Lithium–sulfur (Li–S) batteries has been regarded as one of the most promising next-generation energy storage systems due to their high theoretical energy density. However, the practical application of Li–S batteries is still hindered by the unstable cathode-electrolyte interphase and the early passivation of charge product (Li2S), leading to poor cycling stability and low S utilization. Herein, we propose an electrolyte engineering strategy using highly solvating hexamethylphosphoramide (HMPA) as a co-solvent to elucidate the dissociation–precipitation chemistry of lithium polysulfides (LiPSs). The multimode optical spectroscopies confirm that this electrolyte engineering is able to effectively regulate the solvation of LiPSs to initiate a radical-assisted conversion pathway and control three-dimensional (3D) Li2S electrodeposition to boost sulfur utilization. More importantly, the dynamic evolution of cathode–electrolyte interphase, featuring with S-/P-containing species, is also assessed by both distribution of relaxation times technology and X-ray photoelectron spectroscopy, which can suppress the passivation of Li2S to enhance conversion reversibility. As a proof-of-concept, a Li–S cell with high S loading mass of 7.75 mg cm−2 demonstrates an extremely high area capacity of 7.86 mAh cm−2 at a current density of 1.30 mA cm−2 , representing a significant advancement in promoting the development of practical high-energy-density Li–S batteries.
{"title":"Dissociation–Precipitation Chemistry of Lithium Polysulfides and Its Correlation to Dynamic Evolution of Cathode–Electrolyte Interphase in Highly Solvating Electrolyte","authors":"Luyi Chen, Jiawei Lai, Xiaoxian Guan, Hanqin Zou, Jingwen Liu, Lin Peng, Jian Wang, Yue-Peng Cai, Qifeng Zheng","doi":"10.1002/anie.202423046","DOIUrl":"https://doi.org/10.1002/anie.202423046","url":null,"abstract":"Lithium–sulfur (Li–S) batteries has been regarded as one of the most promising next-generation energy storage systems due to their high theoretical energy density. However, the practical application of Li–S batteries is still hindered by the unstable cathode-electrolyte interphase and the early passivation of charge product (Li2S), leading to poor cycling stability and low S utilization. Herein, we propose an electrolyte engineering strategy using highly solvating hexamethylphosphoramide (HMPA) as a co-solvent to elucidate the dissociation–precipitation chemistry of lithium polysulfides (LiPSs). The multimode optical spectroscopies confirm that this electrolyte engineering is able to effectively regulate the solvation of LiPSs to initiate a radical-assisted conversion pathway and control three-dimensional (3D) Li2S electrodeposition to boost sulfur utilization. More importantly, the dynamic evolution of cathode–electrolyte interphase, featuring with S-/P-containing species, is also assessed by both distribution of relaxation times technology and X-ray photoelectron spectroscopy, which can suppress the passivation of Li2S to enhance conversion reversibility. As a proof-of-concept, a Li–S cell with high S loading mass of 7.75 mg cm−2 demonstrates an extremely high area capacity of 7.86 mAh cm−2 at a current density of 1.30 mA cm−2 , representing a significant advancement in promoting the development of practical high-energy-density Li–S batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"5 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987073","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}
“I would like to discover the interconnectedness of scientists and communities, akin to molecular bonds, reflecting chemistry's role in collaboration and transformation… I lose track of time when I am in the state of flow, immersed in work I'm passionate about…” Find out more about Yi-Hsin Liu in his Introducing… Profile.
{"title":"Yi-Hsin Liu","authors":"","doi":"10.1002/anie.202425555","DOIUrl":"https://doi.org/10.1002/anie.202425555","url":null,"abstract":"<i>“I would like to discover the interconnectedness of scientists and communities, akin to molecular bonds, reflecting chemistry's role in collaboration and transformation… I lose track of time when I am in the state of flow, immersed in work I'm passionate about…”</i> Find out more about Yi-Hsin Liu in his Introducing… Profile.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981733","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}
Engineered immune cell therapy has proven to be a transformative cancer treatment despite the challenges of its prohibitive costs and manufacturing complexity. In this study, we propose a concise “lipid droplet fusion” strategy for engineering macrophages. Because of the integration of hydrophobic alkyl chains and π-conjugated structures, the mildly synthesized sp2C-conjugated covalent organic framework (COF) UM-101 induced lipid droplet fusion and metabolic reprogramming of macrophages, thus promoting their antitumor classical activation. Intravenous injection of UM-101–engineered macrophages effectively inhibited tumor progression. These results represent the first report of room-temperature synthesis of sp2C-conjugated COFs for engineered immune cell therapy, providing a new perspective for the development of therapeutic immune cells via organelle manipulation.
