Nature chemistry最新文献_第10页

Evolution of complex chemical mixtures reveals combinatorial compression and population synchronicity 复杂化学混合物的演化揭示了组合压缩和种群同步性

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-12 DOI: 10.1038/s41557-025-01734-x

Kavita Matange, Vahab Rajaei, Pau Capera-Aragones, John T. Costner, Adelaide Robertson, Jennifer Seoyoung Kim, Anton S. Petrov, Jessica C. Bowman, Loren Dean Williams, Moran Frenkel-Pinter

{"title":"Evolution of complex chemical mixtures reveals combinatorial compression and population synchronicity","authors":"Kavita Matange, Vahab Rajaei, Pau Capera-Aragones, John T. Costner, Adelaide Robertson, Jennifer Seoyoung Kim, Anton S. Petrov, Jessica C. Bowman, Loren Dean Williams, Moran Frenkel-Pinter","doi":"10.1038/s41557-025-01734-x","DOIUrl":"10.1038/s41557-025-01734-x","url":null,"abstract":"Many open questions about the origins of life are centred on the generation of complex chemical species. Past work has characterized specific chemical reactions that might lead to biological molecules. Here we establish an experimental model of chemical evolution to investigate general processes by which chemical systems continuously change. We used water as a chemical reactant, product and medium. We leveraged oscillating water activity at near-ambient temperatures to cause ratcheting of near-equilibrium reactions in mixtures of organic molecules containing carboxylic acids, amines, thiols and hydroxyl groups. Our system (1) undergoes continuous change with transitions to new chemical spaces while not converging throughout the experiment; (2) demonstrates combinatorial compression with stringent chemical selection; and (3) displays synchronicity of molecular populations. Our results suggest that chemical evolution and selection can be observed in organic mixtures and might ultimately be adapted to produce a broad array of molecules with novel structures and functions. Origins-of-life research has focused on specific chemical reactions that might lead to biological molecules. Now an experimental model of chemical evolution based on oscillating water activity has been established. This system undergoes continuous chemical change, and demonstrates combinatorial compression, stringent chemical selection and synchronicity of molecular populations.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 4","pages":"590-597"},"PeriodicalIF":19.2,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393197","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

Synthetic biomolecular condensates enhance translation from a target mRNA in living cells 合成的生物分子凝聚物增强了活细胞中靶mRNA的翻译。

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-10 DOI: 10.1038/s41557-024-01706-7

Daniel Mark Shapiro, Sonal Deshpande, Seyed Ali Eghtesadi, Miranda Zhong, Cassio Mendes Fontes, David Fiflis, Dahlia Rohm, Junseon Min, Taranpreet Kaur, Joanna Peng, Max Ney, Jonathan Su, Yifan Dai, Aravind Asokan, Charles A. Gersbach, Ashutosh Chilkoti

{"title":"Synthetic biomolecular condensates enhance translation from a target mRNA in living cells","authors":"Daniel Mark Shapiro, Sonal Deshpande, Seyed Ali Eghtesadi, Miranda Zhong, Cassio Mendes Fontes, David Fiflis, Dahlia Rohm, Junseon Min, Taranpreet Kaur, Joanna Peng, Max Ney, Jonathan Su, Yifan Dai, Aravind Asokan, Charles A. Gersbach, Ashutosh Chilkoti","doi":"10.1038/s41557-024-01706-7","DOIUrl":"10.1038/s41557-024-01706-7","url":null,"abstract":"Biomolecular condensates composed of proteins and RNA are one approach by which cells regulate post-transcriptional gene expression. Their formation typically involves the phase separation of intrinsically disordered proteins with a target mRNA, sequestering the mRNA into a liquid condensate. This sequestration regulates gene expression by modulating translation or facilitating RNA processing. Here we engineer synthetic condensates using a fusion of an RNA-binding protein, the human Pumilio2 homology domain (Pum2), and a synthetic intrinsically disordered protein, an elastin-like polypeptide (ELP), that can bind and sequester a target mRNA transcript. In protocells, sequestration of a target mRNA largely limits its translation. Conversely, in Escherichia coli, sequestration of the same target mRNA increases its translation. We characterize the Pum2–ELP condensate system using microscopy, biophysical and biochemical assays, and RNA sequencing. This approach enables the modulation of cell function via the formation of synthetic biomolecular condensates that regulate the expression of a target protein. Formation of biomolecular condensates composed of proteins and RNA facilitates the regulation of gene expression by modulating translation or facilitating RNA processing. Now, synthetic ribonucleoprotein granules created with engineered intrinsically disordered proteins selectively sequester mRNA and enhance protein translation in cells. These highly liquid-like condensates exchange biomolecules across the cell and facilitate target mRNA and ribosome partitioning.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 3","pages":"448-456"},"PeriodicalIF":19.2,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143391370","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

