Pub Date : 2021-08-09DOI: 10.22541/au.162850019.93838101/v1
R. Nolte, Pieter J. Gilissen, N. Vanthuyne, B. Feringa, J. Elemans
Molecular motors change conformation under the influence of light and when attached to host molecules they may find applications as sensors and switchable catalysts. Here we present a porphyrin macrocyclic host functionalized with two motor appendages for future catalytic applications. The compound is formed as a mixture of six stereoisomers (three sets of enantiomers), which have been separated by (chiral) chromatography. 1H NMR and chiral spectroscopy revealed that in one set of diastereomers the two motors interact with the cavity of the host (bound-bound), whereas in a second set one interacts and the other one does not (bound-loose). In the third set both motors do not interact with the host compound (loose-loose). The motorized hosts bind guest molecules in the order: (loose-loose) > (bound-loose) > (bound-bound). They can be switched with light to pseudo-identical diastereomers, leading to orthogonal behavior in the light-gated binding of guest molecules. Whereas the photo-isomerization of the diastereomer set loose-loose significantly lowers the binding affinity for viologen guests, the opposite is true for the diastereomer set bound-bound, i.e. the binding affinity increases. For the diastereomer set bound-loose no influence on guest binding is observed as the effect of photoisomerization on the motors is cancelled out.
{"title":"Light-gated binding in double-motorized porphyrin cages","authors":"R. Nolte, Pieter J. Gilissen, N. Vanthuyne, B. Feringa, J. Elemans","doi":"10.22541/au.162850019.93838101/v1","DOIUrl":"https://doi.org/10.22541/au.162850019.93838101/v1","url":null,"abstract":"Molecular motors change conformation under the influence of light and\u0000when attached to host molecules they may find applications as sensors\u0000and switchable catalysts. Here we present a porphyrin macrocyclic host\u0000functionalized with two motor appendages for future catalytic\u0000applications. The compound is formed as a mixture of six stereoisomers\u0000(three sets of enantiomers), which have been separated by (chiral)\u0000chromatography. 1H NMR and chiral spectroscopy revealed that in one set\u0000of diastereomers the two motors interact with the cavity of the host\u0000(bound-bound), whereas in a second set one interacts and the other one\u0000does not (bound-loose). In the third set both motors do not interact\u0000with the host compound (loose-loose). The motorized hosts bind guest\u0000molecules in the order: (loose-loose) > (bound-loose)\u0000> (bound-bound). They can be switched with light to\u0000pseudo-identical diastereomers, leading to orthogonal behavior in the\u0000light-gated binding of guest molecules. Whereas the photo-isomerization\u0000of the diastereomer set loose-loose significantly lowers the binding\u0000affinity for viologen guests, the opposite is true for the diastereomer\u0000set bound-bound, i.e. the binding affinity increases. For the\u0000diastereomer set bound-loose no influence on guest binding is observed\u0000as the effect of photoisomerization on the motors is cancelled out.","PeriodicalId":74244,"journal":{"name":"Natural sciences (Weinheim, Germany)","volume":"99 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76983416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-08-05DOI: 10.1002/ntls.20210038/v2/decision1
Wangyin Wang, Dingyi Li, Xupeng Cao, Song Xue, Can Li
{"title":"Decision letter for \"Liberating photoinhibition through nongenetic drainage of electrons from photosynthesis\"","authors":"Wangyin Wang, Dingyi Li, Xupeng Cao, Song Xue, Can Li","doi":"10.1002/ntls.20210038/v2/decision1","DOIUrl":"https://doi.org/10.1002/ntls.20210038/v2/decision1","url":null,"abstract":"","PeriodicalId":74244,"journal":{"name":"Natural sciences (Weinheim, Germany)","volume":"130 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80261590","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-08-02DOI: 10.22541/au.162792174.46183015/v1
Bretislav Friedrich, G. Meijer, H. Schmidt-Böcking, G. Gruber
Prompted by the centenary of Alfred Landé’s g-factor, we reconstruct Landé’s path to his discovery of half-integer angular momentum quantum numbers and of vector coupling of atomic angular momenta - both encapsulated in the g-factor - as well as point to reverberations of Landé’s breakthroughs in the work of other pioneers of quantum physics.
