Pub Date : 2024-11-28DOI: 10.1038/s41557-024-01677-9
Chia-Heng Hsiung, Xin Zhang
The miniaturization and redesigning of proteins to bear fluorescence signals can broaden their scope for potential applications. Now, one can construct a range of compact artificial fluorescent proteins and develop protein biosensors by genetically encoding a natural fluorescent protein chromophore analogue.
{"title":"Mimicking fluorophores from nature to generate artificial fluorescent proteins and biosensors","authors":"Chia-Heng Hsiung, Xin Zhang","doi":"10.1038/s41557-024-01677-9","DOIUrl":"10.1038/s41557-024-01677-9","url":null,"abstract":"The miniaturization and redesigning of proteins to bear fluorescence signals can broaden their scope for potential applications. Now, one can construct a range of compact artificial fluorescent proteins and develop protein biosensors by genetically encoding a natural fluorescent protein chromophore analogue.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 12","pages":"1934-1935"},"PeriodicalIF":19.2,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142735646","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 : 2024-11-26DOI: 10.1038/s41557-024-01671-1
Hui Wang, Bin Gao, Heli Cheng, Shixuan Cao, Xinyi Ma, Yinjuan Chen, Yuxuan Ye
Carbonyl desaturation is a fundamental reaction widely practised in organic synthesis. While numerous methods have been developed to expand the scope of this important transformation, most of them necessitate multi-step protocols or suffer from the use of high loadings of metal or strong oxidizing conditions. Moreover, approaches that can achieve precise stereochemical control of the desaturation process are extremely rare. Here we report a biocatalytic platform for desymmetrizing desaturation of cyclohexanones to generate diverse cyclohexenones bearing a remote quaternary stereogenic centre, by reengineering ‘ene’-reductases to efficiently mediate dehydrogenation, the reverse process of their native activity. This ‘ene’-reductase-based desaturation system operates under mild conditions with air as the terminal oxidant, tolerates oxidation-sensitive or metal-incompatible functional groups and, more importantly, exhibits unparalleled stereoselectivity compared with those achieved with small-molecule catalysts. Mechanistic investigations suggest that the reaction proceeded through α-deprotonation followed by a rate-determining β-hydride transfer. Expanding the biocatalysis toolbox for selective desaturation is of great value. Now ‘ene’-reductases have been repurposed to mediate dehydrogenation, the reverse process of their native activity. The developed biocatalytic desaturation platform enables desymmetrizing desaturation of cyclohexanones for the synthesis of diverse cyclohexenones that bear a remote quaternary stereogenic centre.
{"title":"Unmasking the reverse catalytic activity of ‘ene’-reductases for asymmetric carbonyl desaturation","authors":"Hui Wang, Bin Gao, Heli Cheng, Shixuan Cao, Xinyi Ma, Yinjuan Chen, Yuxuan Ye","doi":"10.1038/s41557-024-01671-1","DOIUrl":"10.1038/s41557-024-01671-1","url":null,"abstract":"Carbonyl desaturation is a fundamental reaction widely practised in organic synthesis. While numerous methods have been developed to expand the scope of this important transformation, most of them necessitate multi-step protocols or suffer from the use of high loadings of metal or strong oxidizing conditions. Moreover, approaches that can achieve precise stereochemical control of the desaturation process are extremely rare. Here we report a biocatalytic platform for desymmetrizing desaturation of cyclohexanones to generate diverse cyclohexenones bearing a remote quaternary stereogenic centre, by reengineering ‘ene’-reductases to efficiently mediate dehydrogenation, the reverse process of their native activity. This ‘ene’-reductase-based desaturation system operates under mild conditions with air as the terminal oxidant, tolerates oxidation-sensitive or metal-incompatible functional groups and, more importantly, exhibits unparalleled stereoselectivity compared with those achieved with small-molecule catalysts. Mechanistic investigations suggest that the reaction proceeded through α-deprotonation followed by a rate-determining β-hydride transfer. Expanding the biocatalysis toolbox for selective desaturation is of great value. Now ‘ene’-reductases have been repurposed to mediate dehydrogenation, the reverse process of their native activity. The developed biocatalytic desaturation platform enables desymmetrizing desaturation of cyclohexanones for the synthesis of diverse cyclohexenones that bear a remote quaternary stereogenic centre.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 1","pages":"74-82"},"PeriodicalIF":19.2,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142730724","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 : 2024-11-25DOI: 10.1038/s41557-024-01681-z
Casey M. Davis, Lacey S. Roberts, Sasha R. Neefe, Ronan Kennedy, Karen Bailey, Kyri Baker, Daniel Kaffine, Michael F. Toney
Legacy energy production has generated a climate crisis and left in its wake a history of injustices that have disproportionately impacted marginalized communities. Integrating energy justice into the curricula and research of those who aim to fix this crisis is essential to equip students with the expertise needed to create and implement equitable energy solutions.