Isotopic labelling of water reveals the hydrogen transfer route in electrochemical CO2 reduction 水的同位素标记揭示了电化学CO2还原过程中氢的转移途径

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-06 DOI: 10.1038/s41557-024-01721-8

Jiguang Zhang, Chengyi Zhang, Meng Wang, Yu Mao, Bo Wu, Qin Yang, Bingqing Wang, Ziyu Mi, Mingsheng Zhang, Ning Ling, Wan Ru Leow, Ziyun Wang, Yanwei Lum

{"title":"Isotopic labelling of water reveals the hydrogen transfer route in electrochemical CO2 reduction","authors":"Jiguang Zhang, Chengyi Zhang, Meng Wang, Yu Mao, Bo Wu, Qin Yang, Bingqing Wang, Ziyu Mi, Mingsheng Zhang, Ning Ling, Wan Ru Leow, Ziyun Wang, Yanwei Lum","doi":"10.1038/s41557-024-01721-8","DOIUrl":"10.1038/s41557-024-01721-8","url":null,"abstract":"Understanding the hydrogenation pathway in electrochemical CO2 reduction is important for controlling product selectivity. The Eley–Rideal mechanism involving proton-coupled electron transfer directly from solvent water is often considered to be the primary hydrogen transfer route. However, in principle, hydrogenation can also occur via the Langmuir–Hinshelwood mechanism using surface-adsorbed *H. Here, by performing CO2 reduction with Cu in H2O–D2O mixtures, we present evidence that the Langmuir–Hinshelwood mechanism is probably the dominant hydrogenation route. From this, we estimate the extent to which each mechanism contributes towards the formation of six important CO2 reduction products. Through computational simulations, we find that the formation of C–H bonds and O–H bonds is governed by the Langmuir–Hinshelwood and Eley–Rideal mechanism, respectively. We also show that promoting the Eley–Rideal pathway could be crucial towards selective multicarbon product formation and suppressing hydrogen evolution. These findings introduce important considerations for the theoretical modelling of CO2 reduction pathways and electrocatalyst design. CO2 electroreduction to higher-value carbons can occur through adsorbed hydrogen or through proton-coupled electron transfer from water. Understanding the impact of each route on product selectivity is challenging. Now H/D isotopic labelling reveals the contribution of each mechanism towards product formation and shows that adsorbed hydrogen dominates the reaction.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 3","pages":"334-343"},"PeriodicalIF":19.2,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192353","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

Molecular contacts with an orthogonal π-skeleton induce amorphization to enhance perovskite solar cell performance 正交π骨架的分子接触诱导非晶化以提高钙钛矿太阳能电池的性能

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-06 DOI: 10.1038/s41557-025-01732-z

Jingjing Zhou, Yixin Luo, Runda Li, Liuwen Tian, Ke Zhao, Jiahui Shen, Donger Jin, Zixuan Peng, Libing Yao, Li Zhang, Qingqing Liu, Shaochen Zhang, Lu Jin, Shenglong Chu, Sisi Wang, Yuan Tian, Jiazhe Xu, Xu Zhang, Pengju Shi, Xiaonan Wang, Wei Fan, Xuechun Sun, Jingyi Sun, Luo-Zhou Chen, Gang Wu, Wen Shi, Hong-Fei Wang, Tianqi Deng, Rui Wang, Deren Yang, Jingjing Xue

