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An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties.
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-16 DOI: 10.1002/anie.202422702
Richard Rudolf, Andrej Todorovski, Vera Lederer, Nicolas I. Neuman, Hartmut Schubert, Biprajit Sarkar
Neutral mesoionic carbenes (MICs) based on a 1,2,3‐triazole core have had a strong impact on various branches of chemistry such as homogeneous catalysis, electrocatalysis, and photochemistry/photophysics. We present here the first general synthesis of anionic mesoionic carbenes (anMICs) based on a 1,2,3‐triazole core and a borate backbone. The free anMIC is stable in solution under an inert atmosphere at low temperatures, and can be stored for several weeks. Analysis of donor properties shows that these anMICs are extremely strong σ‐donors, bypassing the donor properties of strong donors such as MICs, NHCs, anionic NHCs and N‐heterocyclic olefins. The room temperature conversion of the free anMICs leads to three equally interesting compound classes: an amide‐coordinated borane based on a MIC‐borane backbone, a polymeric triazolide and an amide‐coordinated metallo‐MIC‐borane. The metallo‐MIC‐borane is an interesting precursor for the synthesis of further amide‐coordinated MIC‐borane compounds. Quantum chemical calculations have been used to elucidate the mechanism of transformation of the anMICs. Gold(I) complexes of the anMIC ligands are potent catalysts for the hydroamination of alkynes without the need for any additional reagents. We thus introduce three new categories of mesoionic compounds here with potential for different branches of chemistry and beyond.
{"title":"An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties.","authors":"Richard Rudolf, Andrej Todorovski, Vera Lederer, Nicolas I. Neuman, Hartmut Schubert, Biprajit Sarkar","doi":"10.1002/anie.202422702","DOIUrl":"https://doi.org/10.1002/anie.202422702","url":null,"abstract":"Neutral mesoionic carbenes (MICs) based on a 1,2,3‐triazole core have had a strong impact on various branches of chemistry such as homogeneous catalysis, electrocatalysis, and photochemistry/photophysics. We present here the first general synthesis of anionic mesoionic carbenes (anMICs) based on a 1,2,3‐triazole core and a borate backbone. The free anMIC is stable in solution under an inert atmosphere at low temperatures, and can be stored for several weeks. Analysis of donor properties shows that these anMICs are extremely strong σ‐donors, bypassing the donor properties of strong donors such as MICs, NHCs, anionic NHCs and N‐heterocyclic olefins. The room temperature conversion of the free anMICs leads to three equally interesting compound classes: an amide‐coordinated borane based on a MIC‐borane backbone, a polymeric triazolide and an amide‐coordinated metallo‐MIC‐borane. The metallo‐MIC‐borane is an interesting precursor for the synthesis of further amide‐coordinated MIC‐borane compounds. Quantum chemical calculations have been used to elucidate the mechanism of transformation of the anMICs. Gold(I) complexes of the anMIC ligands are potent catalysts for the hydroamination of alkynes without the need for any additional reagents. We thus introduce three new categories of mesoionic compounds here with potential for different branches of chemistry and beyond.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"74 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986158","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}
引用次数: 0
Accelerating Tumor Immunotherapy Through a Synergistic Strategy of Increasing Throttle and Relaxing Brake
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-16 DOI: 10.1002/anie.202422502
Binbin Ding, Jing Li, Jia Tan, Hao Chen, Pan Zheng, Ping’an Ma, Jun Lin
Tumor immunotherapy has been widely used clinically, but it is still hindered by weak antitumor immunity and immunosuppressive tumor microenvironment (TME). Here, a kind of simple disodium hydrogen phosphate nanoparticle (Na2HPO4 NP) is prepared to "accelerate" tumor immunotherapy by "increasing throttle" and "relaxing brake" simultaneously. The obtained Na2HPO4 NPs release a large amount of Na+ and HPO42‐ ions within tumor cells, thereby activating the caspase 1/GSDMD‐mediated pyroptosis pathway to achieve immune activation. Meanwhile, alkalescent Na2HPO4 NPs can further consume lactic acid through acid‐base neutralization, and regulate adenosine (Ado) metabolism via nanomaterial‐induced biocatalytic process to relieve two‐tier immunosuppression. Collectively, Na2HPO4 NPs effectively activate the antitumor immune process in vivo, and dramatically inhibit primary and distal tumor growth. This work will provide unique inspiration and strategy for the regulation of both positive and negative directions in immunotherapy.