{"title":"An sp2 Carbon-Conjugated Covalent Organic Framework for Fusing Lipid Droplets and Engineered Macrophage Therapy","authors":"Qun Guan, Le-Le Zhou, Zhiqing Yang, Beibei Xie, Yan-An Li, Ruibing Wang","doi":"10.1002/anie.202421416","DOIUrl":"https://doi.org/10.1002/anie.202421416","url":null,"abstract":"Engineered immune cell therapy has proven to be a transformative cancer treatment despite the challenges of its prohibitive costs and manufacturing complexity. In this study, we propose a concise “lipid droplet fusion” strategy for engineering macrophages. Because of the integration of hydrophobic alkyl chains and π-conjugated structures, the mildly synthesized sp2C-conjugated covalent organic framework (COF) UM-101 induced lipid droplet fusion and metabolic reprogramming of macrophages, thus promoting their antitumor classical activation. Intravenous injection of UM-101–engineered macrophages effectively inhibited tumor progression. These results represent the first report of room-temperature synthesis of sp2C-conjugated COFs for engineered immune cell therapy, providing a new perspective for the development of therapeutic immune cells via organelle manipulation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"92 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981738","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}
“The most exciting thing about my research is when we obtain a new crystal structure, you look at it and realize that you are the first to ever study this molecule… My favorite structure is the cyclopentadienyl anion…” Find out more about André Schäfer in his Introducing… Profile.
{"title":"André Schäfer","authors":"","doi":"10.1002/anie.202424599","DOIUrl":"https://doi.org/10.1002/anie.202424599","url":null,"abstract":"<i>“The most exciting thing about my research is when we obtain a new crystal structure, you look at it and realize that you are the first to ever study this molecule… My favorite structure is the cyclopentadienyl anion…”</i> Find out more about André Schäfer in his Introducing… Profile.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"4 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981792","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}
Jose I. Garcia-Peiro, M. Carmen Ortega-Liebana, Catherine Adam, Álvaro Lorente-Macías, Jana Travnickova, E. Elizabeth Patton, Paula Guerrero-López, J. Manuel Garcia-Aznar, Jose L. Hueso, Jesus Santamaria, Asier Unciti-Broceta
Beyond their classical role as cytotoxics, Platinum (Pt) coordination complexes recently joined the selected group of transition metals capable of performing bioorthogonal reactions in living environments. To minimize their reactivity towards nucleophiles, which limit their catalytic performance, we investigated the use of Pt(0) with different forms, sizes and surface functionalization. We report herein the development of PEGylated Pt nanodendrites with the capacity to activate prodyes and prodrugs in cell culture and in vivo. Their dendritic morphology together with their surface shielding through Pt-S-bonded PEGylation synergistically contributed to create catalytic nanoreactors compatible with the highly-crowded and reductive environment of the cell cytoplasm, thereby facilitating in situ bioorthogonal drug uncaging in cancer cells in 2D and 3D culture, including in microfluidic systems, and xenografted in zebrafish.
