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Rewriting lysine reactivity: Lysine-targeted bioconjugation via biomimetic polarity reversal for diversified biomolecule modification 改写赖氨酸反应性:赖氨酸靶向生物偶联,通过仿生极性反转实现多种生物分子修饰
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-12 Epub Date: 2025-09-25 DOI: 10.1016/j.chempr.2025.102744
Lu Wang , Hongxiang Yang , Jianwen Cui , Xiaoping Chen , Biao Yu , Xiaheng Zhang
Here, we present a bioinspired oxidative deamination strategy that reverses the polarity of lysine reactivity and thus allows for lysine bioconjugation in peptides and proteins with unprecedented biocompatibility and chemoselectivity. The in-situ-generated aldehyde intermediates facilitate versatile downstream transformations, including 15N/18O-labeling, reductive amination, Pinnick oxidation, and Wittig, Seyferth-Gilbert, and Van Leusen reactions. To demonstrate the broad applicability of our strategy, we successfully conjugated diverse functional payloads onto the backbone of semaglutide, full-length proteins, and therapeutic antibodies.
在这里,我们提出了一种生物启发的氧化脱胺策略,该策略逆转了赖氨酸反应性的极性,从而允许赖氨酸在肽和蛋白质中的生物偶联,具有前所未有的生物相容性和化学选择性。原位生成的醛中间体促进了多种下游转化,包括15N/ 18o标记,还原胺化,Pinnick氧化和Wittig, Seyferth-Gilbert和Van Leusen反应。为了证明我们的策略的广泛适用性,我们成功地将多种功能有效载荷偶联到semaglutide,全长蛋白和治疗性抗体的主干上。
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引用次数: 0
A dynamic charge-dependent nanofungicide platform for sustainable agrochemical deposition and delivery 一个动态电荷依赖的纳米杀菌剂平台,用于可持续农用化学品的沉积和输送
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-09 DOI: 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.
农药喷洒后对植物角质层粘附较弱,滞留效果不佳,限制了农药的利用效率。增加表面正电荷可以有效地增强附着力,但往往忽略了由于表面结合过强而导致的摄取限制。在这里,我们报道了一个独特的“动态”表面电荷特征的纳米杀菌剂平台,克服了这一困境,实现了沉积和吸收的协同增强。除了通过带相反电荷的聚合物精确地增强纳米载体的正电荷以增强附着力外,我们还结合了一个热响应单元,以便在沉积后响应温度原位降低表面电荷,避免过量的正电荷导致随后的吸收受损。该纳米杀菌剂仅使用标准剂量的一半,就能对番茄番茄灰绿杆菌达到98%的疗效。考虑到闪蒸纳米沉淀工程的规模化生产,纳米杀菌剂的动态电荷为现实世界的可持续农业提供了有希望的可行性,并提供了创新的策略,以最小化农用化学品投入来提高利用效率。
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引用次数: 0
Removing passivation irregularities for seamless electroplating across lithium, zinc, and magnesium metal batteries 消除锂、锌、镁金属电池无缝电镀的钝化不规则现象
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-04 DOI: 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。
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引用次数: 0
Intrinsic circularly polarized luminescence with a record-high dissymmetry factor via dynamic through-space conjugation 具有创纪录的高不对称因子的本征圆偏振光通过动态通过空间共轭
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-02 DOI: 10.1016/j.chempr.2025.102858
Zuping Xiong, Xiong Liu, Ziteng Zhang, Shuaitong Wei, Jiyong Liu, Qingyang Xu, Jing Zhi Sun, Jianyu Zhang, Ben Zhong Tang, Haoke Zhang
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.
如何在多功能材料的设计中利用非共价相互作用来超越传统键框架的限制?受生物系统中的弱相互作用的启发,为了克服价壳电子对排斥所施加的限制,我们探索了相邻氮原子之间的激发态通过空间共轭(TSC)作为调制材料特性的有效策略。光异构分子开关在激发态激活动态TSC,显著提高了光学和力学性能。在晶体阶段,这种动态TSC能够在610 nm处产生强大的红色圆偏振发光(CPL),持续超过300个可逆循环,在非组装的有机小分子中具有创纪录的高不对称因子(约0.20)。同时,该体系在弹性和硬度方面都表现出可逆的变化。这些发现揭示了一种反直觉的孤独对/孤独对共轭机制,为设计集成光开关和光机械功能的智能晶体材料提供了一种新的策略。
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引用次数: 0
Caging-group-free photoactivatable fluorophores with far-red emission 具有远红光发射的无笼基光激活荧光团
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-02 DOI: 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.