{"title":"Accelerating Tumor Immunotherapy Through a Synergistic Strategy of Increasing Throttle and Relaxing Brake","authors":"Binbin Ding, Jing Li, Jia Tan, Hao Chen, Pan Zheng, Ping’an Ma, Jun Lin","doi":"10.1002/anie.202422502","DOIUrl":"https://doi.org/10.1002/anie.202422502","url":null,"abstract":"Tumor immunotherapy has been widely used clinically, but it is still hindered by weak antitumor immunity and immunosuppressive tumor microenvironment (TME). Here, a kind of simple disodium hydrogen phosphate nanoparticle (Na2HPO4 NP) is prepared to \"accelerate\" tumor immunotherapy by \"increasing throttle\" and \"relaxing brake\" simultaneously. The obtained Na2HPO4 NPs release a large amount of Na+ and HPO42‐ ions within tumor cells, thereby activating the caspase 1/GSDMD‐mediated pyroptosis pathway to achieve immune activation. Meanwhile, alkalescent Na2HPO4 NPs can further consume lactic acid through acid‐base neutralization, and regulate adenosine (Ado) metabolism via nanomaterial‐induced biocatalytic process to relieve two‐tier immunosuppression. Collectively, Na2HPO4 NPs effectively activate the antitumor immune process in vivo, and dramatically inhibit primary and distal tumor growth. This work will provide unique inspiration and strategy for the regulation of both positive and negative directions in immunotherapy.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"23 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986165","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}
引用次数: 0
Elemental Germanium Activation and Catalysis Enabled by Mechanical Force
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-16 DOI: 10.1002/anie.202421446
Guangqing Guo, Jie Zhou, Xiaochun He, Na Li, Nan Lin, Xuemei Zhang, Zhong Lian
In the realm of materials science and chemical industry, germanium emerges as a strategic resource with distinctive properties that extend its applicability beyond traditional electronics and optics into the promising field of chemical catalysis. Despite its significant role in advanced technological applications, the potential of elemental germanium as a catalyst remains unexplored. Leveraging recent developments in mechanochemistry, this study introduces a groundbreaking approach to activate elemental germanium via mechanical force, facilitating the Reformatsky reaction without the reliance on external reducing agents. Meanwhile, we have also demonstrated, for the first time, the catalytic activity of elemental germanium, successfully achieving this through the bromoalkylation of alkenes. These achievements mark a significant advancement in the field of catalysis and open up a new promising avenue for both academic research and industrial applications.
