenation of tetrasubstituted olefins and C(sp3)–H functionalization.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 8","pages":"986-997"},"PeriodicalIF":0.0,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510627","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Applications of synthetic polymers directed toward living cells 针对活细胞的合成聚合物的应用
Nature synthesis Pub Date : 2024-06-20 DOI: 10.1038/s44160-024-00560-2
Anqi Zhang, Spencer Zhao, Jonathan Tyson, Karl Deisseroth, Zhenan Bao
{"title":"Applications of synthetic polymers directed toward living cells","authors":"Anqi Zhang, Spencer Zhao, Jonathan Tyson, Karl Deisseroth, Zhenan Bao","doi":"10.1038/s44160-024-00560-2","DOIUrl":"10.1038/s44160-024-00560-2","url":null,"abstract":"Cells execute remarkable functions using biopolymers synthesized from natural building blocks. Engineering cells to leverage the vast array of synthesizable abiotic polymers could provide enhanced or entirely new cellular functions. Here we discuss the applications of in situ-synthesized abiotic polymers in three distinct domains: intracellular polymerization, cell-surface polymerization and extracellular polymerization. These advances have led to novel applications in various areas, such as cancer therapy, cell imaging, cellular activity manipulation, cell protection and electrode assembly. Examples of these synthetic approaches can be applied across all domains of life, ranging from microbes and cultured mammalian cells to plants and animals. Finally, we discuss challenges and future opportunities in this emerging field, which could enable new synthetic approaches to influence biological processes and functions. Cell-based polymerization offers a promising avenue for integrating synthetic chemistry with biological systems. By leveraging cellular machinery, native chemical environments and external stimuli, the in situ-synthesized polymers hold the potential to impact diverse biomedical research domains, from the regulation of cell behaviour to targeted therapeutics.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 8","pages":"943-957"},"PeriodicalIF":0.0,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A one-pot strategy for anchoring single Pt atoms in MOFs with diverse coordination environments 在具有不同配位环境的 MOF 中锚定单个铂原子的一步法策略
Nature synthesis Pub Date : 2024-06-20 DOI: 10.1038/s44160-024-00585-7
Shaoxiong Liu, Yu Wang, Kyein Far Lyu, Xiaocheng Lan, Tiefeng Wang
{"title":"A one-pot strategy for anchoring single Pt atoms in MOFs with diverse coordination environments","authors":"Shaoxiong Liu, Yu Wang, Kyein Far Lyu, Xiaocheng Lan, Tiefeng Wang","doi":"10.1038/s44160-024-00585-7","DOIUrl":"10.1038/s44160-024-00585-7","url":null,"abstract":"It is challenging to precisely control and identify the coordination environment of single-atom active sites due to non-uniform substrate surfaces. This complicates the task of bridging experimental and theoretical investigations. Here, using a one-pot method, we immobilized single Pt(0) atoms within various terephthalic acid-based metal–organic frameworks, thereby constructing well-defined active sites with varied organic coordination environments. In the isoreticular metal–organic framework UiO-6–X (–X = –H, –NH2, –Br and –I), influenced by the functional groups, the resulting Pt1 sites exhibited distinct catalytic activities for hydrogenation and sintering resistance. Mechanistic studies reveal that this is related to alteration of the electronic state of Pt centres and the adsorption behaviour of intermediates on the Pt sites. Pt1@UiO-66–Br gave the highest activity and excellent thermal stability, with no metal agglomeration in H2 up to 300 °C. Our work introduces a strategy for the precise environmental modification of isolated metal atoms for better catalytic performance. Preventing the co-existence of single-atom active sites with differing coordination environments is challenging. Here the coordination environment of single Pt(0) atoms is precisely controlled within terephthalic acid-based metal–organic frameworks, resulting in distinct catalytic activities and sintering resistance.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 9","pages":"1158-1167"},"PeriodicalIF":0.0,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530220","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Efficient ethylene electrosynthesis through C–O cleavage promoted by water dissociation 通过水解离促进 C-O 裂解实现高效乙烯电合成
Nature synthesis Pub Date : 2024-06-20 DOI: 10.1038/s44160-024-00568-8
Yongxiang Liang, Feng Li, Rui Kai Miao, Sunpei Hu, Weiyan Ni, Shuzhen Zhang, Yanjiang Liu, Yang Bai, Haoyue Wan, Pengfei Ou, Xiao-Yan Li, Ning Wang, Sungjin Park, Fengwang Li, Jie Zeng, David Sinton, Edward H. Sargent
{"title":"Efficient ethylene electrosynthesis through C–O cleavage promoted by water dissociation","authors":"Yongxiang Liang, Feng Li, Rui Kai Miao, Sunpei Hu, Weiyan Ni, Shuzhen Zhang, Yanjiang Liu, Yang Bai, Haoyue Wan, Pengfei Ou, Xiao-Yan Li, Ning Wang, Sungjin Park, Fengwang Li, Jie Zeng, David Sinton, Edward H. Sargent","doi":"10.1038/s44160-024-00568-8","DOIUrl":"10.1038/s44160-024-00568-8","url":null,"abstract":"Electrochemical reduction of carbon monoxide is a promising carbonate-free approach to produce ethylene using renewable electricity. However, the performance of this process suffers from low selectivity and energy efficiency. A priority has been to weaken water dissociation with the aim of inhibiting the competing hydrogen evolution reaction but when this path was examined by replacing H2O with D2O, a further-reduced selectivity toward ethylene was observed. Here we examine approaches to promote water adsorption and to decrease the energy barrier to the ensuing water dissociation step, which could promote C–O cleavage in *CHCOH hydrogenation to *CCH. We modified a copper catalyst with the strong electron acceptor 7,7,8,8-tetracyanoquinodimethane, which made the catalyst surface electron deficient. The observed ethylene Faradaic efficiency was 75%, 1.3 times greater than that of unmodified copper control catalysts. A full-cell energy efficiency of 32% was achieved for a total projected energy cost of 154 GJ t−1 in ethylene electrosynthesis in a membrane electrode assembly. CO electroreduction is a promising carbonate-free approach to produce ethylene, but suffers from limited selectivity and low energy efficiency. By modifying copper with a strong electron acceptor, 7,7,8,8-tetracyanoquinodimethane, the water dissociation step is accelerated, leading to excellent ethylene selectivity and full-cell energy efficiency in CO electroreduction.