Pub Date : 2026-02-09DOI: 10.1016/j.chempr.2025.102885
Miaojie Yu, Jia Wang, Yue Wu, Chen Yuan, Ran Cao, Vincent M. Rotello, Qingchun Huang, Yisheng Xu, Wei-Hong Zhu
Utilization efficiency of sprayed agrochemicals is typically limited by weak adhesion to plant cuticles with ineffective retention. Increasing surface positive charge is effective to strengthen the adhesion, while often overlooking the restricted uptake caused by excessively strong surface binding. Here, we report a unique “dynamic” surface-charge-featured nanofungicide platform for overcoming the dilemma, enabling synergistic enhancement of deposition and uptake. Besides precisely enhancing positivity of nanocarriers via oppositely charged polymers for strong adhesion, we incorporate a thermo-responsive unit to enable in situ mitigation of surface charge in response to temperature after deposition, avoiding excessive positive charge with impaired subsequent uptake. The tebuconazole nanofungicide achieves a curative effect of 98% against B. cinerea on tomato plants using only half the standard dosage. Given the scale-up production from flash nanoprecipitation engineering, the dynamic charge of the nanofungicide makes for a promising feasibility for real-world sustainable agriculture and offers innovative strategies to enhance utilization efficiency with minimized agrochemical inputs.
{"title":"A dynamic charge-dependent nanofungicide platform for sustainable agrochemical deposition and delivery","authors":"Miaojie Yu, Jia Wang, Yue Wu, Chen Yuan, Ran Cao, Vincent M. Rotello, Qingchun Huang, Yisheng Xu, Wei-Hong Zhu","doi":"10.1016/j.chempr.2025.102885","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102885","url":null,"abstract":"Utilization efficiency of sprayed agrochemicals is typically limited by weak adhesion to plant cuticles with ineffective retention. Increasing surface positive charge is effective to strengthen the adhesion, while often overlooking the restricted uptake caused by excessively strong surface binding. Here, we report a unique “dynamic” surface-charge-featured nanofungicide platform for overcoming the dilemma, enabling synergistic enhancement of deposition and uptake. Besides precisely enhancing positivity of nanocarriers via oppositely charged polymers for strong adhesion, we incorporate a thermo-responsive unit to enable <em>in situ</em> mitigation of surface charge in response to temperature after deposition, avoiding excessive positive charge with impaired subsequent uptake. The tebuconazole nanofungicide achieves a curative effect of 98% against <em>B. cinerea</em> on tomato plants using only half the standard dosage. Given the scale-up production from flash nanoprecipitation engineering, the dynamic charge of the nanofungicide makes for a promising feasibility for real-world sustainable agriculture and offers innovative strategies to enhance utilization efficiency with minimized agrochemical inputs.","PeriodicalId":268,"journal":{"name":"Chem","volume":"19 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138750","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}
Lithium–sulfur (Li–S) batteries are promising in realizing high energy density. Employing weakly solvating electrolytes (WSEs) further improves the anode stability. However, the lithium polysulfide (LiPS) redox kinetics is hindered in WSEs, and the underlying mechanism remains unclear. Herein, the LiPS kinetics in WSEs is quantitatively deciphered using rotating disk electrode analysis. The electron transfer number during oxidation is reduced in WSEs, evidencing intrinsically suppressed oxidation extent. Meanwhile, the diffusion coefficient and the electrolyte viscosity concurrently increase, implying a reduced LiPS hydrodynamic radius in WSEs based on the Stokes–Einstein relation and corresponding to inhibited LiPS molecular aggregation. Attributed to the reduced aggregation, WSE-based Li–S batteries exhibit record-low-temperature performances, delivering 8.0 mAh cm−2 and 303 Wh kg−1 at 0°C in 6 Ah-level pouch cells. This work establishes a new kinetic analysis methodology to guide rational electrolyte design and highlights the promise of WSEs to enable low-temperature Li–S batteries.