{"title":"The importance of integrating energy justice into chemistry graduate student research and the associated pathways and barriers","authors":"Casey M. Davis, Lacey S. Roberts, Sasha R. Neefe, Ronan Kennedy, Karen Bailey, Kyri Baker, Daniel Kaffine, Michael F. Toney","doi":"10.1038/s41557-024-01681-z","DOIUrl":"10.1038/s41557-024-01681-z","url":null,"abstract":"Legacy energy production has generated a climate crisis and left in its wake a history of injustices that have disproportionately impacted marginalized communities. Integrating energy justice into the curricula and research of those who aim to fix this crisis is essential to equip students with the expertise needed to create and implement equitable energy solutions.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 12","pages":"1921-1926"},"PeriodicalIF":19.2,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142697056","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 : 2024-11-21DOI: 10.1038/s41557-024-01674-y
Jack M. Wootton, William P. Unsworth
Aza-heterocycles with rings of more than 6 members are underrepresented in medicinal chemistry owing to challenges with their synthesis. Now, the conversion of 5- and 6-membered saturated cyclic amines into 7- and 8-membered aza-heterocycles can be achieved via a ring expansion cascade reaction.
{"title":"Cyclic amine ring expansion","authors":"Jack M. Wootton, William P. Unsworth","doi":"10.1038/s41557-024-01674-y","DOIUrl":"10.1038/s41557-024-01674-y","url":null,"abstract":"Aza-heterocycles with rings of more than 6 members are underrepresented in medicinal chemistry owing to challenges with their synthesis. Now, the conversion of 5- and 6-membered saturated cyclic amines into 7- and 8-membered aza-heterocycles can be achieved via a ring expansion cascade reaction.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 12","pages":"1932-1933"},"PeriodicalIF":19.2,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679165","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 : 2024-11-21DOI: 10.1038/s41557-024-01668-w
Licheng Wu, Hanyu Xia, Jiahao Bai, Yang Xi, Xianqing Wu, Li Gao, Jingping Qu, Yifeng Chen
Saturated N-heterocycles are ubiquitous structures among natural products and biologically active compounds. Therefore, the development of synthetic methods for the construction of N-heterocycles is of great importance in the synthetic community. Altering the ring system of these motifs to analogues with different ring sizes by employing molecular editing techniques would be highly appealing in medicinal chemistry. We present herein the direct insertion of glycine derivatives as two-carbon synthons into unstrained five- or six-membered saturated cyclic amines at predictable sites, enabling the construction of synthetically challenging medium-sized azacycles through sequential Ru-catalysed C‒C bond formation, retro-aza-Michael addition and a lactamization process. Upon further derivation, we leverage this homologation platform to realize modular insertion of one- or two-carbon units into the aliphatic rings. The conversion of a single azacycle into up to five others provides a promising toolbox for diversifying existing drug candidates and increasing the prospects for clinical success. Saturated N-heterocycles are ubiquitous structures among natural products and biologically active compounds, but methods to edit the ring size of these substructures are scarce. Now the ring expansion of unactivated cyclic amines has been achieved via sequential Ru-catalysed C‒C bond formation, retro-aza-Michael addition and a lactamization process to construct synthetically challenging medium-sized azacycles.