{"title":"Elemental Germanium Activation and Catalysis Enabled by Mechanical Force","authors":"Guangqing Guo, Jie Zhou, Xiaochun He, Na Li, Nan Lin, Xuemei Zhang, Zhong Lian","doi":"10.1002/anie.202421446","DOIUrl":"https://doi.org/10.1002/anie.202421446","url":null,"abstract":"In the realm of materials science and chemical industry, germanium emerges as a strategic resource with distinctive properties that extend its applicability beyond traditional electronics and optics into the promising field of chemical catalysis. Despite its significant role in advanced technological applications, the potential of elemental germanium as a catalyst remains unexplored. Leveraging recent developments in mechanochemistry, this study introduces a groundbreaking approach to activate elemental germanium via mechanical force, facilitating the Reformatsky reaction without the reliance on external reducing agents. Meanwhile, we have also demonstrated, for the first time, the catalytic activity of elemental germanium, successfully achieving this through the bromoalkylation of alkenes. These achievements mark a significant advancement in the field of catalysis and open up a new promising avenue for both academic research and industrial applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"172 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987173","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}
引用次数: 0
Light-induced Enhancement of Energetic Charge Carrier Extraction and Modulation of Local Charge Density to Impact Selectivity in Plasmonic Nanometals
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1002/anie.202422034
Yanjun Liu, Xingyue He, Xiao Liu, Bo Li, Jian-Gong Ma, Peng Cheng
Localized surface plasmon resonance (LSPR) metals exhibit remarkable light-absorbing property and unique catalytic activity, attracting significant attention in photocatalysts recently. However, the practical application of plasmonic nanometal is hindered by challenge of energetic electrons extraction and low selectivity. The energetic carriers generated in nanometal under illumination have extremely short lifetimes, leading to rapid energy loss. In this work, silver nanometals modified with five distinct sulfhydryl ligands (re-Ag-S-R) were synthesized via photoreduction of superlattice precursors. Modified surface efficiently extracts and preserves excited state electrons of plasmonic nanometals. By modulation the local charge density at catalytic active sites through substituents with varying electron-donating and electron-withdrawing properties, the selectivity of the photocatalytic carbon dioxide reduction reaction and hydrogen evolution reaction was influenced. The results demonstrated opposite selectivity between methoxy-modified re-Ag-S-OCH3 (CO selectivity of 96.73%) and amino-modified re-Ag-S-NH2 (H2 selectivity of 96.66%) despite their similar structures. The changes in excited states and surface contact potentials induced by LSPR were monitored using femtosecond transient absorption (fs-TA) spectroscopy and Kelvin probe force microscopy (KPFM). Meanwhile, the detailed discussion of the LSPR mechanism in plasmonic nanometals will serve as valuable references and foundational elements for future research in this area.
{"title":"Light-induced Enhancement of Energetic Charge Carrier Extraction and Modulation of Local Charge Density to Impact Selectivity in Plasmonic Nanometals","authors":"Yanjun Liu, Xingyue He, Xiao Liu, Bo Li, Jian-Gong Ma, Peng Cheng","doi":"10.1002/anie.202422034","DOIUrl":"https://doi.org/10.1002/anie.202422034","url":null,"abstract":"Localized surface plasmon resonance (LSPR) metals exhibit remarkable light-absorbing property and unique catalytic activity, attracting significant attention in photocatalysts recently. However, the practical application of plasmonic nanometal is hindered by challenge of energetic electrons extraction and low selectivity. The energetic carriers generated in nanometal under illumination have extremely short lifetimes, leading to rapid energy loss. In this work, silver nanometals modified with five distinct sulfhydryl ligands (re-Ag-S-R) were synthesized via photoreduction of superlattice precursors. Modified surface efficiently extracts and preserves excited state electrons of plasmonic nanometals. By modulation the local charge density at catalytic active sites through substituents with varying electron-donating and electron-withdrawing properties, the selectivity of the photocatalytic carbon dioxide reduction reaction and hydrogen evolution reaction was influenced. The results demonstrated opposite selectivity between methoxy-modified re-Ag-S-OCH3 (CO selectivity of 96.73%) and amino-modified re-Ag-S-NH2 (H2 selectivity of 96.66%) despite their similar structures. The changes in excited states and surface contact potentials induced by LSPR were monitored using femtosecond transient absorption (fs-TA) spectroscopy and Kelvin probe force microscopy (KPFM). Meanwhile, the detailed discussion of the LSPR mechanism in plasmonic nanometals will serve as valuable references and foundational elements for future research in this area.