{"title":"Dendritic Platinum Nanoparticles Shielded by Pt-S PEGylation as Intracellular Reactors for Bioorthogonal Uncaging Chemistry","authors":"Jose I. Garcia-Peiro, M. Carmen Ortega-Liebana, Catherine Adam, Álvaro Lorente-Macías, Jana Travnickova, E. Elizabeth Patton, Paula Guerrero-López, J. Manuel Garcia-Aznar, Jose L. Hueso, Jesus Santamaria, Asier Unciti-Broceta","doi":"10.1002/anie.202424037","DOIUrl":"https://doi.org/10.1002/anie.202424037","url":null,"abstract":"Beyond their classical role as cytotoxics, Platinum (Pt) coordination complexes recently joined the selected group of transition metals capable of performing bioorthogonal reactions in living environments. To minimize their reactivity towards nucleophiles, which limit their catalytic performance, we investigated the use of Pt(0) with different forms, sizes and surface functionalization. We report herein the development of PEGylated Pt nanodendrites with the capacity to activate prodyes and prodrugs in cell culture and in vivo. Their dendritic morphology together with their surface shielding through Pt-S-bonded PEGylation synergistically contributed to create catalytic nanoreactors compatible with the highly-crowded and reductive environment of the cell cytoplasm, thereby facilitating in situ bioorthogonal drug uncaging in cancer cells in 2D and 3D culture, including in microfluidic systems, and xenografted in zebrafish.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"28 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981774","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}
Tao Liu, Lianqin Wang, Bin Chen, Haotian Liu, Sipu Wang, Yingjie Feng, Junfeng Zhang, Yan Yin, Guiver Michael
Improving the alkaline hydrogen evolution reaction (HER) efficiency is essential for developing advanced anion exchange membrane water electrolyzers (AEMWEs) that operate at industrial ampere-level currents. Herein, we employ density functional theory (DFT) calculations to identify Ni-RuO2 as the leading candidate among various 3d transition metal-doped M-RuO2 (where metal M includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn). The incorporation of Ni atoms facilitates the partial reduction of RuO2, resulting in the formation of a Ni-Ru/RuO2 interface having a significant built-in electric field (BIEF) during electrochemical reactions. The resulted BIEF enhances electron transfer across the interface, which is critical in lowering energy barriers and accelerating the hydrogen evolution reaction (HER) kinetics. As a result, the Ni-RuO2 catalyst exhibits an overpotential of 134 mV at 1 A cm-2 and a low Tafel slope of 20.85 mV dec-1, with just 0.03 mg cm-2 of Ru loading. The highly effective BIEF, therefore, plays a pivotal role in the catalyst's remarkable performance, allowing the Ni-RuO2-based AEMWE to require only 1.71V to maintain stable operation at 1 A cm-2 over a 1000-hour period.
{"title":"Modulating Built-In Electric Field Strength in Ru/RuO2 Interfaces through Ni Doping to Enhance Hydrogen Conversion at Ampere-level Current","authors":"Tao Liu, Lianqin Wang, Bin Chen, Haotian Liu, Sipu Wang, Yingjie Feng, Junfeng Zhang, Yan Yin, Guiver Michael","doi":"10.1002/anie.202421869","DOIUrl":"https://doi.org/10.1002/anie.202421869","url":null,"abstract":"Improving the alkaline hydrogen evolution reaction (HER) efficiency is essential for developing advanced anion exchange membrane water electrolyzers (AEMWEs) that operate at industrial ampere-level currents. Herein, we employ density functional theory (DFT) calculations to identify Ni-RuO2 as the leading candidate among various 3d transition metal-doped M-RuO2 (where metal M includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn). The incorporation of Ni atoms facilitates the partial reduction of RuO2, resulting in the formation of a Ni-Ru/RuO2 interface having a significant built-in electric field (BIEF) during electrochemical reactions. The resulted BIEF enhances electron transfer across the interface, which is critical in lowering energy barriers and accelerating the hydrogen evolution reaction (HER) kinetics. As a result, the Ni-RuO2 catalyst exhibits an overpotential of 134 mV at 1 A cm-2 and a low Tafel slope of 20.85 mV dec-1, with just 0.03 mg cm-2 of Ru loading. The highly effective BIEF, therefore, plays a pivotal role in the catalyst's remarkable performance, allowing the Ni-RuO2-based AEMWE to require only 1.71V to maintain stable operation at 1 A cm-2 over a 1000-hour period.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981776","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}
Mangwei Cui, Lidong Yu, Jin Hu, Sisi He, Chunyi Zhi, Yan Huang
Conventional SEI in aqueous Zn-ion batteries mainly acts as a physical barrier to prevent HER, which is prone to structural deterioration stemming from uneven Zn deposition at high current densities. Herein, we propose an in-situ structural design of polymer-inorganic bilayer SEI with a proton holder feature by aniline-modulated electrolytes. The inner ZnF2 with high stiffness and strength effectively suppresses Zn dendrites. And the outer PANI regulates the current distribution and delays the Sand's time of dendrites growth. The =N- in PANI is capable of reversible proton holder, thereby inhibiting HER. With this bilayer SEI, the Zn anode achieves an impressive cycle life of 126 h under 40 mA cm-2 & 40 mAh cm-2 (DOD=70.8%), solving the bottleneck of single-layer inorganic SEI that could not be cycled under these conditions. The Zn||NaVO pouch battery with bilayer SEI exhibits a high capacity of 1.2 Ah and a cycle life of 350 h with 78% capacity retention. At -30°C, the battery delivers a capacity of 335 mAh and a cycle life of 507 h with 72% capacity retention. Our findings offer profound insights into the design of SEI with tailored structure and functionality, paving the way for the next generation of advanced batteries.