锂硫电池是实现高能量密度的理想电池。采用弱溶剂化电解质（wse）进一步提高了阳极的稳定性。然而，锂多硫化物（LiPS）在wse中的氧化还原动力学受到阻碍，其潜在机制尚不清楚。在这里，利用旋转圆盘电极分析定量地破译了WSEs中的LiPS动力学。氧化过程中的电子转移数在wse中减少，表明氧化程度受到内在抑制。同时，扩散系数和电解质粘度同时增加，表明基于Stokes-Einstein关系的wse中LiPS流体动力半径减小，对应于LiPS分子聚集受到抑制。由于减少了聚集，基于wse的Li-S电池表现出创纪录的低温性能，在6 ah级别的袋状电池中，在0°C下提供8.0 mAh cm - 2和303 Wh kg - 1。这项工作建立了一种新的动力学分析方法来指导合理的电解质设计，并突出了wse在低温锂硫电池中的应用前景。
{"title":"Reducing polysulfide hydrodynamic radius toward low-temperature lithium–sulfur batteries","authors":"Tian Jin, Meng Zhao, Xi-Yao Li, Zi-Xian Chen, Bo-Quan Li, Jia-Qi Huang, Qiang Zhang","doi":"10.1016/j.chempr.2025.102881","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102881","url":null,"abstract":"Lithium–sulfur (Li–S) batteries are promising in realizing high energy density. Employing weakly solvating electrolytes (WSEs) further improves the anode stability. However, the lithium polysulfide (LiPS) redox kinetics is hindered in WSEs, and the underlying mechanism remains unclear. Herein, the LiPS kinetics in WSEs is quantitatively deciphered using rotating disk electrode analysis. The electron transfer number during oxidation is reduced in WSEs, evidencing intrinsically suppressed oxidation extent. Meanwhile, the diffusion coefficient and the electrolyte viscosity concurrently increase, implying a reduced LiPS hydrodynamic radius in WSEs based on the Stokes–Einstein relation and corresponding to inhibited LiPS molecular aggregation. Attributed to the reduced aggregation, WSE-based Li–S batteries exhibit record-low-temperature performances, delivering 8.0 mAh cm<sup>−2</sup> and 303 Wh kg<sup>−1</sup> at 0°C in 6 Ah-level pouch cells. This work establishes a new kinetic analysis methodology to guide rational electrolyte design and highlights the promise of WSEs to enable low-temperature Li–S batteries.","PeriodicalId":268,"journal":{"name":"Chem","volume":"1 1","pages":"102881"},"PeriodicalIF":23.5,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146209","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-04DOI: 10.1016/j.chempr.2025.102879
Minsung Baek, Jinyoung Kim, Minkwan Kim, Suhwan Kim, Seonmo Yang, Hyo Chul Ahn, Jimin Lee, Kiho Park, Jiheon Kim, Taeyong Lee, Insu Hwang, Nohjoon Lee, Areum Ha, Seongmin Ha, Jongchan Song, Dong-Ik Kim, Heejin Kim, Yong Min Lee, Ki Jae Kim, Jang Wook Choi
Uniform electrodeposition is vital for long-term operation of high-energy metal batteries, yet early interfacial dynamics related to electrodeposition remain underexplored. While irregular native passivation layers can perturb the uniformity of interfacial ion transport flux, their impact on nucleation and deposition behavior has received limited attention. Here, we reveal that nanometer-scale irregularities along initial passivation and nascent solid-electrolyte interphase (SEI) layers critically govern electrodeposition morphology by affecting its directionality and anisotropy. This correlation demonstrates that early interphasial phenomena are key factors in determining the crystallographic texture and structural coherence of electrodeposits. Consequently, we surface-engineered lithium, zinc, and magnesium foils to promote spatially uniform, structurally seamless electrodeposition for improved cycling performance: 75.5% capacity retention after 800 cycles for a full cell pairing a 1.6 mAh cm−2 LiNi0.8Co0.1Mn0.1O2 cathode with a 20-μm-thick Li foil. This work uncovers the regularity of early interphase structure as a key parameter for sustainable cycling of various emerging metal anode batteries.
