Shao-Hua Zhuo, Tian-Yang Wang, Lang Zhao, Jing-Yun Su, Jin-Jian Hu, Yu-Fen Zhao, Yan-Mei Li
Novel pocket-independent STING-activating agonists (piSTINGs), which act through multivalency-driven oligomerization to activate downstream signalling pathways, were developed by Yan-Mei Li et al. in their Research Article (e202407037). piSTINGs could serve as novel STING agonists for vaccines and combination therapies. STING oligomerization is a useful strategy for the development of a new generation of STING agonists.
{"title":"Rücktitelbild: piSTING: A Pocket-Independent Agonist Based on Multivalency-Driven STING Oligomerization (Angew. Chem. 38/2024)","authors":"Shao-Hua Zhuo, Tian-Yang Wang, Lang Zhao, Jing-Yun Su, Jin-Jian Hu, Yu-Fen Zhao, Yan-Mei Li","doi":"10.1002/ange.202413960","DOIUrl":"https://doi.org/10.1002/ange.202413960","url":null,"abstract":"<p><b>Novel pocket-independent</b> STING-activating agonists (piSTINGs), which act through multivalency-driven oligomerization to activate downstream signalling pathways, were developed by Yan-Mei Li et al. in their Research Article (e202407037). piSTINGs could serve as novel STING agonists for vaccines and combination therapies. STING oligomerization is a useful strategy for the development of a new generation of STING agonists.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202413960","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142170175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuqing Yao, Wei Hao, Jin Tang, Kristin Kirschbaum, Christopher G. Gianopoulos, An Ren, Liang Ma, Letian Zheng, Hanying Li, Qi Li
A doping-induced kernel insertion in Cu(I) nanoclusters is reported by Qi Li et al. in their Research Article (e202407214). Its capability to create new types of copper-silver alloy nanoclusters with previously unreported structures, properties, and functionalities is uncovered. The as-obtained copper-silver nanocluster demonstrates high activity to initiate the photopolymerization of inorganic polymers in 3D laser microprinting.
{"title":"Rücktitelbild: Anomalous Structural Transformation of Cu(I) Clusters into Multifunctional CuAg Nanoclusters (Angew. Chem. 36/2024)","authors":"Yuqing Yao, Wei Hao, Jin Tang, Kristin Kirschbaum, Christopher G. Gianopoulos, An Ren, Liang Ma, Letian Zheng, Hanying Li, Qi Li","doi":"10.1002/ange.202414134","DOIUrl":"https://doi.org/10.1002/ange.202414134","url":null,"abstract":"<p><b>A doping-induced kernel insertion</b> in Cu(I) nanoclusters is reported by Qi Li et al. in their Research Article (e202407214). Its capability to create new types of copper-silver alloy nanoclusters with previously unreported structures, properties, and functionalities is uncovered. The as-obtained copper-silver nanocluster demonstrates high activity to initiate the photopolymerization of inorganic polymers in 3D laser microprinting.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202414134","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142077837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We inadvertently omitted an NSF grant acknowledgment. We regret this omission and wish to make a correction to the Acknowledgments by adding the following statement:
“L.Y. and T.J.M. acknowledge partial support of the work provided by NSF-CHE-2247666.”
{"title":"Berichtigung: Correction to “Redesigned Nylon-6 Variants with Enhanced Recyclability, Ductility, and Transparency”","authors":"","doi":"10.1002/ange.202413645","DOIUrl":"https://doi.org/10.1002/ange.202413645","url":null,"abstract":"<p>We inadvertently omitted an NSF grant acknowledgment. We regret this omission and wish to make a correction to the Acknowledgments by adding the following statement:</p><p>“L.Y. and T.J.M. acknowledge partial support of the work provided by NSF-CHE-2247666.”</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202413645","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142123263","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rafia Siddiqui, Sergi Burguera, María de las Nieves Piña, Swati Dhamija, Dr. Hatem M. Titi, Antonio Frontera, Antonio Bauzá, Dr. Ranjan Patra
In the outer space , the π-hole nature of several metalated porphyrins is exploited to form noncovalent Br⋅⋅⋅M interactions (M = Co2+, Ni2+, Cu2+ and Zn2+). In the cover image, a dragon uses its nest as a template to assemble the metal ion into the porphyrin's core, interacting with it using the orbs located on the head and tail. In their Research Article (e202409963), Antonio Bauzá, Ranjan Patra et al. report novel metalated porphyrins, including a computational analysis of the interactions undertaken in the solid state.