{"title":"Tailored Polymer-Inorganic Bilayer SEI with Proton Holder Feature for Aqueous Zn Metal Batteries","authors":"Mangwei Cui, Lidong Yu, Jin Hu, Sisi He, Chunyi Zhi, Yan Huang","doi":"10.1002/anie.202423531","DOIUrl":"https://doi.org/10.1002/anie.202423531","url":null,"abstract":"Conventional SEI in aqueous Zn-ion batteries mainly acts as a physical barrier to prevent HER, which is prone to structural deterioration stemming from uneven Zn deposition at high current densities. Herein, we propose an in-situ structural design of polymer-inorganic bilayer SEI with a proton holder feature by aniline-modulated electrolytes. The inner ZnF2 with high stiffness and strength effectively suppresses Zn dendrites. And the outer PANI regulates the current distribution and delays the Sand's time of dendrites growth. The =N- in PANI is capable of reversible proton holder, thereby inhibiting HER. With this bilayer SEI, the Zn anode achieves an impressive cycle life of 126 h under 40 mA cm-2 & 40 mAh cm-2 (DOD=70.8%), solving the bottleneck of single-layer inorganic SEI that could not be cycled under these conditions. The Zn||NaVO pouch battery with bilayer SEI exhibits a high capacity of 1.2 Ah and a cycle life of 350 h with 78% capacity retention. At -30°C, the battery delivers a capacity of 335 mAh and a cycle life of 507 h with 72% capacity retention. Our findings offer profound insights into the design of SEI with tailored structure and functionality, paving the way for the next generation of advanced batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"53 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981735","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}
Near-infrared (NIR) triplet dyes are the cornerstones of cutting-edge biomedical and material applications. The difficulty in rational development of triplet dyes increases exponentially as the absorption wavelength shifts deeper into the NIR range. Although classical H-/J-typed packing of NIR dyes has the potential to enhance intersystem crossing (ISC) compared with that in single-chromophore dyes, the triplet state quantum yields remain limited in such strategy. Herein, proximal oblique-packed (V-shaped) heptamethine cyanines (SZ780) through spiro-connection were achieved. Multi-channel ultrafast ISC were direct observed in SZ780 and a record high ISC rate constant (up to ~1011 s-1) is registered among all the reported NIR triplet dyes. SZ780 exhibits a triplet state quantum yield of 18.9% upon excitation at 750 nm, which is almost an order of magnitude higher than that of the monomer (IR780, 2.1%) and nearly threefold increase compared to that of the H-packed dimer (SC780) (6.7%). Moreover, SZ780 efficiently generates singlet oxygen under 808 nm light irradiation, inducing cancer cell apoptosis in vivo. These findings demonstrate that constructing V-aggregated dyes system by spiro-connection offers a powerful approach for the design of high-performance NIR triplet sensitizers.