{"title":"Molecular contacts with an orthogonal π-skeleton induce amorphization to enhance perovskite solar cell performance","authors":"Jingjing Zhou, Yixin Luo, Runda Li, Liuwen Tian, Ke Zhao, Jiahui Shen, Donger Jin, Zixuan Peng, Libing Yao, Li Zhang, Qingqing Liu, Shaochen Zhang, Lu Jin, Shenglong Chu, Sisi Wang, Yuan Tian, Jiazhe Xu, Xu Zhang, Pengju Shi, Xiaonan Wang, Wei Fan, Xuechun Sun, Jingyi Sun, Luo-Zhou Chen, Gang Wu, Wen Shi, Hong-Fei Wang, Tianqi Deng, Rui Wang, Deren Yang, Jingjing Xue","doi":"10.1038/s41557-025-01732-z","DOIUrl":"10.1038/s41557-025-01732-z","url":null,"abstract":"Perovskite solar cells represent a promising class of photovoltaics that have achieved exceptional levels of performance within a short time. Such high efficiencies often depend on the use of molecule-based selective contacts that form highly ordered molecular assemblies. Although this high degree of ordering usually benefits charge-carrier transport, it is disrupted by structure deformation and phase transformation when subjected to external stresses, which limits the long-term operational stability of perovskite solar cells. Here we demonstrate a molecular contact with an orthogonal π-skeleton that shows better resilience to external stimuli than commonly used conjugated cores. This molecular design yields a disordered, amorphous structure that is not only highly stable but also demonstrates exceptional charge selectivity and transport capability. The perovskite solar cells fabricated with this orthogonal π-skeleton molecule exhibited enhanced long-term durability in accelerated-ageing tests. This orthogonal π-skeleton functionality opens new opportunities in molecular design for applications in organic electronics. Perovskite solar cells often rely on ordered molecular contacts for favourable charge-carrier transport, and any organizational disruption reduces device efficiency. Now a contact featuring an orthogonal π-skeleton has been shown to afford a high resilience to external stimuli plus long-term durability in accelerated-ageing tests.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 4","pages":"564-570"},"PeriodicalIF":19.2,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192354","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

Efficient and modular synthesis of ibogaine and related alkaloids 高效模块化合成伊博格碱及相关生物碱

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-06 DOI: 10.1038/s41557-024-01714-7

Rishab N. Iyer, David Favela, Andras Domokos, Guoliang Zhang, Arabo A. Avanes, Samuel J. Carter, Andrian G. Basargin, Alexis R. Davis, Dean J. Tantillo, David E. Olson

{"title":"Efficient and modular synthesis of ibogaine and related alkaloids","authors":"Rishab N. Iyer, David Favela, Andras Domokos, Guoliang Zhang, Arabo A. Avanes, Samuel J. Carter, Andrian G. Basargin, Alexis R. Davis, Dean J. Tantillo, David E. Olson","doi":"10.1038/s41557-024-01714-7","DOIUrl":"10.1038/s41557-024-01714-7","url":null,"abstract":"Anecdotal reports and preliminary clinical trials suggest that the psychoactive alkaloid ibogaine and its active metabolite noribogaine have powerful anti-addictive properties, producing long-lasting therapeutic effects across a range of substance use disorders and co-occurring neuropsychiatric diseases such as depression and post-traumatic stress disorder. Here we report a gram-scale, seven-step synthesis of ibogaine from pyridine. Key features of this strategy enabled the synthesis of three additional iboga alkaloids, as well as an enantioselective total synthesis of (+)-ibogaine and the construction of four analogues. Biological testing revealed that the unnatural enantiomer of ibogaine does not produce ibogaine-like effects on cortical neuron growth, while (−)-10-fluoroibogamine exhibits exceptional psychoplastogenic properties and is a potent modulator of the serotonin transporter. This work provides a platform for accessing iboga alkaloids and congeners for further biological study. Preliminary clinical trials suggest that ibogaine and its active metabolite noribogaine have powerful anti-addictive properties, Now, a strategy for the scalable, asymmetric total synthesis of ibogaine has been developed that also provides access to iboga analogues. Biological testing identified a psychoplastogenic iboga analogue that is a potent modulator of the serotonin transporter.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 3","pages":"412-420"},"PeriodicalIF":19.2,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192352","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

Mn12 and the dawn of single-molecule magnets Mn12和单分子磁体的曙光

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-05 DOI: 10.1038/s41557-024-01718-3

Niki Mavragani, Muralee Murugesu

引用次数: 0

Eric the AI research assistant for chemists 埃里克，化学家的人工智能研究助理

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-05 DOI: 10.1038/s41557-024-01725-4

Bruce C. Gibb

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Protons undermine lithium-ion batteries with positively disastrous results 质子破坏锂离子电池，带来灾难性的后果

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-01-29 DOI: 10.1038/s41557-025-01733-y

Noah P. Holzapfel, Veronica Augustyn

引用次数: 0

Enantioselective synthesis of 2-substituted bicyclo[1.1.1]pentanes via sequential asymmetric imine addition of bicyclo[1.1.0]butanes and skeletal editing 序贯不对称亚胺加成二环[1.1.1]丁烷和骨架编辑对映选择性合成2-取代二环[1.1.1]戊烷