{"title":"Innenrücktitelbild: From Coordination to π-Hole Chemistry of Transition Metals: Metalloporphyrins as a Case of Study (Angew. Chem. 38/2024)","authors":"Rafia Siddiqui, Sergi Burguera, María de las Nieves Piña, Swati Dhamija, Dr. Hatem M. Titi, Antonio Frontera, Antonio Bauzá, Dr. Ranjan Patra","doi":"10.1002/ange.202413867","DOIUrl":"https://doi.org/10.1002/ange.202413867","url":null,"abstract":"<p><b>In the outer space</b> , the π-hole nature of several metalated porphyrins is exploited to form noncovalent Br⋅⋅⋅M interactions (M = Co<sup>2+</sup>, Ni<sup>2+</sup>, Cu<sup>2+</sup> and Zn<sup>2+</sup>). In the cover image, a dragon uses its nest as a template to assemble the metal ion into the porphyrin's core, interacting with it using the orbs located on the head and tail. In their Research Article (e202409963), Antonio Bauzá, Ranjan Patra et al. report novel metalated porphyrins, including a computational analysis of the interactions undertaken in the solid state.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202413867","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142170174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiangyang Zhang, Buyue Zhang, Ying Zhang, Yinghao Ding, Zhenghao Zhang, Prof. Qian Liu, Prof. Zhimou Yang, Prof. Ling Wang, Prof. Jie Gao
The immunosuppressive tumor microenvironment leads to insufficient infiltration of effector lymphocytes, significantly weakening the anti-tumor immune response and promoting the tumor to become “cold”. In the cover image, tumor cells are representend as icebergs, with organelles as ice blocks floating on the ice surface. The copper peptide nanoparticles are meteorites falling from the sky, attacking multiple organelles. The ice begins to melt, symbolizing the elicited multiple cell death pathways, and also indicating the transformation of cold tumors into hot tumors, as illustrated by Ling Wang, Jie Gao et al. in their Research Article (e202406602).
{"title":"Rücktitelbild: Copper-Induced Supramolecular Peptide Assemblies for Multi-Pathway Cell Death and Tumor Inhibition (Angew. Chem. 34/2024)","authors":"Xiangyang Zhang, Buyue Zhang, Ying Zhang, Yinghao Ding, Zhenghao Zhang, Prof. Qian Liu, Prof. Zhimou Yang, Prof. Ling Wang, Prof. Jie Gao","doi":"10.1002/ange.202413964","DOIUrl":"https://doi.org/10.1002/ange.202413964","url":null,"abstract":"<p><b>The immunosuppressive tumor microenvironment</b> leads to insufficient infiltration of effector lymphocytes, significantly weakening the anti-tumor immune response and promoting the tumor to become “cold”. In the cover image, tumor cells are representend as icebergs, with organelles as ice blocks floating on the ice surface. The copper peptide nanoparticles are meteorites falling from the sky, attacking multiple organelles. The ice begins to melt, symbolizing the elicited multiple cell death pathways, and also indicating the transformation of cold tumors into hot tumors, as illustrated by Ling Wang, Jie Gao et al. in their Research Article (e202406602).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202413964","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141966751","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wu Sun, Dr. Junyu Hou, Prof. Yunlei Zhou, Tianke Zhu, Qunyao Yuan, Dr. Shaolei Wang, Dr. Farid Manshaii, Changsheng Song, Xingyu Lei, Xiaoyan Wu, Hern Kim, Prof. Yi Yu, Prof. Chuanxiao Xiao, Prof. Hongjun Zhang, Prof. Yun Song, Dalin Sun, Dr. Binbin Jia, Prof. Guangmin Zhou, Jie Zhao
A novel amorphous FeSnOx nanosheet with hierarchical defects, including abundant oxygen vacancies and nano-sized perforations, that can be assembled into a multifunctional layer overlaying commercial separators for room-temperature sodium-sulfur batteries was developed on the Research Article (e202404816) by Junyu Hou, Binbin Jia, Guangmin Zhou, Jie Zhao et al. The oxygen vacancies offer strong adsorption and abundant catalytic sites for polysulfides, while the nano-sized perforations facilitate the regulation of Na-ion transport.
