Pub Date : 2024-08-20DOI: 10.1038/s41557-024-01593-y
Axel Gomez, Ward H. Thompson, Damien Laage
The transport of excess protons in water is central to acid–base chemistry, biochemistry and energy production. However, elucidating its mechanism has been challenging. Recent nonlinear vibrational spectroscopy experiments could not be explained by existing models. Here we use both vibrational spectroscopy calculations and neural-network-based molecular dynamics simulations that account for nuclear quantum effects for all atoms to determine the proton transport mechanism. Our simulations reveal an equilibrium between two stable proton-localized structures with distinct Eigen-like and Zundel-like hydrogen-bond motifs. Proton transport follows a three-step mechanism gated by two successive hydrogen-bond exchanges: the first reduces the proton-acceptor water coordination, leading to proton transfer, and the second, the rate-limiting step, prevents rapid back-transfer by increasing the proton-donor coordination. This sequential mechanism is consistent with experimental characterizations of proton diffusion, explaining the low activation energy and the prolonged intermediate lifetimes in vibrational spectroscopy. These results are crucial for understanding proton dynamics in biochemical and technological systems. Recent vibrational spectroscopy experiments suggested that excess proton transport in water is more complex than previously thought. Now the proton transport mechanism has been explored using neural-network-based simulations and related to experimental measurements through vibrational spectra calculations. It was observed to be a three-step process gated by two successive hydrogen-bond exchanges.
过量质子在水中的迁移是酸碱化学、生物化学和能源生产的核心。然而，阐明其机理一直是一项挑战。现有模型无法解释最近的非线性振动光谱实验。在这里，我们利用振动光谱计算和基于神经网络的分子动力学模拟（考虑到所有原子的核量子效应）来确定质子传输机制。我们的模拟揭示了两种稳定的质子定位结构之间的平衡，这两种结构具有不同的类 Eigen 和类 Zundel 氢键图案。质子迁移遵循一个由两次连续氢键交换驱动的三步机制：第一步降低质子受体水配位，导致质子转移；第二步，即限制速率的一步，通过增加质子供体配位防止快速反向转移。这种顺序机制与质子扩散的实验特征一致，解释了振动光谱中的低活化能和中间寿命延长的原因。这些结果对于理解生化和技术系统中的质子动力学至关重要。
{"title":"Neural-network-based molecular dynamics simulations reveal that proton transport in water is doubly gated by sequential hydrogen-bond exchange","authors":"Axel Gomez, Ward H. Thompson, Damien Laage","doi":"10.1038/s41557-024-01593-y","DOIUrl":"10.1038/s41557-024-01593-y","url":null,"abstract":"The transport of excess protons in water is central to acid–base chemistry, biochemistry and energy production. However, elucidating its mechanism has been challenging. Recent nonlinear vibrational spectroscopy experiments could not be explained by existing models. Here we use both vibrational spectroscopy calculations and neural-network-based molecular dynamics simulations that account for nuclear quantum effects for all atoms to determine the proton transport mechanism. Our simulations reveal an equilibrium between two stable proton-localized structures with distinct Eigen-like and Zundel-like hydrogen-bond motifs. Proton transport follows a three-step mechanism gated by two successive hydrogen-bond exchanges: the first reduces the proton-acceptor water coordination, leading to proton transfer, and the second, the rate-limiting step, prevents rapid back-transfer by increasing the proton-donor coordination. This sequential mechanism is consistent with experimental characterizations of proton diffusion, explaining the low activation energy and the prolonged intermediate lifetimes in vibrational spectroscopy. These results are crucial for understanding proton dynamics in biochemical and technological systems. Recent vibrational spectroscopy experiments suggested that excess proton transport in water is more complex than previously thought. Now the proton transport mechanism has been explored using neural-network-based simulations and related to experimental measurements through vibrational spectra calculations. It was observed to be a three-step process gated by two successive hydrogen-bond exchanges.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1838-1844"},"PeriodicalIF":19.2,"publicationDate":"2024-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142007636","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 : 2024-08-16DOI: 10.1038/s41557-024-01610-0
Chloe E. Markey, Daniel Reker
Drugs that target peptide hormone receptors are of great interest in the treatment of type 2 diabetes. In spite of limited data and vast design spaces, a bespoke computational pipeline has designed peptides that target two receptors with high potency.