最先进的超分辨率显微镜方法在与具有远红色发射的光激活或光切换荧光团结合时受益匪浅,但这些荧光团中的大多数需要专门的缓冲液或依赖于光敏保护基团,这限制了它们的生物相容性。我们在此报道了一种基于含有9-酰基或9-(烷氧羰基)亚基的1-乙烯基-10-硅烷酮衍生物的无笼基策略,使最小尺寸的光活化染料具有≥680 nm的发射。9-(烷氧羰基)亚胺硅酮特别适合于活细胞标记,经过无副产物光激活产生明亮且光稳定的荧光团,可以很容易地通过STED(受激发射耗尽),PALM(光激活定位显微镜)或MINFLUX(最小光子通量)纳米技术成像。从这些光活化染料衍生的标签为多路成像开辟了新的可能性。
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引用次数: 0
Genetically engineered peptides for the biomimetic mineralization of metal-organic frameworks 用于金属-有机框架仿生矿化的基因工程肽
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-02 DOI: 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.
金属-有机骨架(MOF)的仿生矿化是一种很有前途的合成策略,具有广泛的应用前景。尽管mof与几种生物材料之间的相互作用已被广泛研究,但mof与多肽之间的相互作用仍未被探索。在这里,我们使用噬菌体展示来鉴定等孔mof (UiO-66和UiO-66- nh2)的强结合肽。Zeta电位(ZP)和圆二色性(CD)光谱测量,结合分子动力学(MD)模拟,使我们能够表征和解释mof结合肽的结构和动力学,以及构象和结合系数的差异,从而确定mof肽的识别机制。我们还成功地使用肽在合成条件下控制zr基MOF的结晶度和形态,在没有它们的情况下形成无定形产物。我们的研究结果对理解MOF-肽的相互作用具有重要意义,这对于设计和控制MOF结构以及以生物为中心的应用至关重要。
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引用次数: 0
Divergent covalent organic frameworks as antenna reactors for photoredox catalysis 发散共价有机框架作为天线反应器用于光氧化还原催化
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-02 DOI: 10.1016/j.chempr.2025.102864
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
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。
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引用次数: 0
Cruciform-hinged conjugated polymers unlock the conductivity-hydrophilicity-insolubility triad for high-performance aqueous sodium-ion batteries 十字形铰链共轭聚合物解开了高性能水钠离子电池的电导率-亲水性-不溶解度三重特性
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-26 DOI: 10.1016/j.chempr.2025.102835
Jiang Zhang, Qifeng Jiang, Qian Cheng, Ruoxi Wang, Richen Jia, Changyi Liu, Yuanyuan Xiong, Weina Han, Zexin Jin, Colin Nuckolls, Lan Jiang
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引用次数: 0
Write and erase: Macrocyclic effectors regulate imine expression in water 写和擦除:大环效应物调节亚胺在水中的表达
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-23 DOI: 10.1016/j.chempr.2025.102834
Ferran Esteve, Martina Mazzaferro, Jean-Marie Lehn
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引用次数: 0
Probing the free rotary oscillations around a single ruthenium atom in an organometallic complex 探测有机金属配合物中单个钌原子周围的自由旋转振荡
IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-01-15 Epub Date: 2025-08-05 DOI: 10.1016/j.chempr.2025.102691
Xun Li , Yohan Gisbert , Maxime Ledent , Damien Sluysmans , Gwénaël Rapenne , Claire Kammerer , Anne-Sophie Duwez
A variety of rotary molecular machine prototypes powered by light, chemical energy, or electrons have been synthesized and their operation in solution, gels, or on surfaces has been demonstrated. However, little data regarding their performances have been disclosed. Here, we report on the synthesis of molecules incorporating a five-arm rotor and the direct measurement of the work required to block the rotation around the central atom. We used single-molecule force spectroscopy (SMFS) to detect the free rotary oscillations and measure the work performed by the molecules against the mechanical load. We show that the chemical nature of the arms influences the energy barrier, causing differences in the work that the molecules can generate. Our results illustrate that SMFS, which is now widely used to probe linear displacements at a few tens of nanometer scale in macromolecules, can detect rotary motions around a single atom in a tiny synthetic molecule.
各种由光、化学能或电子驱动的旋转分子机器原型已经被合成,并且它们在溶液、凝胶或表面上的操作已经被证明。然而,有关他们的表现的数据很少被披露。在这里,我们报告了结合五臂转子的分子的合成,并直接测量了阻止围绕中心原子旋转所需的功。我们使用单分子力谱(SMFS)来检测自由旋转振荡,并测量分子对机械载荷所做的功。我们表明,臂的化学性质影响能量势垒,导致分子可以产生的功的差异。我们的研究结果表明,SMFS现在广泛用于探测大分子中几十纳米尺度的线性位移,可以检测微小合成分子中单个原子周围的旋转运动。
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引用次数: 0
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Chem
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