{"title":"Proximal Oblique-Packing of Heptamethine Cyanines through Spiro-Connection Boosts Triplet State Generation in Near-Infrared","authors":"Xueli Wang, Jie Zhou, Mingkang Wang, Yuze Wang, Zhetao Shen, Haitao Sun, Zhubin Hu, Xiao Luo, Youjun Yang, Jinquan Chen","doi":"10.1002/anie.202425422","DOIUrl":"https://doi.org/10.1002/anie.202425422","url":null,"abstract":"Near-infrared (NIR) triplet dyes are the cornerstones of cutting-edge biomedical and material applications. The difficulty in rational development of triplet dyes increases exponentially as the absorption wavelength shifts deeper into the NIR range. Although classical H-/J-typed packing of NIR dyes has the potential to enhance intersystem crossing (ISC) compared with that in single-chromophore dyes, the triplet state quantum yields remain limited in such strategy. Herein, proximal oblique-packed (V-shaped) heptamethine cyanines (SZ780) through spiro-connection were achieved. Multi-channel ultrafast ISC were direct observed in SZ780 and a record high ISC rate constant (up to ~1011 s-1) is registered among all the reported NIR triplet dyes. SZ780 exhibits a triplet state quantum yield of 18.9% upon excitation at 750 nm, which is almost an order of magnitude higher than that of the monomer (IR780, 2.1%) and nearly threefold increase compared to that of the H-packed dimer (SC780) (6.7%). Moreover, SZ780 efficiently generates singlet oxygen under 808 nm light irradiation, inducing cancer cell apoptosis in vivo. These findings demonstrate that constructing V-aggregated dyes system by spiro-connection offers a powerful approach for the design of high-performance NIR triplet sensitizers.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981779","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}
Base-stabilized rhodium borylene complex κ2-L(CO)Rh(BMes), 2; κ2-L = κ2-NN’-Rh,κ1-N-B-(2,5-[iPr2P=N(4-iPrC6H4)]2-N’(C4H2)-); Mes = mesityl, reacts with a series of alkynes (PhC≡C—R; R = Ph, Me, CO2Et, H) to yield unique structures whereby the alkyne has regioselectively added across boron and the carbon atom of a CO ligand. The resulting complexes, LRh[C(O)C(Ph)C(R)B(Mes)], 3R, react with additional CO to afford cycle-containing products, L(CO)Rh([[EQUATION]]), 5R, that ultimately release highly functionalized organic heterocycles of the form [[EQUATION]]=NPipp (Pipp = 4-iPrC6H4), 6. These oxaboroles, which were assembled from a primary hydroborane, CO, an alkyne, and an azide-generated NPipp, are structurally analogous to two of the five boron-containing therapeutics approved by the FDA.
碱稳定的硼铑络合物 κ2-L(CO)Rh(BMes), 2; κ2-L = κ2-NN'-Rh, κ1-N-B-(2,5-[iPr2P=N(4-iPrC6H4)]2-N'(C4H2)-); Mes = 甲磺酰基，与一系列炔烃（PhC≡C-R；R=Ph、Me、CO2Et、H）发生反应，生成独特的结构，其中炔烃通过硼和 CO 配体的碳原子进行区域选择性添加。由此产生的配合物 LRh[C(O)C(Ph)C(R)B(Mes)]，3R，与额外的 CO 反应生成含循环的产物 L(CO)Rh([[等式]])，5R，最终释放出高度官能化的有机杂环，其形式为[[等式]]=NPipp（Pipp = 4-iPrC6H4），6。这些氧硼烷是由伯羟基硼烷、CO、炔烃和叠氮化物生成的 NPipp 组合而成的，在结构上类似于美国 FDA 批准的五种含硼疗法中的两种。
{"title":"Rhodium-mediated Assembly of New Heterocycles: From Borylenes to Oxaboroles","authors":"Paul G. Hayes, Shou-Jen Hsiang","doi":"10.1002/anie.202421302","DOIUrl":"https://doi.org/10.1002/anie.202421302","url":null,"abstract":"Base-stabilized rhodium borylene complex κ2-L(CO)Rh(BMes), 2; κ2-L = κ2-NN’-Rh,κ1-N-B-(2,5-[iPr2P=N(4-iPrC6H4)]2-N’(C4H2)-); Mes = mesityl, reacts with a series of alkynes (PhC≡C—R; R = Ph, Me, CO2Et, H) to yield unique structures whereby the alkyne has regioselectively added across boron and the carbon atom of a CO ligand. The resulting complexes, LRh[C(O)C(Ph)C(R)B(Mes)], 3R, react with additional CO to afford cycle-containing products, L(CO)Rh([[EQUATION]]), 5R, that ultimately release highly functionalized organic heterocycles of the form [[EQUATION]]=NPipp (Pipp = 4-iPrC6H4), 6. These oxaboroles, which were assembled from a primary hydroborane, CO, an alkyne, and an azide-generated NPipp, are structurally analogous to two of the five boron-containing therapeutics approved by the FDA.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"20 79 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975519","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}