{"title":"Machine learning trims the peptide drug design process to a sweet spot","authors":"Chloe E. Markey, Daniel Reker","doi":"10.1038/s41557-024-01610-0","DOIUrl":"10.1038/s41557-024-01610-0","url":null,"abstract":"Drugs that target peptide hormone receptors are of great interest in the treatment of type 2 diabetes. In spite of limited data and vast design spaces, a bespoke computational pipeline has designed peptides that target two receptors with high potency.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 9","pages":"1394-1395"},"PeriodicalIF":19.2,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141991813","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 : 2024-08-15DOI: 10.1038/s41557-024-01612-y
Chloe D. Wong, Elizabeth R. Jarvo
The development of enantiospecific sulfone reactions has been hindered by the inherent acidity of sulfones, which result in deleterious racemization. Now, the synthesis of enantioenriched diarylalkanes has been reported via sufficiently fast cross-coupling that circumvents racemization of the chiral sulfone.
{"title":"Sulfone cross-coupling outcompetes proton transfer","authors":"Chloe D. Wong, Elizabeth R. Jarvo","doi":"10.1038/s41557-024-01612-y","DOIUrl":"10.1038/s41557-024-01612-y","url":null,"abstract":"The development of enantiospecific sulfone reactions has been hindered by the inherent acidity of sulfones, which result in deleterious racemization. Now, the synthesis of enantioenriched diarylalkanes has been reported via sufficiently fast cross-coupling that circumvents racemization of the chiral sulfone.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 9","pages":"1392-1393"},"PeriodicalIF":19.2,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141986469","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 : 2024-08-14DOI: 10.1038/s41557-024-01607-9
Photocatalytic overall water splitting (OWS) is highly desirable for hydrogen production but challenging owing to rapid charge recombination. We demonstrate a dynamic metal–organic framework (MOF) photocatalyst that achieves OWS via one-step photoexcitation. Upon excitation by light, the MOF undergoes a structural twist that suppresses charge recombination and achieves OWS.
{"title":"A dynamic metal–organic framework photocatalyst","authors":"","doi":"10.1038/s41557-024-01607-9","DOIUrl":"10.1038/s41557-024-01607-9","url":null,"abstract":"Photocatalytic overall water splitting (OWS) is highly desirable for hydrogen production but challenging owing to rapid charge recombination. We demonstrate a dynamic metal–organic framework (MOF) photocatalyst that achieves OWS via one-step photoexcitation. Upon excitation by light, the MOF undergoes a structural twist that suppresses charge recombination and achieves OWS.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 10","pages":"1580-1581"},"PeriodicalIF":19.2,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141980820","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 : 2024-08-14DOI: 10.1038/s41557-024-01600-2
Chase M. Kayrouz, Kendra A. Ireland, Vanessa Y. Ying, Katherine M. Davis, Mohammad R. Seyedsayamdost
Selenium is an essential micronutrient, but its presence in biology has been limited to protein and nucleic acid biopolymers. The recent identification of a biosynthetic pathway for selenium-containing small molecules suggests that there is a larger family of selenometabolites that remains to be discovered. Here we identify a recently evolved branch of abundant and uncharacterized metalloenzymes that we predict are involved in selenometabolite biosynthesis using a bioinformatic search strategy that relies on the mapping of composite active site motifs. Biochemical studies confirm this prediction and show that these enzymes form an unusual C–Se bond onto histidine, thus giving rise to a distinct selenometabolite and potent antioxidant that we have termed ovoselenol. Aside from providing insights into the evolution of this enzyme class and the structural basis of C–Se bond formation, our work offers a blueprint for charting the microbial selenometabolome in the future. Although biosynthetic pathways of selenium-containing macromolecules have been known for decades, pathways for specific incorporation of selenium into small molecules have only recently begun to be uncovered. Now the selenometabolome is expanded further through the discovery and biosynthetic elucidation of ovoselenol, a selenium-containing antioxidant found in marine microorganisms.