{"title":"Diversified ring expansion of saturated cyclic amines enabled by azlactone insertion","authors":"Licheng Wu, Hanyu Xia, Jiahao Bai, Yang Xi, Xianqing Wu, Li Gao, Jingping Qu, Yifeng Chen","doi":"10.1038/s41557-024-01668-w","DOIUrl":"10.1038/s41557-024-01668-w","url":null,"abstract":"Saturated N-heterocycles are ubiquitous structures among natural products and biologically active compounds. Therefore, the development of synthetic methods for the construction of N-heterocycles is of great importance in the synthetic community. Altering the ring system of these motifs to analogues with different ring sizes by employing molecular editing techniques would be highly appealing in medicinal chemistry. We present herein the direct insertion of glycine derivatives as two-carbon synthons into unstrained five- or six-membered saturated cyclic amines at predictable sites, enabling the construction of synthetically challenging medium-sized azacycles through sequential Ru-catalysed C‒C bond formation, retro-aza-Michael addition and a lactamization process. Upon further derivation, we leverage this homologation platform to realize modular insertion of one- or two-carbon units into the aliphatic rings. The conversion of a single azacycle into up to five others provides a promising toolbox for diversifying existing drug candidates and increasing the prospects for clinical success. Saturated N-heterocycles are ubiquitous structures among natural products and biologically active compounds, but methods to edit the ring size of these substructures are scarce. Now the ring expansion of unactivated cyclic amines has been achieved via sequential Ru-catalysed C‒C bond formation, retro-aza-Michael addition and a lactamization process to construct synthetically challenging medium-sized azacycles.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 12","pages":"1951-1959"},"PeriodicalIF":19.2,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679166","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 : 2024-11-19DOI: 10.1038/s41557-024-01669-9
Dongmin Wang, Wang Chen, Haonan Chen, Yizhen Chen, Shengfa Ye, Gengwen Tan
Nitrene radical compounds are short-lived intermediates in a variety of nitrogen-involved transformations. They feature either a singlet or a triplet ground state, depending on the electronic properties of the substituents. Triplet nitrenes are highly reactive and their isolation in the condensed phase under ambient conditions is challenging. Here we report the synthesis and isolation of a triplet arylnitrene supported by a bulky hydrindacene ligand. The arylnitrene is fully characterized by various spectroscopic and structural techniques including electron paramagnetic resonance spectroscopy and single-crystal X-ray diffraction. Its high stability is largely attributed to the steric hindrance and effective electron delocalization provided by the supporting ligand. Electron paramagnetic resonance spectroscopy in conjunction with highly correlated wavefunction-based ab initio calculations provides support for a triplet ground state nitrene with axial zero-field splitting D = 0.92 cm–1 and vanishing rhombicity E/D = 0.002. Triplet nitrenes are highly reactive species and thus their isolation and characterization are challenging. Now, a bulky hydrindacene ligand has been used to stabilize a triplet arylnitrene synthesized through photolysis of an azide precursor under mild conditions. The triplet nitrene has been fully characterized by various techniques including single-crystal X-ray diffraction, electron paramagnetic resonance spectroscopy and theoretical calculations.
芘基化合物是各种涉氮转化过程中的短效中间体。根据取代基的电子特性，它们具有单重基态或三重基态。三重腈具有高活性，在环境条件下的凝聚相中分离三重腈具有挑战性。在此，我们报告了一种由笨重的水合茚配体支持的三重芳基硝基苯烯的合成和分离。通过各种光谱和结构技术，包括电子顺磁共振波谱和单晶 X 射线衍射，对该芳基烯进行了全面表征。它的高稳定性主要归功于支撑配体提供的立体阻碍和有效的电子析出。电子顺磁共振波谱与高度相关的基于波函数的 ab initio 计算相结合，为三重基态腈提供了支持，其轴向零场分裂 D = 0.92 cm-1，菱形度 E/D = 0.002。
