Nature synthesis最新文献_第10页

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":null,"pages":null},"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":null,"pages":null},"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":null,"pages":null},"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

Horner–Wadsworth–Emmons olefination for bioconjugation 用于生物共轭的霍纳-沃兹沃斯-埃蒙斯烯化作用

Nature synthesis Pub Date : 2024-06-14 DOI: 10.1038/s44160-024-00571-z

Yimon Aye

引用次数: 0

Rational electrochemical design of hierarchical microarchitectures for SERS sensing applications 用于 SERS 传感应用的分层微架构的合理电化学设计

Nature synthesis Pub Date : 2024-06-12 DOI: 10.1038/s44160-024-00553-1

Liyan Zhao, Yanling Wang, Shoutong Jin, Ning An, Mi Yan, Xiaochen Zhang, Zijian Hong, Shikuan Yang

{"title":"Rational electrochemical design of hierarchical microarchitectures for SERS sensing applications","authors":"Liyan Zhao, Yanling Wang, Shoutong Jin, Ning An, Mi Yan, Xiaochen Zhang, Zijian Hong, Shikuan Yang","doi":"10.1038/s44160-024-00553-1","DOIUrl":"10.1038/s44160-024-00553-1","url":null,"abstract":"Electrochemical deposition has been widely used to prepare conformal coatings but has rarely been used to design well-defined micro/nanostructures. Here we report electrochemical synthesis of complex, hierarchical inorganic microarchitectures simply via programming the applied potential waveforms. We identify two distinct electrochemical growth modes—the stacking mode and the flattening mode—under different potential waveforms. We demonstrate how these growth modes can work individually or cooperatively to design previously inaccessible microarchitectures. Each specific potential waveform corresponds to a specific microarchitecture, allowing us to prepare a rich library of microarchitectures. The designed microarchitectures can be converted into other materials by simple redox-potential-driven chemical reactions. We preliminarily studied the applications of converted nanoporous silver microscale torpedoes as high-performance surface-enhanced Raman spectroscopy (SERS) sensing substrates. The reported method opens up a new concept to design complex inorganic microarchitectures with promising applications in metamaterials, chemically or magnetically propelled microrobotics, and miniaturized devices. Rational design of the morphology of inorganic microstructures is challenging. Now an electrochemical method is reported for designing the morphology of inorganic microarchitectures via programming of the potential waveforms applied during microstructure growth. These microstructures have potential application as SERS sensors.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141350998","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 methylation and amination reactions with CO2 and NOxy– 与二氧化碳和氮氧化物的电催化甲基化和胺化反应

Nature synthesis Pub Date : 2024-06-12 DOI: 10.1038/s44160-024-00565-x

Conor L. Rooney, Hailiang Wang

引用次数: 0

Publisher Correction: Rapid automated iterative small-molecule synthesis 出版商更正：快速自动迭代小分子合成

Nature synthesis Pub Date : 2024-06-11 DOI: 10.1038/s44160-024-00601-w

Wesley Wang, Nicholas H. Angello, Daniel J. Blair, Theodore Tyrikos-Ergas, William H. Krueger, Kameron N. S. Medine, Antonio J. LaPorte, Joshua M. Berger, Martin D. Burke

引用次数: 0

Asymmetric allylic C(sp3)–C(sp3) bond functionalization 不对称烯丙基 C(sp3)-C(sp3)键官能化

Nature synthesis Pub Date : 2024-06-10 DOI: 10.1038/s44160-024-00556-y

引用次数: 0

Self-pressurizing nanoscale capsule catalysts for CO2 electroreduction to acetate or propanol 用于将二氧化碳电还原为醋酸或丙醇的自加压纳米级胶囊催化剂

Nature synthesis Pub Date : 2024-06-07 DOI: 10.1038/s44160-024-00552-2

Yanming Cai, Ruixin Yang, Jiaju Fu, Zhe Li, Liangyiqun Xie, Kai Li, Yu-Chung Chang, Shichao Ding, Zhaoyuan Lyu, Jian-Rong Zhang, Jun-Jie Zhu, Yuehe Lin, Wenlei Zhu