{"title":"One Hundred Years of Alfred Landé’s g-Factor","authors":"Bretislav Friedrich, G. Meijer, H. Schmidt-Böcking, G. Gruber","doi":"10.22541/au.162792174.46183015/v1","DOIUrl":"https://doi.org/10.22541/au.162792174.46183015/v1","url":null,"abstract":"Prompted by the centenary of Alfred Landé’s g-factor, we reconstruct\u0000Landé’s path to his discovery of half-integer angular momentum quantum\u0000numbers and of vector coupling of atomic angular momenta - both\u0000encapsulated in the g-factor - as well as point to reverberations of\u0000Landé’s breakthroughs in the work of other pioneers of quantum physics.","PeriodicalId":74244,"journal":{"name":"Natural sciences (Weinheim, Germany)","volume":"137 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86397337","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-07-07DOI: 10.22541/AU.162569010.07717143/V1
Anna Wuttig, F. Toste
Predictive control over the selectivity outcome of an organic synthetic method is an essential hallmark of reaction success. Electricity-driven synthesis offers a reemerging approach to facilitate the design of reaction sequences towards increased molecular complexity. In addition to the desirable sustainability features of electroorganic processes, the inherent interfacial nature of electrochemical systems present unique opportunities to tune reaction selectivity. To illustrate this feature, we outline examples of mechanism-guided interfacial control over CO2 electroreduction selectivity, a well-studied and instructive electrochemical process with multiple reduction products that are thermodynamically accessible. These studies reveal how controlled proton delivery to the electrode surface and substrate electroadsorption with the electrode dictate reaction selectivity. We describe and compare simple, yet salient, examples from the electroorganic literature, where we postulate that similar effects predominate the observed reactivity. This perspective highlights how the interface serves as a tunable dimension in electrochemical processes, delineating unique tools to study, manipulate, and achieve reaction selectivity in electricity-driven organic synthesis.
{"title":"The Interface is a Tunable Dimension in Electricity-Driven Organic Synthesis","authors":"Anna Wuttig, F. Toste","doi":"10.22541/AU.162569010.07717143/V1","DOIUrl":"https://doi.org/10.22541/AU.162569010.07717143/V1","url":null,"abstract":"Predictive control over the selectivity outcome of an organic synthetic\u0000method is an essential hallmark of reaction success. Electricity-driven\u0000synthesis offers a reemerging approach to facilitate the design of\u0000reaction sequences towards increased molecular complexity. In addition\u0000to the desirable sustainability features of electroorganic processes,\u0000the inherent interfacial nature of electrochemical systems present\u0000unique opportunities to tune reaction selectivity. To illustrate this\u0000feature, we outline examples of mechanism-guided interfacial control\u0000over CO2 electroreduction selectivity, a well-studied and instructive\u0000electrochemical process with multiple reduction products that are\u0000thermodynamically accessible. These studies reveal how controlled proton\u0000delivery to the electrode surface and substrate electroadsorption with\u0000the electrode dictate reaction selectivity. We describe and compare\u0000simple, yet salient, examples from the electroorganic literature, where\u0000we postulate that similar effects predominate the observed reactivity.\u0000This perspective highlights how the interface serves as a tunable\u0000dimension in electrochemical processes, delineating unique tools to\u0000study, manipulate, and achieve reaction selectivity in\u0000electricity-driven organic synthesis.","PeriodicalId":74244,"journal":{"name":"Natural sciences (Weinheim, Germany)","volume":"71 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91201355","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-06-14DOI: 10.1002/ntls.10021/v1/decision1
Jian Zhang, Tiantian Chen, Yuanhao Wang, F. Zhou, Zhenfeng Zhang, I. Gridnev, Wanbin Zhang
The efficient construction of γ-chirogenic amines has been realized via asymmetric hydrogenation of γ-branched N-phthaloyl allylamines by using a bisphosphine-Rh catalyst bearing a large bite angle. The desired products possessing different types of γ-substituents were obtained in quantitative yields and with excellent enantioselectivities (up to >99.9% ee). This protocol provided a practical method for the preparation of γ-chirogenic amine derivatives such as the famous antidepressant drug Fluoxetine (up to 50000 S/C). The mechanism calculation shows a weak interaction-promoted activation mode which is completely different from the traditional coordination-promoted activation mode in the Rh-catalyzed hydrogenation.