{"title":"Isolation and characterization of a triplet nitrene","authors":"Dongmin Wang, Wang Chen, Haonan Chen, Yizhen Chen, Shengfa Ye, Gengwen Tan","doi":"10.1038/s41557-024-01669-9","DOIUrl":"10.1038/s41557-024-01669-9","url":null,"abstract":"Nitrene radical compounds are short-lived intermediates in a variety of nitrogen-involved transformations. They feature either a singlet or a triplet ground state, depending on the electronic properties of the substituents. Triplet nitrenes are highly reactive and their isolation in the condensed phase under ambient conditions is challenging. Here we report the synthesis and isolation of a triplet arylnitrene supported by a bulky hydrindacene ligand. The arylnitrene is fully characterized by various spectroscopic and structural techniques including electron paramagnetic resonance spectroscopy and single-crystal X-ray diffraction. Its high stability is largely attributed to the steric hindrance and effective electron delocalization provided by the supporting ligand. Electron paramagnetic resonance spectroscopy in conjunction with highly correlated wavefunction-based ab initio calculations provides support for a triplet ground state nitrene with axial zero-field splitting D = 0.92 cm–1 and vanishing rhombicity E/D = 0.002. Triplet nitrenes are highly reactive species and thus their isolation and characterization are challenging. Now, a bulky hydrindacene ligand has been used to stabilize a triplet arylnitrene synthesized through photolysis of an azide precursor under mild conditions. The triplet nitrene has been fully characterized by various techniques including single-crystal X-ray diffraction, electron paramagnetic resonance spectroscopy and theoretical calculations.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 1","pages":"38-43"},"PeriodicalIF":19.2,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142676357","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 : 2024-11-18DOI: 10.1038/s41557-024-01676-w
Steven J. Malcolmson
Multicomponent couplings offer powerful approaches for rapidly increasing molecular complexity, but typically require functionally distinct reagents. Now, through dynamic combinatorial chemistry, structurally similar amino groups can be efficiently differentiated, enabling the enantioselective aminomethylamination of dienes to prepare 1,3-diamines.
{"title":"Catalysis-enabled amine sorting","authors":"Steven J. Malcolmson","doi":"10.1038/s41557-024-01676-w","DOIUrl":"10.1038/s41557-024-01676-w","url":null,"abstract":"Multicomponent couplings offer powerful approaches for rapidly increasing molecular complexity, but typically require functionally distinct reagents. Now, through dynamic combinatorial chemistry, structurally similar amino groups can be efficiently differentiated, enabling the enantioselective aminomethylamination of dienes to prepare 1,3-diamines.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 12","pages":"1936-1937"},"PeriodicalIF":19.2,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665409","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 : 2024-11-18DOI: 10.1038/s41557-024-01673-z
Shoule Cai, Zeyu Zhao, Guoqing Yang, Hanmin Huang
Precisely differentiating chemicals featuring minor discrepancies is the prerequisite for achieving high selectivities in both chemical synthesis and biological activities. However, efficient strategies to differentiate and sort such congeneric compounds are lacking, posing daunting challenges for synthetic endeavours aimed at their orderly incorporation. Here we report a dynamic amine-sorting strategy that incorporates the chemoselective formation of the aminomethyl cyclopalladated complex to achieve the efficient differentiation of amine congeners. A series of amines sharing similar three-dimensional structures and properties, as well as possessing notoriously strong binding ability to metals, can be efficiently differentiated, enabling the highly chemo-, regio- and enantioselective multicomponent aminomethylamination of dienes to construct a variety of unsymmetrical chiral diamines. This dynamic amine-sorting strategy tackles the long-standing challenge of precise differentiation and orderly incorporation of aliphatic amines with subtle differences. From a broader perspective, the success demonstrates that meticulously designed metal complexes can provide flexible and general solutions for controlling delicate selectivities in sophisticated synthesis. Efficient strategies to differentiate and sort congeneric compounds are lacking. Now a metal-mediated dynamic amine-sorting strategy has been developed to precisely differentiate and assemble different amine congeners in an orderly manner, facilitating highly chemo-, regio- and enantioselective aminomethylamination of dienes for the construction of unsymmetrical chiral diamines.