{"title":"Self-pressurizing nanoscale capsule catalysts for CO2 electroreduction to acetate or propanol","authors":"Yanming Cai, Ruixin Yang, Jiaju Fu, Zhe Li, Liangyiqun Xie, Kai Li, Yu-Chung Chang, Shichao Ding, Zhaoyuan Lyu, Jian-Rong Zhang, Jun-Jie Zhu, Yuehe Lin, Wenlei Zhu","doi":"10.1038/s44160-024-00552-2","DOIUrl":"10.1038/s44160-024-00552-2","url":null,"abstract":"The selective one-step CO2 electroreduction reaction (CO2RR) to acetate and propanol has garnered intense interest. Here we report the design of self-pressurizing nanoscale capsule catalysts for the CO2RR. A high-pressure CO intermediate environment is created around copper catalysts by a permselective enclosure. Microkinetic modelling, 13CO2/12CO co-feed experiments and in situ Raman spectroscopy confirm that a unique CO–CO2 coupling path is involved, which is only initiated at high CO intermediate pressure. This pathway benefits acetate production due to the kinetic and energetic advantages of COCO2*. The acetate Faradaic efficiency is 38.5 ± 2.2% (8 times higher than that achieved without enclosure) and the acetate partial current density is 328 ± 19 mA cm−2, which surpasses the performance of previous CO2RR catalysts. In situ investigation indicates that the CO pressure inside the nanoscale capsule catalysts can reach 8 ± 3 bar. Furthermore, self-pressurizing nanoscale capsule catalysts with a CuI-derived core can reduce CO2 to propanol with a Faradaic efficiency of 25.7 ± 1.2% and a conversion rate of 155 ± 3 mA cm−2. CO2 electroreduction to multicarbon products is desirable but challenging. Now, self-pressurizing nanoscale capsule catalysts are synthesized. The self-pressurising capsules harness high-pressure CO environments for selective acetate or propanol production via a CO–CO2 coupling pathway.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141373860","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

C(sp3)–C(sp3) bond formation through nitrogen deletion of secondary amines using O-diphenylphosphinylhydroxylamine 使用 O-二苯基膦酰羟胺通过仲胺脱氮形成 C(sp3)-C(sp3)键

Nature synthesis Pub Date : 2024-06-07 DOI: 10.1038/s44160-024-00559-9

Ting Guo, Jinghao Li, Zhangkai Cui, Zefan Wang, Hongjian Lu

{"title":"C(sp3)–C(sp3) bond formation through nitrogen deletion of secondary amines using O-diphenylphosphinylhydroxylamine","authors":"Ting Guo, Jinghao Li, Zhangkai Cui, Zefan Wang, Hongjian Lu","doi":"10.1038/s44160-024-00559-9","DOIUrl":"10.1038/s44160-024-00559-9","url":null,"abstract":"The nitrogen deletion of secondary amines has emerged as an effective strategy for direct molecular skeletal editing and carbon–carbon bond formation. However, current methods are often limited to acyclic bis(α-primary) amines and cyclic amines, which possess two stabilizing elements at the α-position of amine. Here we report the use of O-diphenylphosphinylhydroxylamine as a reagent for nitrogen deletion of secondary amines to form C(sp3)–C(sp3) bonds. This method overcomes substrate requirements of other methods and tolerates a range of secondary amine substrates. The process can be readily applied to multiple nitrogen deletion processes, is tolerant of both air and water, forms water-soluble byproducts and can be readily scaled to a hundred-gram scale. The versatility of the method is further showcased through the direct editing of natural products, pharmaceutical compounds, N-coordinated ligands, a three-dimensional amine cage and the synthesis of several bioactive compounds. Methods for nitrogen deletion of secondary amines are often limited by substrate structure requirements. Now the use of O-diphenylphosphinylhydroxylamine for nitrogen deletion of a range of secondary amines is reported. The developed process is tolerant of both air and water and can be scaled easily.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141372954","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