{"title":"Innentitelbild: Amorphous FeSnOx Nanosheets with Hierarchical Vacancies for Room-Temperature Sodium-Sulfur Batteries (Angew. Chem. 38/2024)","authors":"Wu Sun, Dr. Junyu Hou, Prof. Yunlei Zhou, Tianke Zhu, Qunyao Yuan, Dr. Shaolei Wang, Dr. Farid Manshaii, Changsheng Song, Xingyu Lei, Xiaoyan Wu, Hern Kim, Prof. Yi Yu, Prof. Chuanxiao Xiao, Prof. Hongjun Zhang, Prof. Yun Song, Dalin Sun, Dr. Binbin Jia, Prof. Guangmin Zhou, Jie Zhao","doi":"10.1002/ange.202413968","DOIUrl":"https://doi.org/10.1002/ange.202413968","url":null,"abstract":"<p><b>A novel amorphous FeSnOx nanosheet</b> with hierarchical defects, including abundant oxygen vacancies and nano-sized perforations, that can be assembled into a multifunctional layer overlaying commercial separators for room-temperature sodium-sulfur batteries was developed on the Research Article (e202404816) by Junyu Hou, Binbin Jia, Guangmin Zhou, Jie Zhao et al. The oxygen vacancies offer strong adsorption and abundant catalytic sites for polysulfides, while the nano-sized perforations facilitate the regulation of Na-ion transport.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202413968","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142169850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
“The most important future applications of my research are related to the production, use, and storage of renewable fuels… I advise my students to carry out ‘Friday afternoon experiments’ that may not be 100% aligned with their main project but are curiosity-driven experiments with potential to lead to something new…” Find out more about Daniel Esposito in his Introducing… Profile.
{"title":"Daniel Esposito","authors":"","doi":"10.1002/ange.202412391","DOIUrl":"https://doi.org/10.1002/ange.202412391","url":null,"abstract":"<p><i>“The most important future applications of my research are related to the production, use, and storage of renewable fuels… I advise my students to carry out ‘Friday afternoon experiments’ that may not be 100% aligned with their main project but are curiosity-driven experiments with potential to lead to something new…”</i> Find out more about Daniel Esposito in his Introducing… Profile.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202412391","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142123342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shufan Wu, Dr. Philip M. Stanley, Simon N. Deger, Dr. Mian Zahid Hussain, Prof. Dr. Andreas Jentys, Dr. Julien Warnan
<p>Angesichts des weltweit steigenden Energiebedarfs ist eine effiziente Energiesammlung, -speicherung und -nutzung von entscheidender Bedeutung für die Weiterentwicklung der Gesellschaft geworden.<span><sup>1</sup></span> Daher steht das Sonnenlicht als unerschöpfliche, saubere Energiequelle weiterhin im Mittelpunkt der Energieforschung, insbesondere die effiziente Umwandlung in direkt nutzbare und speicherbare Energien.<span><sup>2</sup></span> In der Natur wird die Speicherung von Sonnenenergie mit der Photosynthese ermöglicht, die es Pflanzen, Algen und Cyanobakterien erlaubt, die absorbierte Sonnenenergie unabhängig vom Licht in Chemikalien umzuwandeln. Der Einbau einer solchen Flexibilität in künstlichen Elektrosystemen könnte die entkoppelte Nutzung der Sonnenenergie und die Erzeugung von Kraftstoffen oder die langfristige Speicherung von Elektronen ermöglichen. Auf diese Weise könnten mehrere elektrosynthetische Schritte und die Speicherung chemischer Kraftstoffe vermieden werden, während gleichzeitig die Form des Energieträgers und der zeitliche Bedarf flexibel sind.<span><sup>3</sup></span> In diesem Zusammenhang ist die Weiterentwicklung von Materialien, die sowohl Sonnenenergie gewinnen als auch Elektronen speichern können, von entscheidender Bedeutung, auch wenn sie sich noch im Anfangsstadium befinden.<span><sup>4</sup></span> Polyoxometallat-, Kohlenstoffnitrid- und Metalloxid-Materialien haben bereits ihr Potenzial als aufladbare, netzunabhängige, drahtlose kolloidale Systeme unter Beweis gestellt, jedoch sind weitere Anstrengungen zur Erweiterung der Materialpalette und zur Verbesserung der Gesamtleistung von entscheidender Bedeutung.