Nature synthesis最新文献_第3页

Metallic nanosheets fill the gap 金属纳米片填补了这一空白

Nature synthesis Pub Date : 2024-11-14 DOI: 10.1038/s44160-024-00686-3

Xiaoxi Li, Zheng Vitto Han

引用次数: 0

Mechano-photoexcitation for organic synthesis using mechanoluminescent materials as photon sources

Nature synthesis Pub Date : 2024-11-14 DOI: 10.1038/s44160-024-00681-8

Xiaohua Xin, Jinxing Geng, Duo Zhang, Hwee Ting Ang, Hui Wang, Yongliang Cheng, Yun Liu, Ren Wei Toh, Jie Wu, Han Wang

{"title":"Mechano-photoexcitation for organic synthesis using mechanoluminescent materials as photon sources","authors":"Xiaohua Xin, Jinxing Geng, Duo Zhang, Hwee Ting Ang, Hui Wang, Yongliang Cheng, Yun Liu, Ren Wei Toh, Jie Wu, Han Wang","doi":"10.1038/s44160-024-00681-8","DOIUrl":"10.1038/s44160-024-00681-8","url":null,"abstract":"Implementing photochemical reactions through mechanochemical methods can reduce waste generation by eliminating the need for bulk solvents. The absence of solvent results in exceptionally high concentrations of catalysts and reactants in reactions, substantially improving reaction rates and efficiency in terms of both time and energy utilization. However, the integration of mechano- and photochemical approaches is often hindered by the limited transparency of mechanochemical reaction vessels. Here we present a mechano-photoexcitation strategy that utilizes mechanoluminescent materials, in particular SrAl2O4:Eu2+/Dy3+, as internal photon sources activated by mechanical energy. We demonstrate the efficacy of this strategy in two photochemical processes: the Hofmann–Löffler–Freytag reaction and the activation of electron donor–acceptor complexes in sulfonylation reactions. Mechanistic studies confirm the radical nature of these transformations, and control experiments validate the critical role of mechano-photoactivation. By utilizing mechanical energy alone, this method eliminates the need for external light sources and enables gramme-scale photochemical transformations. Our approach represents a valuable application of mechanical energy in synthetic chemistry, providing a complementary means for integrating photochemistry with mechanochemistry. The combination of mechanochemical and photochemical approaches is often hindered by the limited transparency of reaction vessels. Now, a mechano-photoexcitation strategy is reported using mechanoluminescent materials as internal photon sources activated by mechanical energy. This approach enables solvent-free photochemical reactions, as demonstrated in Hofmann–Löffler–Freytag and sulfonylation reactions.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 2","pages":"177-187"},"PeriodicalIF":0.0,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143397390","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

Diffusion-mediated synthesis of high-quality organic–inorganic hybrid perovskite nanocrystals

Nature synthesis Pub Date : 2024-11-14 DOI: 10.1038/s44160-024-00678-3

Xiang Sun, Lin Yuan, Yang Liu, Guozheng Shi, Yumin Wang, Chunmeng Liu, Xuliang Zhang, Yaxin Zhao, Chenyu Zhao, Mengmeng Ma, Boyuan Shen, Yaxing Wang, Qing Shen, Zeke Liu, Wanli Ma