{"title":"Discovery of the selenium-containing antioxidant ovoselenol derived from convergent evolution","authors":"Chase M. Kayrouz, Kendra A. Ireland, Vanessa Y. Ying, Katherine M. Davis, Mohammad R. Seyedsayamdost","doi":"10.1038/s41557-024-01600-2","DOIUrl":"10.1038/s41557-024-01600-2","url":null,"abstract":"Selenium is an essential micronutrient, but its presence in biology has been limited to protein and nucleic acid biopolymers. The recent identification of a biosynthetic pathway for selenium-containing small molecules suggests that there is a larger family of selenometabolites that remains to be discovered. Here we identify a recently evolved branch of abundant and uncharacterized metalloenzymes that we predict are involved in selenometabolite biosynthesis using a bioinformatic search strategy that relies on the mapping of composite active site motifs. Biochemical studies confirm this prediction and show that these enzymes form an unusual C–Se bond onto histidine, thus giving rise to a distinct selenometabolite and potent antioxidant that we have termed ovoselenol. Aside from providing insights into the evolution of this enzyme class and the structural basis of C–Se bond formation, our work offers a blueprint for charting the microbial selenometabolome in the future. Although biosynthetic pathways of selenium-containing macromolecules have been known for decades, pathways for specific incorporation of selenium into small molecules have only recently begun to be uncovered. Now the selenometabolome is expanded further through the discovery and biosynthetic elucidation of ovoselenol, a selenium-containing antioxidant found in marine microorganisms.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1868-1875"},"PeriodicalIF":19.2,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141980825","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}
Hydrogen bonds profoundly influence the fundamental chemical, physical and biological properties of molecules and materials. Owing to their relatively weaker interactions compared to other chemical bonds, hydrogen bonds alone are generally insufficient to induce substantial changes in electrical properties, thus imposing severe constraints on their applications in related devices. Here we report a metal–insulator transition controlled by hydrogen bonds for an organic–inorganic (1,3-diaminopropane)0.5SnSe2 superlattice that exhibits a colossal on–off ratio of 107 in electrical resistivity. The key to inducing the transition is a change in the amino group’s hydrogen-bonding structure from dynamic to static. In the dynamic state, thermally activated free rotation continuously breaks and forms transient hydrogen bonds with adjacent Se anions. In the static state, the amino group forms three fixed-angle positions, each separated by 120°. Our findings contribute to the understanding of electrical phenomena in organic–inorganic hybrid materials and may be used for the design of future molecule-based electronic materials. Hydrogen bonds impact the chemical, physical and biological properties of molecular materials, but are rarely able to induce significant changes in electrical properties. Now a dynamic-to-static transition of hydrogen bonds in an organic–inorganic superlattice has been shown to yield a metal–insulator transition with an on–off ratio of 107 in electrical resistivity.
{"title":"Dynamic-to-static switch of hydrogen bonds induces a metal–insulator transition in an organic–inorganic superlattice","authors":"Zhenkai Xie, Rui Luo, Tianping Ying, Yurui Gao, Boqin Song, Tongxu Yu, Xu Chen, Munan Hao, Congcong Chai, Jiashu Yan, Zhiheng Huang, Zhiguo Chen, Luojun Du, Chongqin Zhu, Jiangang Guo, Xiaolong Chen","doi":"10.1038/s41557-024-01566-1","DOIUrl":"10.1038/s41557-024-01566-1","url":null,"abstract":"Hydrogen bonds profoundly influence the fundamental chemical, physical and biological properties of molecules and materials. Owing to their relatively weaker interactions compared to other chemical bonds, hydrogen bonds alone are generally insufficient to induce substantial changes in electrical properties, thus imposing severe constraints on their applications in related devices. Here we report a metal–insulator transition controlled by hydrogen bonds for an organic–inorganic (1,3-diaminopropane)0.5SnSe2 superlattice that exhibits a colossal on–off ratio of 107 in electrical resistivity. The key to inducing the