<span><sup>5</sup></span></p><p>Metall-organische Gerüstverbindungen (MOFs), die aus organischen Liganden und Metallknoten bestehen, bieten ideale Plattformen zur Entwicklung von Energieanwendungen aufgrund ihrer Kristallinität, Porosität und anpassbaren dreidimensionalen Strukturen.<span><sup>6</sup></span> Vielversprechende Beispiele für die lichtinduzierte Elektronenspeicherung umfassen Ti-basierte MIL-125 und MOF-253, die mit Lehn-ähnlichen Re-Komplexen an den Linkern modifiziert sind. Diese ermöglichen dann durch Lichtabsorption, die Oxidation eines Elektronendonors (SED) und die daraus folgende Elektronenakkumulation innerhalb des Gerüsts, um diese später in der Dunkelphotokatalyse zu verwenden.<span><sup>7</sup></span> Trotz dieser jüngsten Fortschritte unterstreichen die begrenzte Zugänglichkeit zu den elektroaktiven Stellen, die geringe Absorption von sichtbarem Licht sowie die geringe Stabilität die Notwendigkeit weiterer Anstrengungen.</p><p>Hier stellen wir <b>MnBr-253</b> als ein photoaufladbares Hybridmaterial ohne seltene Metalle vor, das aus Al-Metallknoten, Bipyridin-Linkern und <i>fac</i>-[MnBr(CO)<sub>3</sub>(dcbpy)] (dcbpy=5,5’-Dicarbonsäure-2,2′-Bipyridin) Komplexen (Abbildung 1) besteht. Mn-2,2′-Bipyridyl (bpy) Tricarbonyl Halogenid (X) Komplexe bilden eine vielseitige Familie v
{"title":"Durch Licht Aufladbare Mn-Basierte Metall-Organische Gerüstverbindungen und Davon Entkoppelte Photokatalyse","authors":"Shufan Wu, Dr. Philip M. Stanley, Simon N. Deger, Dr. Mian Zahid Hussain, Prof. Dr. Andreas Jentys, Dr. Julien Warnan","doi":"10.1002/ange.202406385","DOIUrl":"https://doi.org/10.1002/ange.202406385","url":null,"abstract":"<p>Angesichts des weltweit steigenden Energiebedarfs ist eine effiziente Energiesammlung, -speicherung und -nutzung von entscheidender Bedeutung für die Weiterentwicklung der Gesellschaft geworden.<span><sup>1</sup></span> Daher steht das Sonnenlicht als unerschöpfliche, saubere Energiequelle weiterhin im Mittelpunkt der Energieforschung, insbesondere die effiziente Umwandlung in direkt nutzbare und speicherbare Energien.<span><sup>2</sup></span> In der Natur wird die Speicherung von Sonnenenergie mit der Photosynthese ermöglicht, die es Pflanzen, Algen und Cyanobakterien erlaubt, die absorbierte Sonnenenergie unabhängig vom Licht in Chemikalien umzuwandeln. Der Einbau einer solchen Flexibilität in künstlichen Elektrosystemen könnte die entkoppelte Nutzung der Sonnenenergie und die Erzeugung von Kraftstoffen oder die langfristige Speicherung von Elektronen ermöglichen. Auf diese Weise könnten mehrere elektrosynthetische Schritte und die Speicherung chemischer Kraftstoffe vermieden werden, während gleichzeitig die Form des Energieträgers und der zeitliche Bedarf flexibel sind.<span><sup>3</sup></span> In diesem Zusammenhang ist die Weiterentwicklung von Materialien, die sowohl Sonnenenergie gewinnen als auch Elektronen speichern können, von entscheidender Bedeutung, auch wenn sie sich noch im Anfangsstadium befinden.<span><sup>4</sup></span> Polyoxometallat-, Kohlenstoffnitrid- und Metalloxid-Materialien haben bereits ihr Potenzial als aufladbare, netzunabhängige, drahtlose kolloidale Systeme unter Beweis gestellt, jedoch sind weitere Anstrengungen zur Erweiterung der Materialpalette und zur Verbesserung der Gesamtleistung von entscheidender Bedeutung.<span><sup>5</sup></span></p><p>Metall-organische Gerüstverbindungen (MOFs), die aus organischen Liganden und Metallknoten bestehen, bieten ideale Plattformen zur Entwicklung von Energieanwendungen aufgrund ihrer Kristallinität, Porosität und anpassbaren dreidimensionalen Strukturen.<span><sup>6</sup></span> Vielversprechende Beispiele für die lichtinduzierte Elektronenspeicherung umfassen Ti-basierte MIL-125 und MOF-253, die mit Lehn-ähnlichen Re-Komplexen an den Linkern modifiziert sind. Diese ermöglichen dann durch Lichtabsorption, die Oxidation eines Elektronendonors (SED) und die daraus folgende Elektronenakkumulation innerhalb des Gerüsts, um diese später in der Dunkelphotokatalyse zu verwenden.