{"title":"Dynamic amine sorting enables multiselective construction of unsymmetrical chiral diamines","authors":"Shoule Cai, Zeyu Zhao, Guoqing Yang, Hanmin Huang","doi":"10.1038/s41557-024-01673-z","DOIUrl":"10.1038/s41557-024-01673-z","url":null,"abstract":"Precisely differentiating chemicals featuring minor discrepancies is the prerequisite for achieving high selectivities in both chemical synthesis and biological activities. However, efficient strategies to differentiate and sort such congeneric compounds are lacking, posing daunting challenges for synthetic endeavours aimed at their orderly incorporation. Here we report a dynamic amine-sorting strategy that incorporates the chemoselective formation of the aminomethyl cyclopalladated complex to achieve the efficient differentiation of amine congeners. A series of amines sharing similar three-dimensional structures and properties, as well as possessing notoriously strong binding ability to metals, can be efficiently differentiated, enabling the highly chemo-, regio- and enantioselective multicomponent aminomethylamination of dienes to construct a variety of unsymmetrical chiral diamines. This dynamic amine-sorting strategy tackles the long-standing challenge of precise differentiation and orderly incorporation of aliphatic amines with subtle differences. From a broader perspective, the success demonstrates that meticulously designed metal complexes can provide flexible and general solutions for controlling delicate selectivities in sophisticated synthesis. Efficient strategies to differentiate and sort congeneric compounds are lacking. Now a metal-mediated dynamic amine-sorting strategy has been developed to precisely differentiate and assemble different amine congeners in an orderly manner, facilitating highly chemo-, regio- and enantioselective aminomethylamination of dienes for the construction of unsymmetrical chiral diamines.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 12","pages":"1972-1981"},"PeriodicalIF":19.2,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665408","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 : 2024-11-15DOI: 10.1038/s41557-024-01672-0
Yong-Jun Tian, Chenghua Deng, Li Zhao, Jin-Sheng Zou, Xue-Cui Wu, Yanan Jia, Ze-Yang Zhang, Jie Zhang, Yun-Lei Peng, Guangjin Chen, Michael J. Zaworotko
Developing porous adsorbents for the complete sieving of propylene/propane mixtures represents an alternative method to energy-intensive cryogenic distillation processes. However, the similar physical properties of these molecules and the inherent trade-off among adsorption capacity, selectivity, diffusion kinetic and host–guest binding interactions in molecular sieving adsorbents makes their separation challenging. Here we report the separation of propylene/propane mixtures through a crystalline porous material (HAF-1) that features channels and shrinkage throats—the latter defined as narrower channels that connect the main channels and a molecular pocket—where the throat aperture is between the kinetic diameters of propylene and propane. Single-crystal X-ray diffraction and computational simulation reveal that the shrinkage channels and hanging molecular pockets are key to ensure high sieving efficiency and high propylene adsorption capacity. Dynamic breakthrough experiments show that HAF-1 enables the achievement of high-purity (≥99.7%) propylene with a productivity of 33.9 l kg−1 by just one adsorption–desorption circle from propylene/propane mixtures. Propylene and propane have similar physicochemical properties, and thus their separation is challenging. Now, as an alternative to energy-intensive cryogenic distillation methods, a molecular sieving adsorbent with high propylene adsorption capacity has been shown to sieve propylene from propylene/propane mixtures to yield high-purity propylene.
开发用于完全筛分丙烯/丙烷混合物的多孔吸附剂是能源密集型低温蒸馏工艺的一种替代方法。然而，这些分子具有相似的物理特性，而且分子筛吸附剂在吸附容量、选择性、扩散动力学和主客体结合相互作用之间存在固有的权衡，这使得它们的分离具有挑战性。在此，我们报告了通过一种结晶多孔材料（HAF-1）分离丙烯/丙烷混合物的情况，该材料具有通道和收缩喉道（后者定义为连接主通道和分子袋的较窄通道），其中喉道孔径介于丙烯和丙烷的动力学直径之间。单晶 X 射线衍射和计算模拟显示，收缩通道和悬挂分子袋是确保高筛分效率和高丙烯吸附能力的关键。动态突破实验表明，HAF-1 只需从丙烯/丙烷混合物中进行一次吸附-解吸循环，就能获得生产率为 33.9 l kg-1 的高纯度（≥99.7%）丙烯。