transition is a change in the amino group’s hydrogen-bonding structure from dynamic to static. In the dynamic state, thermally activated free rotation continuously breaks and forms transient hydrogen bonds with adjacent Se anions. In the static state, the amino group forms three fixed-angle positions, each separated by 120°. Our findings contribute to the understanding of electrical phenomena in organic–inorganic hybrid materials and may be used for the design of future molecule-based electronic materials. Hydrogen bonds impact the chemical, physical and biological properties of molecular materials, but are rarely able to induce significant changes in electrical properties. Now a dynamic-to-static transition of hydrogen bonds in an organic–inorganic superlattice has been shown to yield a metal–insulator transition with an on–off ratio of 107 in electrical resistivity.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1803-1810"},"PeriodicalIF":19.2,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141980822","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 : 2024-08-13DOI: 10.1038/s41557-024-01625-7
Fabian B. H. Rehm, Tristan J. Tyler, Yan Zhou, Yen-Hua Huang, Conan K. Wang, Nicole Lawrence, David J. Craik, Thomas Durek
{"title":"Author Correction: Repurposing a plant peptide cyclase for targeted lysine acylation","authors":"Fabian B. H. Rehm, Tristan J. Tyler, Yan Zhou, Yen-Hua Huang, Conan K. Wang, Nicole Lawrence, David J. Craik, Thomas Durek","doi":"10.1038/s41557-024-01625-7","DOIUrl":"10.1038/s41557-024-01625-7","url":null,"abstract":"","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 9","pages":"1565-1565"},"PeriodicalIF":19.2,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41557-024-01625-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141976180","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}
Pub Date : 2024-08-13DOI: 10.1038/s41557-024-01615-9
Atanu Ghosh, Jonathan T. Yarranton, James K. McCusker
{"title":"Publisher Correction: Establishing the origin of Marcus-inverted-region behaviour in the excited-state dynamics of cobalt(III) polypyridyl complexes","authors":"Atanu Ghosh, Jonathan T. Yarranton, James K. McCusker","doi":"10.1038/s41557-024-01615-9","DOIUrl":"10.1038/s41557-024-01615-9","url":null,"abstract":"","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 10","pages":"1732-1732"},"PeriodicalIF":19.2,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41557-024-01615-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141976181","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}
Pub Date : 2024-08-13DOI: 10.1038/s41557-024-01601-1
Evert Njomen, Rachel E. Hayward, Kristen E. DeMeester, Daisuke Ogasawara, Melissa M. Dix, Tracey Nguyen, Paige Ashby, Gabriel M. Simon, Stuart L. Schreiber, Bruno Melillo, Benjamin F. Cravatt
Covalent chemistry is a versatile approach for expanding the ligandability of the human proteome. Activity-based protein profiling (ABPP) can infer the specific residues modified by electrophilic compounds through competition with broadly reactive probes. However, the extent to which such residue-directed platforms fully assess the protein targets of electrophilic compounds in cells remains unclear. Here we evaluate a complementary protein-directed ABPP method that identifies proteins showing stereoselective reactivity with alkynylated, chiral electrophilic compounds—termed stereoprobes. Integration of protein- and cysteine-directed data from cancer cells treated with tryptoline acrylamide stereoprobes revealed generally well-correlated ligandability maps and highlighted features, such as protein size and the proteotypicity of cysteine-containing peptides, that explain gaps in each ABPP platform. In total, we identified stereoprobe binding events for >300 structurally and functionally diverse proteins, including compounds that stereoselectively and site-specifically disrupt MAD2L1BP interactions with the spindle assembly checkpoint complex leading to delayed mitotic exit in cancer cells. The ligandability of the human proteome can be expanded using covalent chemistry. A multi-tiered chemical proteomic strategy now provides in-depth maps of tryptoline acrylamide–protein interactions in cancer cells. This platform afforded the discovery of stereoselective covalent ligands for hundreds of human proteins, including compounds that disrupt protein–protein interactions regulating the cell cycle.