{"title":"Diffusion-mediated synthesis of high-quality organic–inorganic hybrid perovskite nanocrystals","authors":"Xiang Sun, Lin Yuan, Yang Liu, Guozheng Shi, Yumin Wang, Chunmeng Liu, Xuliang Zhang, Yaxin Zhao, Chenyu Zhao, Mengmeng Ma, Boyuan Shen, Yaxing Wang, Qing Shen, Zeke Liu, Wanli Ma","doi":"10.1038/s44160-024-00678-3","DOIUrl":"10.1038/s44160-024-00678-3","url":null,"abstract":"Organic–inorganic hybrid perovskite nanocrystals (PNCs) (APbX3, A = formamidinium, methylammonium, X = Cl, Br, I) are semiconductor materials with important implications for fundamental research and optoelectronic applications. However, the development of hybrid PNCs lags behind their all-inorganic counterparts (CsPbX3), primarily due to their fast growth time (tens of seconds) caused by the uncontrollable kinetics of their synthesis. Here we present a diffusion-mediated synthesis approach by selecting lead precursors with desired solubility in the reaction solvent. Pb(SCN)2, which has limited solubility, serves as a lead reservoir, providing a continuous source of lead throughout the reaction process. This strategy significantly slows down the reaction kinetics. The synthesis time for hybrid PNCs can be drastically prolonged to 180 min, while maintaining the size-focusing stage. As a result, the diffusion-mediated kinetics enables the scalable synthesis of high-quality hybrid PNCs with high monodispersity and near-unity photoluminescence quantum yield. The high-quality hybrid PNCs obtained by this method will stimulate explorations into their properties and drive the development of efficient optoelectronic devices. A diffusion-mediated synthesis strategy for organic–inorganic hybrid perovskite nanocrystals is reported, which can substantially slow down the reaction kinetics, improving size uniformity and achieving near-unity photoluminescence quantum yield.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 2","pages":"167-176"},"PeriodicalIF":0.0,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143397418","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

Analysis of siderochelin biosynthesis reveals that a type II polyketide synthase catalyses diketide formation

Nature synthesis Pub Date : 2024-11-06 DOI: 10.1038/s44160-024-00677-4

Yao Qian, Jinmin Gao, Ming Chen, Bo Pang, Zhijun Tang, Wei Huang, Wen Liu

{"title":"Analysis of siderochelin biosynthesis reveals that a type II polyketide synthase catalyses diketide formation","authors":"Yao Qian, Jinmin Gao, Ming Chen, Bo Pang, Zhijun Tang, Wei Huang, Wen Liu","doi":"10.1038/s44160-024-00677-4","DOIUrl":"10.1038/s44160-024-00677-4","url":null,"abstract":"Polyketide synthases (PKSs) programme the assembly of polyketides that possess a wide range of pharmacological properties. In addition to assembly logic, carboxylic-acid-derived substrates underpin the structures and associated biological activities of these biosynthetically related natural products. Known type II PKSs exclusively use a malonyl extender unit for decarboxylative condensation and elongation, restricting the structural diversity. Based on investigations into the biosynthesis of siderochelins, a group of ferrous ion chelators, here we report a distinct five-component type II PKS that catalyses diketide formation and uses a methylmalonyl extender unit for condensation with the 3-hydroxypicolinyl starter unit during the formation of the pyrroline ring. Genome mining, gene inactivation, isotopic labelling and detailed biochemical characterization rationalize the capability of this type II PKS to use non-malonyl carboxylic substrates for starting and extending polyketide synthesis. The utility of this type II PKS is further recognized by its high compatibility with carboxylic acid substrate variation and by its ability to evolve to tolerate unnatural and/or unacceptable extenders. Type II polyketide synthases (PKSs) comprise multiple enzymes and control the biosynthesis of polyketides by using a malonyl extender unit for decarboxylative elongation. Now, genome mining, gene inactivation, isotopic labelling and biochemical analysis reveal that the biosynthetic pathway of siderochelin proceeds through a five-component type II PKS which uses a methylmalonyl extender for diketide formation.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 2","pages":"219-232"},"PeriodicalIF":0.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143397410","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

Sugar-modified nucleosides from simple ingredients

Nature synthesis Pub Date : 2024-11-05 DOI: 10.1038/s44160-024-00645-y

Felix Kaspar

引用次数: 0

An engineered aldolase enables the biocatalytic synthesis of 2′-functionalized nucleoside analogues

Nature synthesis Pub Date : 2024-11-05 DOI: 10.1038/s44160-024-00671-w

Matthew Willmott, William Finnigan, William R. Birmingham, Sasha R. Derrington, Rachel S. Heath, Christian Schnepel, Martin A. Hayes, Peter D. Smith, Francesco Falcioni, Nicholas J. Turner