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-01-28 DOI: 10.1038/s41557-024-01710-x

Jin-Teng Che, Wei-Yi Ding, Hong-Bo Zhang, Yong-Bin Wang, Shao-Hua Xiang, Bin Tan

{"title":"Enantioselective synthesis of 2-substituted bicyclo[1.1.1]pentanes via sequential asymmetric imine addition of bicyclo[1.1.0]butanes and skeletal editing","authors":"Jin-Teng Che, Wei-Yi Ding, Hong-Bo Zhang, Yong-Bin Wang, Shao-Hua Xiang, Bin Tan","doi":"10.1038/s41557-024-01710-x","DOIUrl":"10.1038/s41557-024-01710-x","url":null,"abstract":"The substitution of an aromatic ring with a C(sp3)-rich bicyclic hydrocarbon, known as bioisosteric replacement, plays a crucial role in modern drug discovery. Substituted bicyclo[1.1.1]pentanes (BCPs) are particularly noteworthy owing to their uniquely three-dimensional stereochemical complexity. 1,3-Difunctionalized BCPs have been widely used as bioisosteres for para-substituted phenyl rings, and they have been incorporated into numerous lead pharmaceutical candidates. 2-Substituted BCPs (substituted at the bridge position) can function as alternatives to ortho- or meta-substituted arene rings; however, the general and efficient construction of these scaffolds remains challenging, particularly if performed in an enantioselective manner. Here we present an approach for synthesizing enantioenriched 2-substituted BCPs by a nitrogen-atom insertion-and-deletion strategy, involving a chiral Brønsted acid-catalytic enantioselective cycloaddition of bicyclo[1.1.0]butanes with imines and nitrogen deletion of resulting aza-bicyclo[2.1.1]hexanes (aza-BCHs) with generally good enantiopurity retention. Mechanistic experiments verify the radical pathway. Chiral BCPs have been readily incorporated into medicinally relevant molecules, and a drug analogue has been successfully prepared enantioselectively. Substituted bicyclo[1.1.1]pentanes (BCPs) are widely used as bioisosteres for para-substituted phenyl rings, providing improved pharmacological profiles for drug candidates, but strategies for the preparation of chiral BCPs remain limited. Now a route to chiral bridge-substituted BCPs has been developed via a nitrogen-atom insertion-and-deletion strategy, enabling a practical avenue towards chiral BCP bioisosteres of lomitapide.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 3","pages":"393-402"},"PeriodicalIF":19.2,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050300","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

Supramolecular dyads as photogenerated qubit candidates 作为光生量子比特候选者的超分子二元体

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-01-27 DOI: 10.1038/s41557-024-01716-5

Ivan V. Khariushin, Philipp Thielert, Elisa Zöllner, Maximilian Mayländer, Theresia Quintes, Sabine Richert, Andreas Vargas Jentzsch

{"title":"Supramolecular dyads as photogenerated qubit candidates","authors":"Ivan V. Khariushin, Philipp Thielert, Elisa Zöllner, Maximilian Mayländer, Theresia Quintes, Sabine Richert, Andreas Vargas Jentzsch","doi":"10.1038/s41557-024-01716-5","DOIUrl":"10.1038/s41557-024-01716-5","url":null,"abstract":"Molecular spin qubits have the advantages of synthetic flexibility and amenability to be tailored to specific applications. Among them, chromophore–radical systems have emerged as appealing qubit candidates. These systems can be initiated by light to form triplet–radical pairs that can result in the formation of quartet states by spin mixing. For a triplet–radical pair to undergo spin mixing, the molecular bridge joining the spin centres must permit effective spin communication, which has previously been ensured using covalent, π-conjugated linkers. Here we used perylenediimides and nitroxide radicals designed to self-assemble in solution via hydrogen bonding and observed, using electron paramagnetic resonance spectroscopy, the formation of quartet states that can be manipulated coherently using microwaves. This unprecedented finding that non-covalent bonds can enable spin mixing advances supramolecular chemistry as a valuable tool for exploring, developing and scaling up materials for quantum information science. Molecular approaches in quantum information science are highly promising, but the synthesis and scale-up of suitable covalently linked moieties represent major challenges. Here it is demonstrated that efficient spin mixing between photogenerated spin centres is possible through hydrogen bonds, advancing supramolecular chemistry as a valuable tool to address these challenges.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 4","pages":"493-499"},"PeriodicalIF":19.2,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044179","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