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"131 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987076","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}
引用次数: 0
Retrieving the Stability and Practical Performance of Activation-Unstable Mesoporous Zr(IV)-MOF for Highly Efficient Self-Calibrating Acidity Sensing
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1002/anie.202422517
Feifan Lang, Lulu Zhang, Yang Li, Xiao-Juan Xi, Jiandong Pang, Wenjun Zheng, Hong-Cai Zhou, Xian-He Bu
The practical applications of activation-unstable mesoporous metal-organic frameworks (MOFs) are often constrained by their structural instability. However, enhancing their stability could unlock valuable functionalities. Herein, we stabilized the otherwise unstable, post-activated structure of a novel mesoporous Zr(IV)-MOF, NKM-809, which uses a pyridine-containing amphiprotic linker (PPTB). We applied two strategies: mixed-linker synthesis and linker installation. In the mixed-linker approach, we incorporated an auxiliary linker, TPTB, which resembles PPTB, during synthesis to improve the framework's stability. In the linker installation approach, we introduced a ditopic carboxylate linker (BPDC) into the coordination-unsaturated sites of NKM-809. These strategies produced stabilized derivatives, named NKM-808.X (X = χPPTB) and NKM-809-BPDC, which exhibit pH-responsive dual-wavelength fluorescence at distinct emission wavelengths. Remarkably, these emissions shift oppositely upon protonation and dissociation, distinguishing them as highly sensitive, self-calibrating acidity sensors. In NKM-809-BPDC, an additional quenching of the linker-emission (419 nm) minimizes inherent interference, enabling integrated quality and lifespan self-monitoring. Theoretical calculations identified transitions between (n, π*) and (π, π*) emission states during the sensing process and highlighted the role of a stable mesoporous network in achieving stronger protonation response. These findings showcase the potential of stabilized mesoporous MOFs for practical applications, alongside valuable insights into strategies for optimizing such materials.
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引用次数: 0
Interfacial Water Orientation in Neutral Oxygen Catalysis for Reversible Ampere-scale Zinc-air Batteries
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1002/anie.202421640
yixin hao, Luqi Wang, Hongjiao Huang, Hao Zhou, Gengyu Xing, Dongxiao Ji, Tianran Zhang, Aoming Huang, Ai-Yin Wang, Xiang-Rong Chen, Tsung-Yi Chen, Han-Yi Chen, Seeram Ramakrishna, Shengjie Peng
The neutral oxygen catalysis is an electrochemical reaction of the utmost importance in energy generation, storage application, and chemical synthesis. However, the restricted availability of protons poses a challenge to achieving kinetically favorable oxygen catalytic reactions. Here, we alter the interfacial water orientation by adjusting the Brønsted acidity at the catalyst surface, to break the proton transfer limitation of neutral oxygen electrocatalysis. An unexpected role of water molecules in improving the activity of neutral oxygen catalysis is revealed, namely, increasing the H-down configuration water in electric double layers rather than merely affecting the energy barriers for reaction limiting steps. The proposed porous nanofibers with atomically dispersed MnN3 exhibit record-breaking activity (EORR@1/2/EOER@10 mA = 0.85/1.65 V vs. RHE) and reversibility (2500 h), outperforming all previously reported neutral catalysts and rivaling conventional alkaline systems. In particular, practical ampere-scale zinc-air batteries (ZABs) stack are constructed with a capacity of 5.93 Ah and can stably operate under 1.0 A and 1.0 Ah conditions, demonstrating broad application prospects. This work provides a novel and feasible perspective for designing neutral oxygen electrocatalysts and reveals the future commercial potential in mobile power supply and large-scale energy storage.