Yanxin Shang, Nan Chen, Yuejiao Li, Shi Chen, Zhujie Li, Shengxi Li, Xuening Ren, Yusheng Ye, Li Li, Feng Wu, Renjie Chen
The H-bond network among H2O molecules enables ultrafast diffusion of H+ and OH- via a hopping mechanism, making aqueous batteries attractive competitors for next-generation fast-charging energy storages. Ideal aqueous electrolyte for the widely used lithium-ion batteries is expected to have the wide electrochemical stability window (>5 volts), fast charging (≤15 minutes) without gas evolution, and low cost. However, the hydrogen evolution reaction (HER) associated with narrow voltage window of water (1.23 V) limits their practical applications. Herein, we built a new guideline for designing tiny-ligand electrolytes by utilizing sterically hindered groups with low binding energy. Cosolvent tetraethyl orthocarbonate (TEOC), with large-sized ethoxy groups and hydrogen-bond-captured ability, forces free H2O and anion TFSI- into the Li+ first solvation shell. Hence, inhibition of HER takes place by means of immobilized H2O activity and formation of hydrogen-bonding networks—C-O···H between TEOC and H2O. This unique structure with ultra-small sheath volume thereby facilitates the formation of LiF-rich SEI and fast ion-conduction. The lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in TEOC/H2O electrolyte exhibits wide electrochemical window of 5.7 V, enabling LiMn2O4/Li4Ti5O12 pouch cells to achieve 1200 cycles under rapid 10 C rate. This engineering of tiny-ligand solvation opens new pathways for developing advanced electrolyte that balance performance with sustainability.
{"title":"Tiny-Ligand Solvation Electrolyte Enabled Fast-charging Aqueous Batteries","authors":"Yanxin Shang, Nan Chen, Yuejiao Li, Shi Chen, Zhujie Li, Shengxi Li, Xuening Ren, Yusheng Ye, Li Li, Feng Wu, Renjie Chen","doi":"10.1002/anie.202423808","DOIUrl":"https://doi.org/10.1002/anie.202423808","url":null,"abstract":"The H-bond network among H2O molecules enables ultrafast diffusion of H+ and OH- via a hopping mechanism, making aqueous batteries attractive competitors for next-generation fast-charging energy storages. Ideal aqueous electrolyte for the widely used lithium-ion batteries is expected to have the wide electrochemical stability window (>5 volts), fast charging (≤15 minutes) without gas evolution, and low cost. However, the hydrogen evolution reaction (HER) associated with narrow voltage window of water (1.23 V) limits their practical applications. Herein, we built a new guideline for designing tiny-ligand electrolytes by utilizing sterically hindered groups with low binding energy. Cosolvent tetraethyl orthocarbonate (TEOC), with large-sized ethoxy groups and hydrogen-bond-captured ability, forces free H2O and anion TFSI- into the Li+ first solvation shell. Hence, inhibition of HER takes place by means of immobilized H2O activity and formation of hydrogen-bonding networks—C-O···H between TEOC and H2O. This unique structure with ultra-small sheath volume thereby facilitates the formation of LiF-rich SEI and fast ion-conduction. The lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in TEOC/H2O electrolyte exhibits wide electrochemical window of 5.7 V, enabling LiMn2O4/Li4Ti5O12 pouch cells to achieve 1200 cycles under rapid 10 C rate. This engineering of tiny-ligand solvation opens new pathways for developing advanced electrolyte that balance performance with sustainability.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"6 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142974934","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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