{"title":"Pore configuration control in hybrid azolate ultra-microporous frameworks for sieving propylene from propane","authors":"Yong-Jun Tian, Chenghua Deng, Li Zhao, Jin-Sheng Zou, Xue-Cui Wu, Yanan Jia, Ze-Yang Zhang, Jie Zhang, Yun-Lei Peng, Guangjin Chen, Michael J. Zaworotko","doi":"10.1038/s41557-024-01672-0","DOIUrl":"10.1038/s41557-024-01672-0","url":null,"abstract":"Developing porous adsorbents for the complete sieving of propylene/propane mixtures represents an alternative method to energy-intensive cryogenic distillation processes. However, the similar physical properties of these molecules and the inherent trade-off among adsorption capacity, selectivity, diffusion kinetic and host–guest binding interactions in molecular sieving adsorbents makes their separation challenging. Here we report the separation of propylene/propane mixtures through a crystalline porous material (HAF-1) that features channels and shrinkage throats—the latter defined as narrower channels that connect the main channels and a molecular pocket—where the throat aperture is between the kinetic diameters of propylene and propane. Single-crystal X-ray diffraction and computational simulation reveal that the shrinkage channels and hanging molecular pockets are key to ensure high sieving efficiency and high propylene adsorption capacity. Dynamic breakthrough experiments show that HAF-1 enables the achievement of high-purity (≥99.7%) propylene with a productivity of 33.9 l kg−1 by just one adsorption–desorption circle from propylene/propane mixtures. Propylene and propane have similar physicochemical properties, and thus their separation is challenging. Now, as an alternative to energy-intensive cryogenic distillation methods, a molecular sieving adsorbent with high propylene adsorption capacity has been shown to sieve propylene from propylene/propane mixtures to yield high-purity propylene.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 1","pages":"141-147"},"PeriodicalIF":19.2,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637021","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 : 2024-11-08DOI: 10.1038/s41557-024-01665-z
Kai Liu, Alex W. P. Blokhuis, Sietse J. Dijt, Juntian Wu, Shana Hamed, Armin Kiani, Bartosz M. Matysiak, Sijbren Otto
Fuelled chemical systems have considerable functional potential that remains largely unexplored. Here we report an approach to transient amide bond formation and use it to harness chemical energy and convert it to mechanical motion by integrating dissipative self-assembly and the Marangoni effect in a source–sink system. Droplets are formed through dissipative self-assembly following the reaction of octylamine with 2,3-dimethylmaleic anhydride. The resulting amides are hydrolytically labile, making the droplets transient, which enables them to act as a source of octylamine. A sink for octylamine was created by placing a drop of oleic acid at the air–water interface. This source–sink system sets up a gradient in surface tension, which gives rise to a macroscopic Marangoni flow that can transport the droplets in solution with tunable speed. Carbodiimides can fuel this motion by converting diacid waste back to anhydride. This study shows how fuelling at the molecular level can, via assembly at the supramolecular level, lead to liquid flow at the macroscopic level. The use of molecules as fuels to achieve function is largely unexplored. Now it has been shown that fuelled dissipative self-assembly can yield transient droplets that release a surfactant, driving the macroscopic transport of these droplets.
{"title":"Molecular-scale dissipative chemistry drives the formation of nanoscale assemblies and their macroscale transport","authors":"Kai Liu, Alex W. P. Blokhuis, Sietse J. Dijt, Juntian Wu, Shana Hamed, Armin Kiani, Bartosz M. Matysiak, Sijbren Otto","doi":"10.1038/s41557-024-01665-z","DOIUrl":"10.1038/s41557-024-01665-z","url":null,"abstract":"Fuelled chemical systems have considerable functional potential that remains largely unexplored. Here we report an approach to transient amide bond formation and use it to harness chemical energy and convert it to mechanical motion by integrating dissipative self-assembly and the Marangoni effect in a source–sink system. Droplets are formed through dissipative self-assembly following the reaction of octylamine with 2,3-dimethylmaleic anhydride. The resulting amides are hydrolytically labile, making the droplets transient, which enables them to act as a source of octylamine. A sink for octylamine was created by placing a drop of oleic acid at the air–water interface. This source–sink system sets up a gradient in surface tension, which gives rise to a macroscopic Marangoni flow that can transport the droplets in solution with tunable speed. Carbodiimides can fuel this motion by converting diacid waste back to anhydride. This study shows how fuelling at the molecular level can, via assembly at the supramolecular level, lead to liquid flow at the macroscopic level. The use of molecules as fuels to achieve function is largely unexplored. Now it has been shown that fuelled dissipative self-assembly can yield transient droplets that release a surfactant, driving the macroscopic transport of these droplets.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 1","pages":"124-131"},"PeriodicalIF":19.2,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142623932","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：