Pub Date : 2025-01-06DOI: 10.1038/s41557-024-01690-y
Shengxu Li, Shunqi Xu, En Lin, Tonghai Wang, Haoyong Yang, Junyi Han, Yuxiang Zhao, Qunji Xue, Paolo Samorì, Zhenjie Zhang, Tao Zhang
sp2-carbon-linked covalent organic frameworks (sp2c-COFs) are crystalline porous polymers with repeat organic units linked by sp2 carbons, and have attracted increasing interest due to their robust skeleton and tunable semiconducting properties. Single-crystalline sp2c-COFs with well-defined structures can represent an ideal platform for investigating fundamental physics properties and device performance. However, the robust olefin bonds inhibit the reversible-reaction-based crystal self-correction, thus yielding polycrystalline or amorphous polymers. Here we report an imine-to-olefin transformation strategy to form single-crystal sp2c-COFs. The isolated single crystals display rectangular nanotube-like domains with sizes up to approximately 24 μm × 0.8 μm × 0.8 μm, and permanent pore distribution around 1.1 nm. The highly conjugated olefin linkage endows the crystals with enhanced electronic connectivity which determines a remarkable room-temperature metal-free ferromagnetism (8.6 × 10−3 emu g−1). Our protocol is robust and generally applicable for the synthesis of single-crystalline sp2c-COFs for future spin-electron devices.
{"title":"Synthesis of single-crystalline sp2-carbon-linked covalent organic frameworks through imine-to-olefin transformation","authors":"Shengxu Li, Shunqi Xu, En Lin, Tonghai Wang, Haoyong Yang, Junyi Han, Yuxiang Zhao, Qunji Xue, Paolo Samorì, Zhenjie Zhang, Tao Zhang","doi":"10.1038/s41557-024-01690-y","DOIUrl":"https://doi.org/10.1038/s41557-024-01690-y","url":null,"abstract":"<p><i>sp</i><sup>2</sup>-carbon-linked covalent organic frameworks (<i>sp</i><sup>2</sup>c-COFs) are crystalline porous polymers with repeat organic units linked by <i>sp</i><sup>2</sup> carbons, and have attracted increasing interest due to their robust skeleton and tunable semiconducting properties. Single-crystalline <i>sp</i><sup>2</sup>c-COFs with well-defined structures can represent an ideal platform for investigating fundamental physics properties and device performance. However, the robust olefin bonds inhibit the reversible-reaction-based crystal self-correction, thus yielding polycrystalline or amorphous polymers. Here we report an imine-to-olefin transformation strategy to form single-crystal <i>sp</i><sup>2</sup>c-COFs. The isolated single crystals display rectangular nanotube-like domains with sizes up to approximately 24 μm × 0.8 μm × 0.8 μm, and permanent pore distribution around 1.1 nm. The highly conjugated olefin linkage endows the crystals with enhanced electronic connectivity which determines a remarkable room-temperature metal-free ferromagnetism (8.6 × 10<sup>−3</sup> emu g<sup>−1</sup>). Our protocol is robust and generally applicable for the synthesis of single-crystalline <i>sp</i><sup>2</sup>c-COFs for future spin-electron devices.</p><figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"42 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929695","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}
Pub Date : 2025-01-06DOI: 10.1038/s41557-024-01693-9
Zirui Lv, Runfeng Lin, Yi Yang, Kun Lan, Chin-Te Hung, Pengfei Zhang, Jinxiu Wang, Wanhai Zhou, Zaiwang Zhao, Zhongyao Wang, Jiawen Zou, Taoyang Wang, Tiancong Zhao, Yifei Xu, Dongliang Chao, Weimin Tan, Bo Yan, Qiaowei Li, Dongyuan Zhao, Xiaomin Li
The synthesis of mesoporous metal–organic frameworks (meso-MOFs) is desirable as these materials can be used in various applications. However, owing to the imbalance in structural tension at the micro-scale (MOF crystallization) and the meso-scales (assembly of micelles with MOF subunits), the formation of single-crystal meso-MOFs is challenging. Here we report the preparation of uniform single-crystal meso-MOF nanoparticles with ordered mesopore channels in microporous frameworks with definite arrangements, through a cooperative assembly method co-mediated by strong and weak acids. These nanoparticles feature a truncated octahedron shape with variable size and well-defined two-dimensional hexagonally structured (p6mm) columnar mesopores. Notably, the match between the crystallization kinetics of MOFs and the assembly kinetics of micelles is critical for forming the single-crystal meso-MOFs. On the basis of this strategy, we have constructed a library of meso-MOFs with tunable large pore sizes, controllable mesophases, various morphologies and multivariate components.