均匀电沉积对于高能金属电池的长期运行至关重要，但与电沉积相关的早期界面动力学尚未得到充分研究。虽然不规则的原生钝化层会扰乱界面离子传输通量的均匀性，但它们对成核和沉积行为的影响却很少得到关注。在这里，我们揭示了沿初始钝化和新生固体电解质界面（SEI）层的纳米尺度不规则性通过影响其方向性和各向异性来关键地控制电沉积形貌。这种相关性表明，早期相间现象是决定电镀层晶体结构和结构相干性的关键因素。因此，我们对锂、锌和镁箔进行表面工程，以促进空间均匀、结构无缝的电沉积，从而提高循环性能：将1.6 mAh cm - 2 LiNi0.8Co0.1Mn0.1O2阴极与20 μm厚的Li箔结合，在充满电池的情况下，800次循环后容量保持率为75.5%。本研究揭示了早期相结构的规律性是各种新型金属阳极电池可持续循环的关键参数。
{"title":"Removing passivation irregularities for seamless electroplating across lithium, zinc, and magnesium metal batteries","authors":"Minsung Baek, Jinyoung Kim, Minkwan Kim, Suhwan Kim, Seonmo Yang, Hyo Chul Ahn, Jimin Lee, Kiho Park, Jiheon Kim, Taeyong Lee, Insu Hwang, Nohjoon Lee, Areum Ha, Seongmin Ha, Jongchan Song, Dong-Ik Kim, Heejin Kim, Yong Min Lee, Ki Jae Kim, Jang Wook Choi","doi":"10.1016/j.chempr.2025.102879","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102879","url":null,"abstract":"Uniform electrodeposition is vital for long-term operation of high-energy metal batteries, yet early interfacial dynamics related to electrodeposition remain underexplored. While irregular native passivation layers can perturb the uniformity of interfacial ion transport flux, their impact on nucleation and deposition behavior has received limited attention. Here, we reveal that nanometer-scale irregularities along initial passivation and nascent solid-electrolyte interphase (SEI) layers critically govern electrodeposition morphology by affecting its directionality and anisotropy. This correlation demonstrates that early interphasial phenomena are key factors in determining the crystallographic texture and structural coherence of electrodeposits. Consequently, we surface-engineered lithium, zinc, and magnesium foils to promote spatially uniform, structurally seamless electrodeposition for improved cycling performance: 75.5% capacity retention after 800 cycles for a full cell pairing a 1.6 mAh cm<sup>−2</sup> LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> cathode with a 20-μm-thick Li foil. This work uncovers the regularity of early interphase structure as a key parameter for sustainable cycling of various emerging metal anode batteries.","PeriodicalId":268,"journal":{"name":"Chem","volume":"132 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-03DOI: 10.1016/j.chempr.2026.102950
Elie Benchimol, Jacopo Tessarolo
{"title":"Synergistic effects: From the coffee room to coordination cages","authors":"Elie Benchimol, Jacopo Tessarolo","doi":"10.1016/j.chempr.2026.102950","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102950","url":null,"abstract":"","PeriodicalId":268,"journal":{"name":"Chem","volume":"39 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110758","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}
How can non-covalent interactions be harnessed in the design of multifunctional materials beyond the constraints of traditional bonding frameworks? Inspired by weak interactions in biological systems and motivated to overcome the constraints imposed by valence-shell electron-pair repulsion, we explore excited-state through-space conjugation (TSC) between adjacent nitrogen atoms as an efficient strategy for modulating material properties. Photoisomerizable molecular switches activate dynamic TSC in the excited state, markedly enhancing both optical and mechanical properties. In the crystalline phase, this dynamic TSC enables robust red circularly polarized luminescence (CPL) at 610 nm, sustained over 300 reversible cycles, with a record-high asymmetry factor (∼0.20) among non-assembled organic small molecules. Concurrently, the system exhibits reversible changes in both elasticity and hardness. These findings uncover a counterintuitive lone-pair/lone-pair conjugation mechanism, presenting a novel strategy for designing smart crystalline materials that integrate photoswitchable and photomechanical functionalities.