{"title":"Multi-tiered chemical proteomic maps of tryptoline acrylamide–protein interactions in cancer cells","authors":"Evert Njomen, Rachel E. Hayward, Kristen E. DeMeester, Daisuke Ogasawara, Melissa M. Dix, Tracey Nguyen, Paige Ashby, Gabriel M. Simon, Stuart L. Schreiber, Bruno Melillo, Benjamin F. Cravatt","doi":"10.1038/s41557-024-01601-1","DOIUrl":"10.1038/s41557-024-01601-1","url":null,"abstract":"Covalent chemistry is a versatile approach for expanding the ligandability of the human proteome. Activity-based protein profiling (ABPP) can infer the specific residues modified by electrophilic compounds through competition with broadly reactive probes. However, the extent to which such residue-directed platforms fully assess the protein targets of electrophilic compounds in cells remains unclear. Here we evaluate a complementary protein-directed ABPP method that identifies proteins showing stereoselective reactivity with alkynylated, chiral electrophilic compounds—termed stereoprobes. Integration of protein- and cysteine-directed data from cancer cells treated with tryptoline acrylamide stereoprobes revealed generally well-correlated ligandability maps and highlighted features, such as protein size and the proteotypicity of cysteine-containing peptides, that explain gaps in each ABPP platform. In total, we identified stereoprobe binding events for >300 structurally and functionally diverse proteins, including compounds that stereoselectively and site-specifically disrupt MAD2L1BP interactions with the spindle assembly checkpoint complex leading to delayed mitotic exit in cancer cells. The ligandability of the human proteome can be expanded using covalent chemistry. A multi-tiered chemical proteomic strategy now provides in-depth maps of tryptoline acrylamide–protein interactions in cancer cells. This platform afforded the discovery of stereoselective covalent ligands for hundreds of human proteins, including compounds that disrupt protein–protein interactions regulating the cell cycle.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 10","pages":"1592-1604"},"PeriodicalIF":19.2,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141974106","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 : 2024-08-12DOI: 10.1038/s41557-024-01599-6
Kang Sun, Yan Huang, Fusai Sun, Qingyu Wang, Yujie Zhou, Jingxue Wang, Qun Zhang, Xusheng Zheng, Fengtao Fan, Yi Luo, Jun Jiang, Hai-Long Jiang
Photocatalytic overall water splitting holds great promise for solar-to-hydrogen conversion. Maintaining charge separation is a major challenge but is key to unlocking this potential. Here we discovered a metal–organic framework (MOF) that shows suppressed charge recombination. This MOF features electronically insulated Zn2+ nodes and two chemically equivalent, yet crystallographically independent, linkers. These linkers behave as an electron donor–acceptor pair with non-overlapping band edges. Upon photoexcitation, the MOF undergoes a dynamic excited-state structural twist, inducing orbital rearrangements that forbid radiative relaxation and thereby promote a long-lived charge-separated state. As a result, the MOF achieves visible-light photocatalytic overall water splitting, in the presence of co-catalysts, with an apparent quantum efficiency of 3.09 ± 0.32% at 365 nm and shows little activity loss in 100 h of consecutive runs. Furthermore, the dynamic excited-state structural twist is also successfully extended to other photocatalysts. This strategy for suppressing charge recombination will be applicable to diverse photochemical processes beyond overall water splitting. Solar water splitting holds great promise for hydrogen production but is significantly hindered by rapid recombination of photogenerated charges. Now a metal–organic framework photocatalyst has been shown to undergo, upon photoexcitation, a dynamic excited-state structural twist that greatly suppresses charge recombination to enable efficient photocatalytic overall water splitting.
{"title":"Dynamic structural twist in metal–organic frameworks enhances solar overall water splitting","authors":"Kang Sun, Yan Huang, Fusai Sun, Qingyu Wang, Yujie Zhou, Jingxue Wang, Qun Zhang, Xusheng Zheng, Fengtao Fan, Yi Luo, Jun Jiang, Hai-Long Jiang","doi":"10.1038/s41557-024-01599-6","DOIUrl":"10.1038/s41557-024-01599-6","url":null,"abstract":"Photocatalytic overall water splitting holds great promise for solar-to-hydrogen conversion. Maintaining charge separation is a major challenge but is key to unlocking this potential. Here we discovered a metal–organic framework (MOF) that shows suppressed charge recombination. This MOF features electronically insulated Zn2+ nodes and two chemically equivalent, yet crystallographically independent, linkers. These linkers behave as an electron donor–acceptor pair with non-overlapping band edges. Upon photoexcitation, the MOF undergoes a dynamic excited-state structural twist, inducing orbital rearrangements that forbid radiative relaxation and thereby promote a long-lived charge-separated state. As a result, the MOF achieves visible-light photocatalytic overall water splitting, in the presence of co-catalysts, with an apparent quantum efficiency of 3.09 ± 0.32% at 365 nm and shows little activity loss in 100 h of consecutive runs. Furthermore, the dynamic excited-state structural twist is also successfully extended to other photocatalysts. This strategy for suppressing charge recombination will be applicable to diverse photochemical processes beyond overall water splitting. Solar water splitting holds great promise for hydrogen production but is significantly hindered by rapid recombination of photogenerated charges. Now a metal–organic framework photocatalyst has been shown to undergo, upon photoexcitation, a dynamic excited-state structural twist that greatly suppresses charge recombination to enable efficient photocatalytic overall water splitting.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 10","pages":"1638-1646"},"PeriodicalIF":19.2,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141918788","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}
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