{"title":"Uniform single-crystal mesoporous metal–organic frameworks","authors":"Zirui Lv, Runfeng Lin, Yi Yang, Kun Lan, Chin-Te Hung, Pengfei Zhang, Jinxiu Wang, Wanhai Zhou, Zaiwang Zhao, Zhongyao Wang, Jiawen Zou, Taoyang Wang, Tiancong Zhao, Yifei Xu, Dongliang Chao, Weimin Tan, Bo Yan, Qiaowei Li, Dongyuan Zhao, Xiaomin Li","doi":"10.1038/s41557-024-01693-9","DOIUrl":"https://doi.org/10.1038/s41557-024-01693-9","url":null,"abstract":"<p>The synthesis of mesoporous metal–organic frameworks (meso-MOFs) is desirable as these materials can be used in various applications. However, owing to the imbalance in structural tension at the micro-scale (MOF crystallization) and the meso-scales (assembly of micelles with MOF subunits), the formation of single-crystal meso-MOFs is challenging. Here we report the preparation of uniform single-crystal meso-MOF nanoparticles with ordered mesopore channels in microporous frameworks with definite arrangements, through a cooperative assembly method co-mediated by strong and weak acids. These nanoparticles feature a truncated octahedron shape with variable size and well-defined two-dimensional hexagonally structured (<i>p</i>6<i>mm</i>) columnar mesopores. Notably, the match between the crystallization kinetics of MOFs and the assembly kinetics of micelles is critical for forming the single-crystal meso-MOFs. On the basis of this strategy, we have constructed a library of meso-MOFs with tunable large pore sizes, controllable mesophases, various morphologies and multivariate components.</p><figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"34 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929700","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}
Pub Date : 2025-01-06DOI: 10.1038/s41557-024-01698-4
Burckhard Seelig, Irene A. Chen
Understanding the emergence of complex biochemical systems, such as protein translation, is a great challenge. Although synthetic approaches can provide insight into the potential early stages of life, they do not address the equally important question of why the complex systems of life would have evolved. In particular, the intricacies of the mechanisms governing the transfer of information from nucleic acid sequences to proteins make it difficult to imagine how coded protein synthesis could have emerged from a prebiotic soup. Here we discuss the use of intellectual frameworks in studying the emergence of life. We discuss how one such framework, namely the RNA world theory, has spurred research, and provide an overview of its limitations. We suggest that the emergence of coded protein synthesis could be broken into experimentally tractable problems by treating it as a molecular bricolage—a complex system integrating many different parts, each of which originally evolved for uses unrelated to its modern function—to promote a concrete understanding of its origin. It has been challenging to rationalize the emergence of complex biochemical systems because many parts with different functions needed to come together. This Perspective proposes a molecular bricolage—an evolutionary tinkering involving parts that initially evolved for unrelated functions—to provide an intellectual framework to study the origin of protein translation.
{"title":"Intellectual frameworks to understand complex biochemical systems at the origin of life","authors":"Burckhard Seelig, Irene A. Chen","doi":"10.1038/s41557-024-01698-4","DOIUrl":"10.1038/s41557-024-01698-4","url":null,"abstract":"Understanding the emergence of complex biochemical systems, such as protein translation, is a great challenge. Although synthetic approaches can provide insight into the potential early stages of life, they do not address the equally important question of why the complex systems of life would have evolved. In particular, the intricacies of the mechanisms governing the transfer of information from nucleic acid sequences to proteins make it difficult to imagine how coded protein synthesis could have emerged from a prebiotic soup. Here we discuss the use of intellectual frameworks in studying the emergence of life. We discuss how one such framework, namely the RNA world theory, has spurred research, and provide an overview of its limitations. We suggest that the emergence of coded protein synthesis could be broken into experimentally tractable problems by treating it as a molecular bricolage—a complex system integrating many different parts, each of which originally evolved for uses unrelated to its modern function—to promote a concrete understanding of its origin. It has been challenging to rationalize the emergence of complex biochemical systems because many parts with different functions needed to come together. This Perspective proposes a molecular bricolage—an evolutionary tinkering involving parts that initially evolved for unrelated functions—to provide an intellectual framework to study the origin of protein translation.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 1","pages":"11-19"},"PeriodicalIF":19.2,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929697","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}
Pub Date : 2025-01-06DOI: 10.1038/s41557-024-01691-x
Davide Spinnato, Nils Nöthling, Markus Leutzsch, Maurice van Gastel, Lucas Wagner, Frank Neese, Josep Cornella
The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featuring a cationic core based on three contiguous Bi(I) centres. The triatomic bismuth-based core exhibits an electronic configuration that mimics the canonical description of the archetypical carbon-based π-allyl cation. Structural, spectroscopic and theoretical analyses validate the unique π-delocalization between the bismuth’s highly diffused 6p orbitals, resulting in a bonding situation in which the three bismuth atoms are interconnected by two bonds, formally possessing a 1.5 bond order each. This electronic situation defines this complex as the heaviest and stable π-allyl cation of the periodic table. Furthermore, we demonstrate that the newly synthesized complex is able to act as a synthon for the transfer of a Bi(I) cation to forge other low-valent organobismuth complexes.