{"title":"An engineered aldolase enables the biocatalytic synthesis of 2′-functionalized nucleoside analogues","authors":"Matthew Willmott, William Finnigan, William R. Birmingham, Sasha R. Derrington, Rachel S. Heath, Christian Schnepel, Martin A. Hayes, Peter D. Smith, Francesco Falcioni, Nicholas J. Turner","doi":"10.1038/s44160-024-00671-w","DOIUrl":"10.1038/s44160-024-00671-w","url":null,"abstract":"Nucleosides functionalized at the 2′-position play a crucial role in therapeutics, serving as both small-molecule drugs and modifications in therapeutic oligonucleotides. However, the synthesis of these molecules often presents substantial synthetic challenges. Here we present an approach to the synthesis of 2′-functionalized nucleosides based on enzymes from the purine nucleoside salvage pathway. Initially, active-site variants of deoxyribose-5-phosphate aldolase were generated for the highly stereoselective synthesis of d-ribose-5-phosphate analogues with a broad range of functional groups at the 2-position. Thereafter, these 2-modified pentose phosphates were converted into 2′-modified purine analogues by construction of one-pot multienzyme cascade reactions, leading to the synthesis of guanosine (2′-OH) and adenosine (2′-OH, 2′-Me, 2′-F) analogues. This cascade allows for the control of the 2′-functional group alongside 2-stereochemistry. Our findings demonstrate the capability of these biocatalytic cascades to efficiently generate 2′-functionalized nucleosides, starting from simple starting materials. The chemical synthesis of nucleoside analogues with modifications at the 2-position often requires multiple steps and the extensive use of protecting groups. Now, biocatalytic cascades are reported for the synthesis of 2-functionalized sugars and 2′-functionalized nucleosides, using enzymes derived from those of the purine nucleoside salvage pathway.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 2","pages":"156-166"},"PeriodicalIF":0.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s44160-024-00671-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143397420","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

Carbonate shell regulates CuO surface reconstruction for enhanced CO2 electroreduction 碳酸盐壳调节CuO表面重构，增强CO2电还原

Nature synthesis Pub Date : 2024-10-31 DOI: 10.1038/s44160-024-00672-9

Xianhui Ma, Tong Yang, Dayin He, Xiaoping Gao, Wei Jiang, Deming Li, Yuanhua Sun, Xingen Lin, Jie Xu, Huijuan Wang, Xiaolin Tai, Yue Lin, Tao Yao, Huang Zhou, Yuen Wu

{"title":"Carbonate shell regulates CuO surface reconstruction for enhanced CO2 electroreduction","authors":"Xianhui Ma, Tong Yang, Dayin He, Xiaoping Gao, Wei Jiang, Deming Li, Yuanhua Sun, Xingen Lin, Jie Xu, Huijuan Wang, Xiaolin Tai, Yue Lin, Tao Yao, Huang Zhou, Yuen Wu","doi":"10.1038/s44160-024-00672-9","DOIUrl":"10.1038/s44160-024-00672-9","url":null,"abstract":"The surface structure of catalysts greatly impacts the performance of the electrochemical CO2 reduction reaction. However, the reconstruction caused by applied potential can affect the surface structure and is difficult to control. Here, inspired by drug capsules with extended-release structures, we construct a water-soluble carbonate shell on metal oxide catalysts. The shell acts as a protective coating, effectively slowing down the surface evolution process of the catalyst from high to low valence state under the applied electric field. Therefore, by tuning the shell thickness and dissolution rates, the surface reconstruction can be regulated, steering it towards the formation of an abundant low-coordinated structure. This strategy could promote the generation of Cu(0) with rich grain boundaries and small particles. The C2+ Faradaic efficiency was 82.8 ± 2.2% with a current density of 2.0 A cm−2, exceeding the performance of conventional CuO catalysts. Ex situ and in situ characterizations indicate that these generated surface structures enhance *CO intermediate stabilization and C–C coupling. Our approach for regulating surface reconstruction can be applied to other catalysts, such as ZnO, In2O3, SnO2 and Bi2O3, elevating their selectivity towards CO and formate. Electrochemical reconstruction impacts the surface structure of electrocatalysts and is challenging to control in CO2 electroreduction. Here, by regulating a carbonate shell around an oxide catalyst, the reconstruction is guided towards an abundant low-coordinated structure, achieving a C2+ Faradaic efficiency of 82.8 ± 2.2% at a current density of 2 A cm−2.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 1","pages":"53-66"},"PeriodicalIF":0.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142995910","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