{"title":"Interfacial Water Orientation in Neutral Oxygen Catalysis for Reversible Ampere-scale Zinc-air Batteries","authors":"yixin hao, Luqi Wang, Hongjiao Huang, Hao Zhou, Gengyu Xing, Dongxiao Ji, Tianran Zhang, Aoming Huang, Ai-Yin Wang, Xiang-Rong Chen, Tsung-Yi Chen, Han-Yi Chen, Seeram Ramakrishna, Shengjie Peng","doi":"10.1002/anie.202421640","DOIUrl":"https://doi.org/10.1002/anie.202421640","url":null,"abstract":"The neutral oxygen catalysis is an electrochemical reaction of the utmost importance in energy generation, storage application, and chemical synthesis. However, the restricted availability of protons poses a challenge to achieving kinetically favorable oxygen catalytic reactions. Here, we alter the interfacial water orientation by adjusting the Brønsted acidity at the catalyst surface, to break the proton transfer limitation of neutral oxygen electrocatalysis. An unexpected role of water molecules in improving the activity of neutral oxygen catalysis is revealed, namely, increasing the H-down configuration water in electric double layers rather than merely affecting the energy barriers for reaction limiting steps. The proposed porous nanofibers with atomically dispersed MnN3 exhibit record-breaking activity (EORR@1/2/EOER@10 mA = 0.85/1.65 V vs. RHE) and reversibility (2500 h), outperforming all previously reported neutral catalysts and rivaling conventional alkaline systems. In particular, practical ampere-scale zinc-air batteries (ZABs) stack are constructed with a capacity of 5.93 Ah and can stably operate under 1.0 A and 1.0 Ah conditions, demonstrating broad application prospects. This work provides a novel and feasible perspective for designing neutral oxygen electrocatalysts and reveals the future commercial potential in mobile power supply and large-scale energy storage.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"36 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981790","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}
引用次数: 0
Semirational Protein Engineering of a Decarboxylative Aldolase for Regiodivergent and Stereodivergent Synthesis of Cyclic Imino Acids
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1002/anie.202500080
Yuqiu Lan, Chenghua Zhang, Chunping Tang, Yang Ye, Rui Zhang, Xiang Sheng, Cangsong Liao
Aldolases are powerful C−C bond-forming enzymes for asymmetric organic synthesis because of their supreme stereoselectivity, diverse electrophiles and nucleophiles, and promising scalability. Stereodivergent engineering of aldolases to tune the selectivity for the synthesis of stereoisomers of chiral molecules is highly desirable but has rarely been reported. This study documented the semirational engineering of the decarboxylative aldolase UstD with the focused rational iterative site-specific mutagenesis (FRISM) strategy to perform a C−C bond-forming reaction with dione electrophiles. The variant obtained from a small mutant library showed divergent regioselectivity and diastereoselectivity to the wild-type enzyme, which resulted in the production of thirty cyclic imino acids with stereocenters at the α and γ positions. Molecular dynamics simulation and kinetic data revealed the basis of selectivity.
醛醇酶是用于不对称有机合成的强大的 C-C 键形成酶,因为它们具有极高的立体选择性、多种亲电体和亲核体以及良好的可扩展性。利用醛缩酶的立体异构工程来调整手性分子立体异构体合成的选择性是非常理想的,但却鲜有报道。本研究记录了利用聚焦理性迭代位点特异性诱变(FRISM)策略对脱羧醛缩酶 UstD 进行的半手性工程,以实现与二酮亲电物的 C-C 键形成反应。从一个小型突变体库中获得的变体显示出与野生型酶不同的区域选择性和非对映选择性,从而产生了 30 个在α和γ位置具有立体中心的环状亚胺酸。分子动力学模拟和动力学数据揭示了选择性的基础。
{"title":"Semirational Protein Engineering of a Decarboxylative Aldolase for Regiodivergent and Stereodivergent Synthesis of Cyclic Imino Acids","authors":"Yuqiu Lan, Chenghua Zhang, Chunping Tang, Yang Ye, Rui Zhang, Xiang Sheng, Cangsong Liao","doi":"10.1002/anie.202500080","DOIUrl":"https://doi.org/10.1002/anie.202500080","url":null,"abstract":"Aldolases are powerful C−C bond-forming enzymes for asymmetric organic synthesis because of their supreme stereoselectivity, diverse electrophiles and nucleophiles, and promising scalability. Stereodivergent engineering of aldolases to tune the selectivity for the synthesis of stereoisomers of chiral molecules is highly desirable but has rarely been reported. This study documented the semirational engineering of the decarboxylative aldolase UstD with the focused rational iterative site-specific mutagenesis (FRISM) strategy to perform a C−C bond-forming reaction with dione electrophiles. The variant obtained from a small mutant library showed divergent regioselectivity and diastereoselectivity to the wild-type enzyme, which resulted in the production of thirty cyclic imino acids with stereocenters at the α and γ positions. Molecular dynamics simulation and kinetic data revealed the basis of selectivity.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"22 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981777","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}