{"title":"A trimetallic bismuth(I)-based allyl cation","authors":"Davide Spinnato, Nils Nöthling, Markus Leutzsch, Maurice van Gastel, Lucas Wagner, Frank Neese, Josep Cornella","doi":"10.1038/s41557-024-01691-x","DOIUrl":"https://doi.org/10.1038/s41557-024-01691-x","url":null,"abstract":"<p>The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featuring a cationic core based on three contiguous Bi(I) centres. The triatomic bismuth-based core exhibits an electronic configuration that mimics the canonical description of the archetypical carbon-based <i>π</i>-allyl cation. Structural, spectroscopic and theoretical analyses validate the unique <i>π</i>-delocalization between the bismuth’s highly diffused 6<i>p</i> orbitals, resulting in a bonding situation in which the three bismuth atoms are interconnected by two bonds, formally possessing a 1.5 bond order each. This electronic situation defines this complex as the heaviest and stable <i>π</i>-allyl cation of the periodic table. Furthermore, we demonstrate that the newly synthesized complex is able to act as a synthon for the transfer of a Bi(I) cation to forge other low-valent organobismuth complexes.</p><figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"46 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929809","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}
Pub Date : 2025-01-03DOI: 10.1038/s41557-024-01692-w
Hyungdo Cho, Xiaoyu Tong, Giuseppe Zuccarello, Robert L. Anderson, Gregory C. Fu
In view of the high propensity of tertiary alkyl amines to be bioactive, the development of new methods for their synthesis is an important challenge. Transition-metal catalysis has the potential to greatly expand the scope of nucleophilic substitution reactions of alkyl electrophiles; unfortunately, in the case of alkyl amines as nucleophiles, only one success has been described so far: the selective mono-alkylation of primary amines to form secondary amines. Here, using photoinduced copper catalysis, we report the synthesis of tertiary alkyl amines from secondary amines and unactivated alkyl electrophiles, two readily available coupling partners. Utilizing an array of tools, we have analysed the mechanism of this process; specifically, we have structurally characterized the three principal copper-based intermediates that are detected during catalysis and provided support for the key steps of the proposed catalytic cycle, including the coupling of a copper(II)–amine intermediate with an alkyl radical to form a C–N bond.
{"title":"Synthesis of tertiary alkyl amines via photoinduced copper-catalysed nucleophilic substitution","authors":"Hyungdo Cho, Xiaoyu Tong, Giuseppe Zuccarello, Robert L. Anderson, Gregory C. Fu","doi":"10.1038/s41557-024-01692-w","DOIUrl":"https://doi.org/10.1038/s41557-024-01692-w","url":null,"abstract":"<p>In view of the high propensity of tertiary alkyl amines to be bioactive, the development of new methods for their synthesis is an important challenge. Transition-metal catalysis has the potential to greatly expand the scope of nucleophilic substitution reactions of alkyl electrophiles; unfortunately, in the case of alkyl amines as nucleophiles, only one success has been described so far: the selective mono-alkylation of primary amines to form secondary amines. Here, using photoinduced copper catalysis, we report the synthesis of tertiary alkyl amines from secondary amines and unactivated alkyl electrophiles, two readily available coupling partners. Utilizing an array of tools, we have analysed the mechanism of this process; specifically, we have structurally characterized the three principal copper-based intermediates that are detected during catalysis and provided support for the key steps of the proposed catalytic cycle, including the coupling of a copper(II)–amine intermediate with an alkyl radical to form a C–N bond.</p><figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"8 1 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917228","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}
Pub Date : 2025-01-03DOI: 10.1038/s41557-024-01695-7
Jiawei Sun, Shuanghu Wang, Kaid C. Harper, Yu Kawamata, Phil S. Baran