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 9","pages":"1104-1112"},"PeriodicalIF":0.0,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510628","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Reproducible high-quality perovskite single crystals by flux-regulated crystallization with a feedback loop 通过带反馈回路的通量调节结晶技术获得可重复的高质量过氧化物单晶体
Nature synthesis Pub Date : 2024-06-18 DOI: 10.1038/s44160-024-00576-8
Yuki Haruta, Hanyang Ye, Paul Huber, Nicholas Sandor, Antoine Pavesic Junior, Sergey Dayneko, Shuang Qiu, Vishal Yeddu, Makhsud I. Saidaminov
{"title":"Reproducible high-quality perovskite single crystals by flux-regulated crystallization with a feedback loop","authors":"Yuki Haruta, Hanyang Ye, Paul Huber, Nicholas Sandor, Antoine Pavesic Junior, Sergey Dayneko, Shuang Qiu, Vishal Yeddu, Makhsud I. Saidaminov","doi":"10.1038/s44160-024-00576-8","DOIUrl":"10.1038/s44160-024-00576-8","url":null,"abstract":"Controlling the linear growth rate, a critical factor that determines crystal quality, has been a challenge in solution-grown single crystals due to complex crystallization kinetics influenced by multiple parameters. Here we introduce a flux-regulated crystallization (FRC) method to directly monitor and feedback-control the linear growth rate, circumventing the need to control individual growth conditions. When applied to metal halide perovskites, the FRC maintains a stable linear growth rate for over 40 h in synthesizing CH3NH3PbBr3 and CsPbBr3 single crystals, achieving outstanding crystallinity (quantified by a full width at half-maximum of 15.3 arcsec in the X-ray rocking curve) in a centimetre-scale single crystal. The FRC is a reliable platform for synthesizing high-quality crystals essential for commercialization and systematically exploring crystallization conditions, maintaining a key parameter—the linear growth rate—constant, which enables a comprehensive understanding of the impact of other influencing factors. Controlling linear growth rate is challenging in solution-grown single crystals. Now, flux-regulated crystallization (FRC) is developed to directly feedback-control the growth rate. When applied to metal halide perovskites, FRC achieves reproducible high crystallinity, offering a platform for synthesizing high-quality single crystals and exploring crystallization conditions.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 10","pages":"1212-1220"},"PeriodicalIF":0.0,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s44160-024-00576-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530223","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Horner–Wadsworth–Emmons olefination of proteins and glycoproteins 蛋白质和糖蛋白的霍纳-沃兹沃斯-埃蒙斯油化作用
Nature synthesis Pub Date : 2024-06-14 DOI: 10.1038/s44160-024-00563-z
Antonio Angelastro, Alexey Barkhanskiy, Toby Journeaux, Rohan Sivapalan, Thomas A. King, Laura Rodríguez Pérez, William R. F. Goundry, Perdita Barran, Sabine L. Flitsch
{"title":"Horner–Wadsworth–Emmons olefination of proteins and glycoproteins","authors":"Antonio Angelastro, Alexey Barkhanskiy, Toby Journeaux, Rohan Sivapalan, Thomas A. King, Laura Rodríguez Pérez, William R. F. Goundry, Perdita Barran, Sabine L. Flitsch","doi":"10.1038/s44160-024-00563-z","DOIUrl":"10.1038/s44160-024-00563-z","url":null,"abstract":"Chemo-selective modifications of proteins are fundamental to the advancement of biological and pharmaceutical sciences. The search for biocompatible chemical reactions has prompted us to investigate Horner–Wadsworth–Emmons (HWE) olefinations, iconic reactions in organic synthesis that would give rise to new selective protein olefinations. Our choice of HWE olefinations was inspired by the growing number of methods for generating aldehydes as transient reactive groups in proteins and the potential for mild and simple reaction conditions. Here we show that HWE olefination reactions on aldehydes, produced by both chemical and enzymatic methods, are compatible with physiological conditions and highly selective in small and large proteins, including therapeutic antibodies and stable recombinant proteins exemplified by green fluorescent protein. Reaction kinetics can be fine-tuned over orders of magnitude both by judicious use of substituents and pH regulation. The electrophilic nature of the HWE olefination products can be tuned to allow for subsequent nucleophilic additions, including thiol- and phospha-Michael additions. Our results demonstrate that HWE olefination of aldehydes in proteins provides efficient and selective bioconjugation chemistries that are orthogonal to existing methods. Aldehyde-bearing proteins are shown to be suitable substrates for Horner–Wadsworth–Emmons reactions. Applying this process to proteins and glycoproteins enables site-specific bioconjugation with tunable reaction kinetics.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 8","pages":"976-985"},"PeriodicalIF":0.0,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s44160-024-00563-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141342629","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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