引用次数: 0
2H-NMR as a Practical Tool for Following MOF Formation: A Case Study of UiO-66
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1002/anie.202420157
Amanda P. Parsons, Céline M. Schneider, Michael J. Katz
Developing the mechanism for MOF formation is crucial for the rapid development of new materials. This work demonstrates that Deuterium-NMR spectroscopy is the optimal inter-laboratory methodology for understanding the in-situ kinetics of metal-organic framework (MOF) formation. This method is facile, affordable, and allows for the isolation and monitoring of individual reagents by using one deuterated component while the remaining components are protonated. This study utilizes 2H-NMR, via the spectrometer’s lock channel, to investigate the formation of UiO-66 as influenced by different modulators: acetic acid, benzoic acid, and hydrochloric acid. By monitoring the concentration of the deuterated linker and observing the chemical shift and peak width of deuterated water over time, key elements of the mechanism are unraveled. Paradoxically, conditions that cause the ligand to be consumed more slowly result in MOFs forming more quickly and with fewer defects. This phenomenon is attributed to the dissociative mechanism associated with the Zr(IV)-containing node.
开发 MOF 的形成机理对于快速开发新材料至关重要。这项研究表明,氘-核磁共振光谱法是了解金属有机框架(MOF)原位形成动力学的最佳实验室间方法。这种方法简便易行、经济实惠,可通过使用一种氘化成分而同时使用质子化的其余成分来分离和监测单个试剂。本研究通过光谱仪的锁定通道利用 2H-NMR 来研究 UiO-66 的形成受不同调制剂(醋酸、苯甲酸和盐酸)的影响。通过监测氘化连接体的浓度和观察氘化水随时间变化的化学位移和峰宽,揭示了该机制的关键要素。矛盾的是,在配体消耗较慢的条件下,MOF 的形成速度更快,缺陷更少。这一现象归因于与含 Zr(IV) 节点相关的离解机制。
{"title":"2H-NMR as a Practical Tool for Following MOF Formation: A Case Study of UiO-66","authors":"Amanda P. Parsons, Céline M. Schneider, Michael J. Katz","doi":"10.1002/anie.202420157","DOIUrl":"https://doi.org/10.1002/anie.202420157","url":null,"abstract":"Developing the mechanism for MOF formation is crucial for the rapid development of new materials. This work demonstrates that Deuterium-NMR spectroscopy is the optimal inter-laboratory methodology for understanding the in-situ kinetics of metal-organic framework (MOF) formation. This method is facile, affordable, and allows for the isolation and monitoring of individual reagents by using one deuterated component while the remaining components are protonated. This study utilizes 2H-NMR, via the spectrometer’s lock channel, to investigate the formation of UiO-66 as influenced by different modulators: acetic acid, benzoic acid, and hydrochloric acid. By monitoring the concentration of the deuterated linker and observing the chemical shift and peak width of deuterated water over time, key elements of the mechanism are unraveled. Paradoxically, conditions that cause the ligand to be consumed more slowly result in MOFs forming more quickly and with fewer defects. This phenomenon is attributed to the dissociative mechanism associated with the Zr(IV)-containing node.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"24 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981789","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}
引用次数: 0
Design of an Ultrafast and Controlled Visible Light-Mediated Photoiniferter RAFT Polymerization for Polymerization-Induced Self-Assembly (PISA)
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1002/anie.202422975
Zilong Wu, Zhengyan He, Yuchen Zhou, Tongtong Kou, Kaili Gong, Fuchun Nan, Terefe Tafese Bezuneh, Shiguo Han, Cyrille Andre Jean Marie Boyer, William W. Yu
In this contribution, we designed a new xanthate RAFT agent by introducing (5,6,7,8-tetrahydro-2-naphthalenyl)oxy (TNO) as the Z group, namely 2-[(((5,6,7,8-Tetrahydro-2-naphthalenyl)oxycarbonothioyl)thio)ethyl propanoate] (TNXEP). Due to the presence of the TNO group, TNXEP enabled highly controlled and ultrafast photoiniferter RAFT polymerization under violet (λ = 405 nm) and blue (λ = 450 nm) light. This approach was effectively extended to aqueous media for polymerization-induced self-assembly (PISA), facilitating the synthesis of polymeric nanoparticles. Leveraging the rapid photolysis and extended absorption of TNXEP, we demonstrated the first photoiniferter PISA system realizing ultrafast polymerization (> 90% monomer conversion in minutes) under visible light irradiation. Enhanced visible light penetration improved photopolymerization uniformity, enabling rapid and scalable production of polymeric nanoparticles at a 30 g scale in just 10 minutes, with tunable morphologies, including spheres, worms, and vesicles.