Amino alcohols are vital in natural products, pharmaceuticals and agrochemicals, and as key building blocks for various applications. Traditional synthesis methods often rely on polar bond retrosynthetic analysis, requiring extensive protecting group manipulations that complicate direct access. Here we show a streamlined approach using a serine-derived chiral carboxylic acid in stereoselective electrocatalytic decarboxylative transformations, enabling efficient access to enantiopure amino alcohols. Unlike conventional strategies, this radical method is both modular and general, offering stereoselective and chemoselective synthesis of diverse substituted amino alcohols. For example, aryl, alkenyl, alkyl and acyl fragments can be coupled efficiently with the serine-derived chiral acid under electrocatalytic decarboxylative conditions. We demonstrate its utility through the rapid synthesis of medicinally important compounds, as well as useful building blocks, highlighting its ability to simplify complex synthetic pathways through entirely different bond disconnections. This electrocatalytic method is robust and scalable, as demonstrated in a 72-gram-scale flow reaction. Amino alcohols are essential in pharmaceuticals, agrochemicals and other applications. Now, using a serine-derived chiral carboxylic acid, an electrocatalytic decarboxylative transformation enables efficient and stereoselective access to diverse amino alcohols. This method is scalable, modular and could offer rapid synthesis of medicinal compounds and key building blocks.
{"title":"Stereoselective amino alcohol synthesis via chemoselective electrocatalytic radical cross-couplings","authors":"Jiawei Sun, Shuanghu Wang, Kaid C. Harper, Yu Kawamata, Phil S. Baran","doi":"10.1038/s41557-024-01695-7","DOIUrl":"10.1038/s41557-024-01695-7","url":null,"abstract":"Amino alcohols are vital in natural products, pharmaceuticals and agrochemicals, and as key building blocks for various applications. Traditional synthesis methods often rely on polar bond retrosynthetic analysis, requiring extensive protecting group manipulations that complicate direct access. Here we show a streamlined approach using a serine-derived chiral carboxylic acid in stereoselective electrocatalytic decarboxylative transformations, enabling efficient access to enantiopure amino alcohols. Unlike conventional strategies, this radical method is both modular and general, offering stereoselective and chemoselective synthesis of diverse substituted amino alcohols. For example, aryl, alkenyl, alkyl and acyl fragments can be coupled efficiently with the serine-derived chiral acid under electrocatalytic decarboxylative conditions. We demonstrate its utility through the rapid synthesis of medicinally important compounds, as well as useful building blocks, highlighting its ability to simplify complex synthetic pathways through entirely different bond disconnections. This electrocatalytic method is robust and scalable, as demonstrated in a 72-gram-scale flow reaction. Amino alcohols are essential in pharmaceuticals, agrochemicals and other applications. Now, using a serine-derived chiral carboxylic acid, an electrocatalytic decarboxylative transformation enables efficient and stereoselective access to diverse amino alcohols. This method is scalable, modular and could offer rapid synthesis of medicinal compounds and key building blocks.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 1","pages":"44-53"},"PeriodicalIF":19.2,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917227","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}
Pub Date : 2025-01-03DOI: 10.1038/s41557-024-01688-6
Georgia M. Richardson, Thayalan Rajeshkumar, Finlay M. Burke, Scott A. Cameron, Brooke D. Nicholls, Joanne E. Harvey, Robert A. Keyzers, Tane Butler, Simon Granville, Lujia Liu, Julien Langley, Li F. Lim, Nicholas Cox, Nicholas F. Chilton, Jamie Hicks, Nathaniel J. L. K. Davis, Laurent Maron, Mathew D. Anker
Benzene reduction by molecular complexes remains an important synthetic challenge, requiring harsh reaction conditions involving group I metals. Reductions of benzene, to date, typically result in a loss of aromaticity, although the benzene tetra-anion, a 10π-electron system, has been calculated to be stable and aromatic. Due to the lack of sufficiently potent reductants, four-electron reduction of benzene usually requires the use of group I metals. Here we demonstrate the four-electron reduction of benzene and some of its derivatives using a samarium(ii) alkyl reagent, with no requirement for group I metals. Whereas organosamarium(ii) typically reacts through one-electron processes, the compounds reported here feature a rare two-electron process. Combined experimental and computational results implicate a transient samarium(i) intermediate involved in this reduction process, which ultimately provides the benzene tetra-anion. The remarkably strong reducing power of this samarium(ii) alkyl implies a rich reactivity, providing scope for its application as a reducing agent. Benzene reduction by molecular complexes remains a considerable synthetic challenge, and typically requires harsh reaction conditions involving group I metals. Now it has been shown that a highly polar organometallic samarium alkyl complex enables the reduction of benzene to its tetra-anion without the need for a group I metal.