Anomalous in-plane electrical anisotropy in elemental metal nanosheets 单质金属纳米片的面内异常电各向异性

Nature synthesis Pub Date : 2024-10-31 DOI: 10.1038/s44160-024-00669-4

Taehoon Kim, Dongchul Seo, Sungsoon Kim, Gyu Won Kim, Seung-Jae Shin, Se Young Kim, Minwoo Lee, Jihong Bae, Hansol Ra, Minjun Kim, Taeyoung Kim, Soyeon Lee, Seung-Rok Kim, Hyunmin Cho, Han Joo Lee, Jaehyeok Choi, Seongil Im, Jin-Woo Park, Jinwoo Cheon, Joon Sang Lee, Aron Walsh, Wooyoung Shim

{"title":"Anomalous in-plane electrical anisotropy in elemental metal nanosheets","authors":"Taehoon Kim, Dongchul Seo, Sungsoon Kim, Gyu Won Kim, Seung-Jae Shin, Se Young Kim, Minwoo Lee, Jihong Bae, Hansol Ra, Minjun Kim, Taeyoung Kim, Soyeon Lee, Seung-Rok Kim, Hyunmin Cho, Han Joo Lee, Jaehyeok Choi, Seongil Im, Jin-Woo Park, Jinwoo Cheon, Joon Sang Lee, Aron Walsh, Wooyoung Shim","doi":"10.1038/s44160-024-00669-4","DOIUrl":"10.1038/s44160-024-00669-4","url":null,"abstract":"Two-dimensional (2D) elemental metals, often overlooked owing to their lack of switching or dielectric properties, have the potential to exhibit unique properties unachievable by their bulk counterparts if their microstructure can be controlled. Here we propose an electrodeposition method that utilizes a confined 2D template to prepare elemental metal nanosheets with an aligned grain orientation, resulting in an exceptionally high in-plane electrical anisotropy of >103. Heterogeneous nucleation is initiated and the directed growth of the metal at the cathode is controlled within a channel whose size is smaller than the critical size of the nuclei. This leads to the formation of anisotropic microstructures, and consequently, the nanosheets exhibit anisotropic electrical properties. Unlike conventional field-effect transistors, devices employing a channel with two orthogonally separated conduction paths yield an exceptional on–off switching ratio exceeding 104. Our approach offers a promising route to produce various 2D elemental metals with properties different from those observed in their bulk counterparts and highlights the potential of anisotropic metallic nanosheets as switching elements. An electrodeposition method is proposed for the growth of elemental metal nanosheets with aligned grain orientation using a confined 2D template. Nucleation and growth are controlled within a confined 2D channel, resulting in nanosheets with high in-plane electrical anisotropy (>103), highlighting their potential as switching elements.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 1","pages":"31-42"},"PeriodicalIF":0.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142995874","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

Extended-release capsule-inspired electrocatalyst design 缓释胶囊式电催化剂设计

Nature synthesis Pub Date : 2024-10-31 DOI: 10.1038/s44160-024-00674-7

Yuanjun Chen, Edward H. Sargent

引用次数: 0

From furans to pyrroles 从呋喃到吡咯

Nature synthesis Pub Date : 2024-10-28 DOI: 10.1038/s44160-024-00682-7

Thomas West

引用次数: 0