<span><sup>7</sup></span> Trotz dieser jüngsten Fortschritte unterstreichen die begrenzte Zugänglichkeit zu den elektroaktiven Stellen, die geringe Absorption von sichtbarem Licht sowie die geringe Stabilität die Notwendigkeit weiterer Anstrengungen.</p><p>Hier stellen wir <b>MnBr-253</b> als ein photoaufladbares Hybridmaterial ohne seltene Metalle vor, das aus Al-Metallknoten, Bipyridin-Linkern und <i>fac</i>-[MnBr(CO)<sub>3</sub>(dcbpy)] (dcbpy=5,5’-Dicarbonsäure-2,2′-Bipyridin) Komplexen (Abbildung 1) besteht. Mn-2,2′-Bipyridyl (bpy) Tricarbonyl Halogenid (X) Komplexe bilden eine vielseitige Familie v","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202406385","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142123408","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Norbert Varga, M. Smieško, Xiaohua Jiang, R. Jakob, Beatrice Wagner, Tobias Mühlethaler, P. Dätwyler, P. Zihlmann, S. Rabbani, Tim Maier, O. Schwardt, Beat Ernst
In this research article, we report on the strengthening of a non-classical hydrogen bond (C-H···O) by introducing electron withdrawing groups at the carbon atom. The approach is demonstrated on the example of derivatives of the physiological E-selectin ligand sialyl Lewisx (1, sLex). Its affinity is mainly due to a beneficial entropy term, which is predominantly caused by the pre-organization of sLex in its binding conformation. We have shown, that among the elements responsible for the pre-organization, the stabilization by a non-classical hydrogen bond between the H-C5 of l-fucose and the ring oxygen O5 of the neighboring d-galactose moiety is essential and yields 7.4 kJ mol-1. This effect could be further strengthened by replacing l-fucose by 6,6,6-trifluoro-l-fucose leading to an improved non-classical H-bond of 14.9 kJ mol-1, i.e., an improved pre-organization in the bioactive conformation. For a series of glycomimetics of sLex (1), this outcome could be confirmed by high field NMR-shifts of the H-C5Fuc, by X-ray diffraction analysis of glycomimetics co-crystallized with E-selectin as well as by isothermal titration calorimetry. Furthermore, the electron-withdrawing character of the CF3-group beneficially influences the pharmacokinetic properties of sLex mimetics. Thus, acid-stability a prerequisite for gastrointestinal stability could be substantially improved.
{"title":"Strengthening an Intramolecular Non-Classical Hydrogen Bond to Get in Shape for Binding.","authors":"Norbert Varga, M. Smieško, Xiaohua Jiang, R. Jakob, Beatrice Wagner, Tobias Mühlethaler, P. Dätwyler, P. Zihlmann, S. Rabbani, Tim Maier, O. Schwardt, Beat Ernst","doi":"10.1002/ange.202406024","DOIUrl":"https://doi.org/10.1002/ange.202406024","url":null,"abstract":"In this research article, we report on the strengthening of a non-classical hydrogen bond (C-H···O) by introducing electron withdrawing groups at the carbon atom. The approach is demonstrated on the example of derivatives of the physiological E-selectin ligand sialyl Lewisx (1, sLex). Its affinity is mainly due to a beneficial entropy term, which is predominantly caused by the pre-organization of sLex in its binding conformation. We have shown, that among the elements responsible for the pre-organization, the stabilization by a non-classical hydrogen bond between the H-C5 of l-fucose and the ring oxygen O5 of the neighboring d-galactose moiety is essential and yields 7.4 kJ mol-1. This effect could be further strengthened by replacing l-fucose by 6,6,6-trifluoro-l-fucose leading to an improved non-classical H-bond of 14.9 kJ mol-1, i.e., an improved pre-organization in the bioactive conformation. For a series of glycomimetics of sLex (1), this outcome could be confirmed by high field NMR-shifts of the H-C5Fuc, by X-ray diffraction analysis of glycomimetics co-crystallized with E-selectin as well as by isothermal titration calorimetry. Furthermore, the electron-withdrawing character of the CF3-group beneficially influences the pharmacokinetic properties of sLex mimetics. Thus, acid-stability a prerequisite for gastrointestinal stability could be substantially improved.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141797292","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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