{"title":"Four-electron reduction of benzene by a samarium(ii)-alkyl without the addition of external reducing agents","authors":"Georgia M. Richardson, Thayalan Rajeshkumar, Finlay M. Burke, Scott A. Cameron, Brooke D. Nicholls, Joanne E. Harvey, Robert A. Keyzers, Tane Butler, Simon Granville, Lujia Liu, Julien Langley, Li F. Lim, Nicholas Cox, Nicholas F. Chilton, Jamie Hicks, Nathaniel J. L. K. Davis, Laurent Maron, Mathew D. Anker","doi":"10.1038/s41557-024-01688-6","DOIUrl":"10.1038/s41557-024-01688-6","url":null,"abstract":"Benzene reduction by molecular complexes remains an important synthetic challenge, requiring harsh reaction conditions involving group I metals. Reductions of benzene, to date, typically result in a loss of aromaticity, although the benzene tetra-anion, a 10π-electron system, has been calculated to be stable and aromatic. Due to the lack of sufficiently potent reductants, four-electron reduction of benzene usually requires the use of group I metals. Here we demonstrate the four-electron reduction of benzene and some of its derivatives using a samarium(ii) alkyl reagent, with no requirement for group I metals. Whereas organosamarium(ii) typically reacts through one-electron processes, the compounds reported here feature a rare two-electron process. Combined experimental and computational results implicate a transient samarium(i) intermediate involved in this reduction process, which ultimately provides the benzene tetra-anion. The remarkably strong reducing power of this samarium(ii) alkyl implies a rich reactivity, providing scope for its application as a reducing agent. Benzene reduction by molecular complexes remains a considerable synthetic challenge, and typically requires harsh reaction conditions involving group I metals. Now it has been shown that a highly polar organometallic samarium alkyl complex enables the reduction of benzene to its tetra-anion without the need for a group I metal.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 1","pages":"20-28"},"PeriodicalIF":19.2,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917230","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}
Pub Date : 2025-01-03DOI: 10.1038/s41557-024-01697-5
Sebastian Novosedlik, Felix Reichel, Thijs van Veldhuisen, Yudong Li, Hanglong Wu, Henk Janssen, Jochen Guck, Jan van Hest
The cytoskeleton is a crucial determinant of mammalian cell structure and function, providing mechanical resilience, supporting the cell membrane and orchestrating essential processes such as cell division and motility. Because of its fundamental role in living cells, developing a reconstituted or artificial cytoskeleton is of major interest. Here we present an approach to construct an artificial cytoskeleton that imparts mechanical support and regulates membrane dynamics. Our system involves amylose-based coacervates stabilized by a terpolymer membrane, with a cytoskeleton formed from polydiacetylene fibrils. The fibrils bundle due to interactions with the positively charged amylose derivative, forming micrometre-sized structures mimicking a cytoskeleton. Given the intricate interplay between cellular structure and function, the design and integration of this artificial cytoskeleton represent a crucial advancement, paving the way for the development of artificial cell platforms exhibiting enhanced life-like behaviour.
{"title":"Cytoskeleton-functionalized synthetic cells with life-like mechanical features and regulated membrane dynamicity","authors":"Sebastian Novosedlik, Felix Reichel, Thijs van Veldhuisen, Yudong Li, Hanglong Wu, Henk Janssen, Jochen Guck, Jan van Hest","doi":"10.1038/s41557-024-01697-5","DOIUrl":"https://doi.org/10.1038/s41557-024-01697-5","url":null,"abstract":"<p>The cytoskeleton is a crucial determinant of mammalian cell structure and function, providing mechanical resilience, supporting the cell membrane and orchestrating essential processes such as cell division and motility. Because of its fundamental role in living cells, developing a reconstituted or artificial cytoskeleton is of major interest. Here we present an approach to construct an artificial cytoskeleton that imparts mechanical support and regulates membrane dynamics. Our system involves amylose-based coacervates stabilized by a terpolymer membrane, with a cytoskeleton formed from polydiacetylene fibrils. The fibrils bundle due to interactions with the positively charged amylose derivative, forming micrometre-sized structures mimicking a cytoskeleton. Given the intricate interplay between cellular structure and function, the design and integration of this artificial cytoskeleton represent a crucial advancement, paving the way for the development of artificial cell platforms exhibiting enhanced life-like behaviour.</p><figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"72 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917229","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}
Pub Date : 2025-01-02DOI: 10.1038/s41557-024-01709-4
Oxide–water interfaces are ubiquitous in nature and technological processes, but their characterization is difficult. Now, an in situ nonlinear optical spectroscopy approach enables the characterization of such buried interfaces. Aided by ab initio molecular dynamic simulations, unexpected reaction pathways are revealed for the silicon dioxide–water interface.