{"title":"Intrinsic circularly polarized luminescence with a record-high dissymmetry factor via dynamic through-space conjugation","authors":"Zuping Xiong, Xiong Liu, Ziteng Zhang, Shuaitong Wei, Jiyong Liu, Qingyang Xu, Jing Zhi Sun, Jianyu Zhang, Ben Zhong Tang, Haoke Zhang","doi":"10.1016/j.chempr.2025.102858","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102858","url":null,"abstract":"How can non-covalent interactions be harnessed in the design of multifunctional materials beyond the constraints of traditional bonding frameworks? Inspired by weak interactions in biological systems and motivated to overcome the constraints imposed by valence-shell electron-pair repulsion, we explore excited-state through-space conjugation (TSC) between adjacent nitrogen atoms as an efficient strategy for modulating material properties. Photoisomerizable molecular switches activate dynamic TSC in the excited state, markedly enhancing both optical and mechanical properties. In the crystalline phase, this dynamic TSC enables robust red circularly polarized luminescence (CPL) at 610 nm, sustained over 300 reversible cycles, with a record-high asymmetry factor (∼0.20) among non-assembled organic small molecules. Concurrently, the system exhibits reversible changes in both elasticity and hardness. These findings uncover a counterintuitive lone-pair/lone-pair conjugation mechanism, presenting a novel strategy for designing smart crystalline materials that integrate photoswitchable and photomechanical functionalities.","PeriodicalId":268,"journal":{"name":"Chem","volume":"44 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101829","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-02DOI: 10.1016/j.chempr.2025.102866
Richard Lincoln, Alexey N. Butkevich, Clara-Marie Gürth, Alena Fischer, Jessica Matthias, Anna R. Emmerich, Maximilian Fidlin, Mariano L. Bossi, Stefan W. Hell
State-of-the-art super-resolution microscopy methods benefit greatly when combined with photoactivatable or photoswitchable fluorophores with far-red emission, but the majority of these fluorophores require specialized buffers or rely on photolabile protecting groups that limit their biocompatibility. We report here a caging-group-free strategy for photoactivatable dyes based on 1-vinyl-10-silaxanthone derivatives containing 9-acylimino or 9-(alkoxycarbonyl)imino groups, enabling minimally sized photoactivatable dyes with ≥680 nm emission. The 9-(alkoxycarbonyl)imino silaxanthones are particularly suitable for live-cell labeling, undergoing byproduct-free photoactivation to yield bright and photostable fluorophores that can be readily imaged by STED (stimulated emission depletion), PALM (photoactivated localization microscopy), or MINFLUX (minimal photon fluxes) nanoscopy techniques. The labels derived from these photoactivatable dyes open up new possibilities for multiplexed imaging.
{"title":"Caging-group-free photoactivatable fluorophores with far-red emission","authors":"Richard Lincoln, Alexey N. Butkevich, Clara-Marie Gürth, Alena Fischer, Jessica Matthias, Anna R. Emmerich, Maximilian Fidlin, Mariano L. Bossi, Stefan W. Hell","doi":"10.1016/j.chempr.2025.102866","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102866","url":null,"abstract":"State-of-the-art super-resolution microscopy methods benefit greatly when combined with photoactivatable or photoswitchable fluorophores with far-red emission, but the majority of these fluorophores require specialized buffers or rely on photolabile protecting groups that limit their biocompatibility. We report here a caging-group-free strategy for photoactivatable dyes based on 1-vinyl-10-silaxanthone derivatives containing 9-acylimino or 9-(alkoxycarbonyl)imino groups, enabling minimally sized photoactivatable dyes with ≥680 nm emission. The 9-(alkoxycarbonyl)imino silaxanthones are particularly suitable for live-cell labeling, undergoing byproduct-free photoactivation to yield bright and photostable fluorophores that can be readily imaged by STED (stimulated emission depletion), PALM (photoactivated localization microscopy), or MINFLUX (minimal photon fluxes) nanoscopy techniques. The labels derived from these photoactivatable dyes open up new possibilities for multiplexed imaging.","PeriodicalId":268,"journal":{"name":"Chem","volume":"3 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135433","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-02DOI: 10.1016/j.chempr.2025.102865
Smaragda Lymperopoulou, Samuel Hoff, Anna Sola-Rabada, Monika Michaelis, Igor Efimov, Zayd C. Westcott, India J. Willimott, Mauro Chiacchia, Hendrik Heinz, Carole C. Perry, Darren Bradshaw
The biomimetic mineralization of metal-organic frameworks (MOFs) is a promising synthetic strategy for MOF and hybrid bio-MOF composites and has significant potential in a variety of applications. Although interactions between MOFs and several biological materials have been extensively studied, interactions between MOFs and peptides remain unexplored. Here, we used phage display to identify strongly binding peptides for isoreticular MOFs (UiO-66 and UiO-66-NH2). Zeta potential (ZP) and circular dichroism (CD) spectroscopy measurements, combined with molecular dynamics (MD) simulations, enabled us to characterize and explain the structure and dynamics of the MOF-binding peptides, as well as differences in conformation and binding coefficients, thereby allowing determination of the MOF-peptide recognition mechanisms. We also successfully used the peptides to control MOF crystallinity and morphology for Zr-based MOFs under synthesis conditions where amorphous products form in their absence. Our findings have significant implications for understanding MOF-peptide interactions, which will be critical for designing and controlling MOF structures and for bio-centered applications.