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引用次数: 0
Pi-Stacking Geometry Directed Supramolecular Secondary Building Units Shaping Hydrogen-Bonded Frameworks for Intensive NH3 Adsorption
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1002/anie.202500268
Xiaojun Ding, Qiang Gao, Yi Su, Jing Chen, Gang Ye
Exploiting supramolecular secondary building units (SSBUs) for developing porous crystalline materials represents an exciting breakthrough that extends the boundaries of reticular chemistry. However, shaping polynuclear clusters sustained by non-covalent interactions for the assembly of hydrogen-bonded frameworks remains a critical challenge. This study presents a novel strategy to stabilize SSBUs by tuning the π-stacking geometry of conjugated building blocks, facilitating the creation of hydrogen-bonded frameworks with tailored architectures for demanding gas separation. Specifically, parallel-displaced π-π stackings of aromatic heterocycles bearing carboxyls promote the formation of SSBUs bridged by ammonium cations [NH4+]8[COO-]8 (SSBU-4), enabling the assembly of hydrogen-bonded frameworks with permanent porosity and structural diversity influenced by the solvent effect. Comparatively, the non-heterocyclic building units exhibit geometrically- or energetically-unfavorable π stackings, resulting in fragile frameworks that collapse after removing disordered guests. Significantly, the heterocycle conjugated frameworks contain abundant open Brønsted acid N-H sites within pore channels, demonstrating remarkable NH3 adsorption ability among diverse industrial gases with a high capacity (275.7 mL/g, at 273 K, 100 kPa) as compared to reported porous molecular crystals.
利用超分子二级构建单元(SSBUs)开发多孔晶体材料是一项令人兴奋的突破,它拓展了网状化学的边界。然而,如何通过非共价相互作用形成多核团簇,以组装氢键框架,仍然是一个严峻的挑战。本研究提出了一种新策略,通过调整共轭结构单元的 π 堆积几何形状来稳定 SSBU,从而促进创建具有定制结构的氢键框架,以满足气体分离的要求。具体来说,带有羧基的芳香杂环的平行置位π-π堆叠促进了由铵阳离子[NH4+]8[COO-]8(SSBU-4)桥接的 SSBU 的形成,从而组装出具有永久孔隙率和受溶剂效应影响的结构多样性的氢键框架。相比之下,非杂环构建单元表现出几何上或能量上不利的 π 堆叠,导致脆弱的框架在移除无序客体后坍塌。值得注意的是,杂环共轭框架的孔道内含有丰富的开放式布氏酸 N-H 位点,与已报道的多孔分子晶体相比,它对各种工业气体具有显著的 NH3 吸附能力,吸附容量高(275.7 mL/g,273 K,100 kPa)。
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引用次数: 0
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Angewandte Chemie International Edition
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