{"title":"In situ nonlinear optical spectroscopy for probing buried oxide–water interfaces","authors":"","doi":"10.1038/s41557-024-01709-4","DOIUrl":"https://doi.org/10.1038/s41557-024-01709-4","url":null,"abstract":"Oxide–water interfaces are ubiquitous in nature and technological processes, but their characterization is difficult. Now, an in situ nonlinear optical spectroscopy approach enables the characterization of such buried interfaces. Aided by ab initio molecular dynamic simulations, unexpected reaction pathways are revealed for the silicon dioxide–water interface.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"6 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912011","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}
Pub Date : 2024-12-23DOI: 10.1038/s41557-024-01682-y
Sayuri L. Higashi, Yanjun Zheng, Taniya Chakraborty, Azadeh Alavizargar, Andreas Heuer, Seraphine V. Wegner
Pluripotent cells can yield different cell types determined by the specific sequence of differentiation signals that they encounter as the cell activates or deactivates functions and retains memory of previous inputs. Here, we achieved pluripotency in synthetic cells by incorporating three dormant apo-metalloenzymes such that they could differentiate towards distinct fates, depending on the sequence of specific metal ion transport with ionophores. In the first differentiation step, we selectively transported one of three extracellular metal ion cofactors into pluripotent giant unilamellar vesicles (GUVs), which resulted in elevation of intracellular pH, hydrogen peroxide production or GUV lysis. Previously added ionophores suppress transport with subsequent ionophores owing to interactions among them in the membrane, as corroborated by atomistic simulations. Consequently, the addition of a second ionophore elicits a dampened response in the multipotent GUV and a third ionophore results in no further response, reminiscent of a terminally differentiated GUV. The pluripotent GUV can differentiate into five final fates, depending on the sequence in which the three ionophores are added. The sequence of specific differentiation signals determines the fate of a pluripotent cell. Here pluripotency was introduced into synthetic cells by loading them with three dormant apo-metalloenzymes, which were activated through selective metal ion transport by one of three ionophores. Depending on the sequence of metal ion intake, the synthetic cells differentiated towards five distinct fates.
{"title":"Adaptive metal ion transport and metalloregulation-driven differentiation in pluripotent synthetic cells","authors":"Sayuri L. Higashi, Yanjun Zheng, Taniya Chakraborty, Azadeh Alavizargar, Andreas Heuer, Seraphine V. Wegner","doi":"10.1038/s41557-024-01682-y","DOIUrl":"10.1038/s41557-024-01682-y","url":null,"abstract":"Pluripotent cells can yield different cell types determined by the specific sequence of differentiation signals that they encounter as the cell activates or deactivates functions and retains memory of previous inputs. Here, we achieved pluripotency in synthetic cells by incorporating three dormant apo-metalloenzymes such that they could differentiate towards distinct fates, depending on the sequence of specific metal ion transport with ionophores. In the first differentiation step, we selectively transported one of three extracellular metal ion cofactors into pluripotent giant unilamellar vesicles (GUVs), which resulted in elevation of intracellular pH, hydrogen peroxide production or GUV lysis. Previously added ionophores suppress transport with subsequent ionophores owing to interactions among them in the membrane, as corroborated by atomistic simulations. Consequently, the addition of a second ionophore elicits a dampened response in the multipotent GUV and a third ionophore results in no further response, reminiscent of a terminally differentiated GUV. The pluripotent GUV can differentiate into five final fates, depending on the sequence in which the three ionophores are added. The sequence of specific differentiation signals determines the fate of a pluripotent cell. Here pluripotency was introduced into synthetic cells by loading them with three dormant apo-metalloenzymes, which were activated through selective metal ion transport by one of three ionophores. Depending on the sequence of metal ion intake, the synthetic cells differentiated towards five distinct fates.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 1","pages":"54-65"},"PeriodicalIF":19.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41557-024-01682-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880027","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}