{"title":"Genetically engineered peptides for the biomimetic mineralization of metal-organic frameworks","authors":"Smaragda Lymperopoulou, Samuel Hoff, Anna Sola-Rabada, Monika Michaelis, Igor Efimov, Zayd C. Westcott, India J. Willimott, Mauro Chiacchia, Hendrik Heinz, Carole C. Perry, Darren Bradshaw","doi":"10.1016/j.chempr.2025.102865","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102865","url":null,"abstract":"The biomimetic mineralization of metal-organic frameworks (MOFs) is a promising synthetic strategy for MOF and hybrid bio-MOF composites and has significant potential in a variety of applications. Although interactions between MOFs and several biological materials have been extensively studied, interactions between MOFs and peptides remain unexplored. Here, we used phage display to identify strongly binding peptides for isoreticular MOFs (UiO-66 and UiO-66-NH<sub>2</sub>). Zeta potential (ZP) and circular dichroism (CD) spectroscopy measurements, combined with molecular dynamics (MD) simulations, enabled us to characterize and explain the structure and dynamics of the MOF-binding peptides, as well as differences in conformation and binding coefficients, thereby allowing determination of the MOF-peptide recognition mechanisms. We also successfully used the peptides to control MOF crystallinity and morphology for Zr-based MOFs under synthesis conditions where amorphous products form in their absence. Our findings have significant implications for understanding MOF-peptide interactions, which will be critical for designing and controlling MOF structures and for bio-centered applications.","PeriodicalId":268,"journal":{"name":"Chem","volume":"289 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101828","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}
Photoredox catalysis is a useful toolbox for organic synthetic chemistry through not only creating more possibilities for the known reactions but also developing new pathways for the inaccessible compounds. The development of transition metal complexes greatly boosts this field, while there remain a variety of challenges such as poor photostability, non-recyclability, limited activity, and red-light inaccessibility. Herein, we develop a divergent strategy to construct covalent organic frameworks (COFs) featuring dense and aligned porphyrin antenna and docking sites. Various metal species are well immobilized on the pore walls of COFs to form antenna-reactor structures COF-M (M = Ir, Ru, and Cu) with good photostability and recyclability. The segregated porphyrin donor and metal complex acceptor promote the separation and suppress the recombination of photo-induced charge carriers. As a result, the as-prepared COF-M presents high activity toward several reactions, including photocatalytic [2 + 2] cycloadditions, trifluoromethylation reactions, and reductive pinacol-type couplings.