{"title":"Decision letter for \"Asymmetric hydrogenation of γ ‐branched allylamines for the efficient synthesis of γ ‐chirogenic amines\"","authors":"Jian Zhang, Tiantian Chen, Yuanhao Wang, F. Zhou, Zhenfeng Zhang, I. Gridnev, Wanbin Zhang","doi":"10.1002/ntls.10021/v1/decision1","DOIUrl":"https://doi.org/10.1002/ntls.10021/v1/decision1","url":null,"abstract":"The efficient construction of γ-chirogenic amines has been realized via\u0000asymmetric hydrogenation of γ-branched N-phthaloyl allylamines by using\u0000a bisphosphine-Rh catalyst bearing a large bite angle. The desired\u0000products possessing different types of γ-substituents were obtained in\u0000quantitative yields and with excellent enantioselectivities (up to\u0000>99.9% ee). This protocol provided a practical method for\u0000the preparation of γ-chirogenic amine derivatives such as the famous\u0000antidepressant drug Fluoxetine (up to 50000 S/C). The mechanism\u0000calculation shows a weak interaction-promoted activation mode which is\u0000completely different from the traditional coordination-promoted\u0000activation mode in the Rh-catalyzed hydrogenation.","PeriodicalId":74244,"journal":{"name":"Natural sciences (Weinheim, Germany)","volume":"52 9 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91120270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Decision letter for \"Commentary: Chemical dynamics from the gas‐phase to surfaces\"","authors":"D. Herschbach","doi":"10.1002/NTLS.10007","DOIUrl":"https://doi.org/10.1002/NTLS.10007","url":null,"abstract":"","PeriodicalId":74244,"journal":{"name":"Natural sciences (Weinheim, Germany)","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82348418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A trio of outstanding physical chemists, Daniel Auerbach, John Tully, andAlecWodtke, has produced a superb reviewof the field of chemical dynamics.1 They stress “linkages between gas phase and surface chemical dynamics . . . a fruitful interplay of theory and experiment . . . which may often seem impenetrably complex and challenging.” Their review offers a sparkling table of contents with 48 entries, along with references to congenial articles and books, totaling 493 items. They worked withmultifaceted exuberance, intrepid questing, and zestful spirit. Back in 1955, molecular beam study of chemical dynamics was “a lunatic fringe.” However, a precious gem by Simplicius of Cilicia (490– 560) dating to even earlier times provided its vivid anticipation2:
三位杰出的物理化学家，Daniel Auerbach, John Tully和alecwodtke，对化学动力学领域进行了极好的评述他们强调“气相和表面化学动力学之间的联系……理论与实验卓有成效的相互作用……这可能看起来非常复杂和具有挑战性。”他们的评论提供了一个闪闪发光的目录，有48个条目，以及相关文章和书籍的参考，共计493项。他们以多方面的热情、无畏的探索和热情的精神工作。早在1955年，化学动力学的分子束研究是“极端的”。然而，基利西亚的辛普利西乌斯(490 - 560)的一颗宝石提供了它生动的预测，它可以追溯到更早的时代:
{"title":"Commentary: Chemical dynamics from the gas‐phase to surfaces","authors":"G. Ertl","doi":"10.1002/NTLS.10006","DOIUrl":"https://doi.org/10.1002/NTLS.10006","url":null,"abstract":"A trio of outstanding physical chemists, Daniel Auerbach, John Tully, andAlecWodtke, has produced a superb reviewof the field of chemical dynamics.1 They stress “linkages between gas phase and surface chemical dynamics . . . a fruitful interplay of theory and experiment . . . which may often seem impenetrably complex and challenging.” Their review offers a sparkling table of contents with 48 entries, along with references to congenial articles and books, totaling 493 items. They worked withmultifaceted exuberance, intrepid questing, and zestful spirit. Back in 1955, molecular beam study of chemical dynamics was “a lunatic fringe.” However, a precious gem by Simplicius of Cilicia (490– 560) dating to even earlier times provided its vivid anticipation2:","PeriodicalId":74244,"journal":{"name":"Natural sciences (Weinheim, Germany)","volume":"26 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74764342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Decision letter for \"A breakthrough from 60 years ago: “General nature of the genetic code for proteins” (1961)\"","authors":"Matthew Cobb","doi":"10.1002/NTLS.10018","DOIUrl":"https://doi.org/10.1002/NTLS.10018","url":null,"abstract":"","PeriodicalId":74244,"journal":{"name":"Natural sciences (Weinheim, Germany)","volume":"124 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80366417","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Disclosed: quasiparticle properties and dynamics in real and momentum spaceUrsula Wurstbauer
公开:实空间和动量空间中的准粒子性质和动力学
{"title":"Disclosed: quasiparticle properties and dynamics in real and momentum space","authors":"U. Wurstbauer","doi":"10.1002/NTLS.10017","DOIUrl":"https://doi.org/10.1002/NTLS.10017","url":null,"abstract":"Disclosed: quasiparticle properties and dynamics in real and momentum spaceUrsula Wurstbauer","PeriodicalId":74244,"journal":{"name":"Natural sciences (Weinheim, Germany)","volume":"114 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79008459","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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