光氧化还原催化是有机合成化学的一个有用的工具箱，它不仅为已知的反应创造了更多的可能性，而且为难以获得的化合物开辟了新的途径。过渡金属配合物的发展极大地推动了这一领域的发展，但仍存在各种挑战，如光稳定性差、不可回收、活性有限、红灯不可达性等。在此，我们开发了一种发散策略来构建具有密集和排列的卟啉天线和对接位点的共价有机框架（COFs）。COF-M （M = Ir, Ru, Cu）具有良好的光稳定性和可回收性。卟啉给体和金属配合物受体的分离促进了光诱导载流子的分离，抑制了载流子的复合。因此，制备的COF-M对几种反应表现出高活性，包括光催化[2 + 2]环加成、三氟甲基化反应和还原性pinacol型偶联。
{"title":"Divergent covalent organic frameworks as antenna reactors for photoredox catalysis","authors":"Ting He, Ziyue Huang, Zhongzheng Zhang, Jingjing Guo, Yuanyuan Guo, Brynne Shu Ni Tan, Shihuai Wang, Yanping Wei, Yinglong Wu, Xinkun Ma, Wenbin Zhong, Yanli Zhao","doi":"10.1016/j.chempr.2025.102864","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102864","url":null,"abstract":"Photoredox catalysis is a useful toolbox for organic synthetic chemistry through not only creating more possibilities for the known reactions but also developing new pathways for the inaccessible compounds. The development of transition metal complexes greatly boosts this field, while there remain a variety of challenges such as poor photostability, non-recyclability, limited activity, and red-light inaccessibility. Herein, we develop a divergent strategy to construct covalent organic frameworks (COFs) featuring dense and aligned porphyrin antenna and docking sites. Various metal species are well immobilized on the pore walls of COFs to form antenna-reactor structures COF-M (M = Ir, Ru, and Cu) with good photostability and recyclability. The segregated porphyrin donor and metal complex acceptor promote the separation and suppress the recombination of photo-induced charge carriers. As a result, the as-prepared COF-M presents high activity toward several reactions, including photocatalytic [2 + 2] cycloadditions, trifluoromethylation reactions, and reductive pinacol-type couplings.","PeriodicalId":268,"journal":{"name":"Chem","volume":"1 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-02DOI: 10.1016/j.chempr.2025.102867
Honglei Yu, Lin Ai, Siyu Lu
Fluorescence imaging in the second near-infrared window (NIR-II, 1,000–3,000 nm), where biological tissues exhibit optical transparency, has garnered significant attention. Owing to the minimal tissue absorption, scattering, and autofluorescence in this spectral region, NIR-II fluorescence imaging enables non-invasive in vivo imaging at millimeter-scale depths. Over the past decade, studies have focused on the development of NIR-II fluorophores with minimal background interference from tissues. This review focuses on strategies to optimize fluorophore performance, aiming to enhance the tissue penetration depth and imaging contrast. First, we discuss recent strategies for wavelength tuning and brightness enhancement of functional NIR-II fluorophores, categorized by their composition into organic and inorganic fluorophores. Subsequently, we summarize the latest biomedical applications and discuss the opportunities and challenges of their clinical translation, aiming to advance the clinical application of the NIR-II imaging technology. Overall, this review provides a forward-looking perspective to guide the future development of NIR-II fluorophores.
{"title":"Second near-infrared fluorophores: Rational design, optical enhancement strategies, and recent advances in imaging-guided biomedical applications","authors":"Honglei Yu, Lin Ai, Siyu Lu","doi":"10.1016/j.chempr.2025.102867","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102867","url":null,"abstract":"Fluorescence imaging in the second near-infrared window (NIR-II, 1,000–3,000 nm), where biological tissues exhibit optical transparency, has garnered significant attention. Owing to the minimal tissue absorption, scattering, and autofluorescence in this spectral region, NIR-II fluorescence imaging enables non-invasive <em>in vivo</em> imaging at millimeter-scale depths. Over the past decade, studies have focused on the development of NIR-II fluorophores with minimal background interference from tissues. This review focuses on strategies to optimize fluorophore performance, aiming to enhance the tissue penetration depth and imaging contrast. First, we discuss recent strategies for wavelength tuning and brightness enhancement of functional NIR-II fluorophores, categorized by their composition into organic and inorganic fluorophores. Subsequently, we summarize the latest biomedical applications and discuss the opportunities and challenges of their clinical translation, aiming to advance the clinical application of the NIR-II imaging technology. Overall, this review provides a forward-looking perspective to guide the future development of NIR-II fluorophores.","PeriodicalId":268,"journal":{"name":"Chem","volume":"87 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101831","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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