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Engineering a photoenzyme to use red light 利用红光改造光酵素
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-16 DOI: 10.1016/j.chempr.2024.09.017
Jose M. Carceller, Bhumika Jayee, Claire G. Page, Daniel G. Oblinsky, Gustavo Mondragón-Solórzano, Nithin Chintala, Jingzhe Cao, Zayed Alassad, Zheyu Zhang, Nathaniel White, Danny J. Diaz, Andrew D. Ellington, Gregory D. Scholes, Sijia S. Dong, Todd K. Hyster
Photoenzymatic reactions involving flavin-dependent “ene”-reductases (EREDs) rely on protein-templated charge transfer (CT) complexes between the cofactor and substrate for radical initiation. These complexes typically absorb in the blue region of the electromagnetic spectrum. Here, we engineered an ERED to form CT complexes that absorb red light. Mechanistic studies indicate that red-light activity is due to the growth of a red-absorbing shoulder off the previously identified cyan absorption feature. Molecular dynamics simulations, docking, and excited-state calculations suggest that the cyan feature involves a π→π∗ transition on flavin, whereas the red-light absorption is a π→π∗ transition between flavin and the substrate. Differences in the electronic transition are due to changes in the substrate-binding conformation and allosteric tuning of the electronic structure of the cofactor-substrate complex. Microenvironment tuning of the CT complex for red-light activity is observed with other engineered photoenzymatic reactions, highlighting this effect’s generality.
涉及黄素依赖性 "烯 "还原酶(EREDs)的光酶促反应依赖于辅助因子和底物之间由蛋白质引发的电荷转移(CT)复合物来启动自由基。这些复合物通常在电磁波谱的蓝色区域吸收。在这里,我们设计了一种ERED,以形成能吸收红光的CT复合物。机理研究表明,红光活性是由于在先前确定的青色吸收特征上增加了一个红色吸收肩。分子动力学模拟、对接和激发态计算表明,青色特征涉及黄素上的π→π∗转变,而红光吸收则是黄素和底物之间的π→π∗转变。电子转变的差异是由于底物结合构象的变化和辅因子-底物复合物电子结构的异构调整造成的。在其他工程光酶促反应中也观察到了 CT 复合物在红光下活性的微环境调整,这突显了这种效应的普遍性。
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引用次数: 0
Exerting control of self-assembly pathways via morphological switching and patterning in amino-acid-based benzene-1,3,5-tricarboxamide conjugates 通过氨基酸基苯-1,3,5-三甲酰胺共轭物的形态切换和图案化控制自组装途径
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-16 DOI: 10.1016/j.chempr.2024.09.020
Aramballi J. Savyasachi, Oxana Kotova, Ena T. Luis, Amy D. Lynes, Shaun Mills, Sandra A. Bright, Gavin J. McManus, Matthias E. Möbius, D. Clive Williams, Robert Pal, John J. Boland, Thorfinnur Gunnlaugsson
Small structural changes to benzene-1,3,5-tricarboxamide (BTA) dictate its self-assembly behavior and morphological outcome. Functionalization with an α-amino acid close to the BTA core, which also possesses a terminal terpyridine (tpy) unit, led to a robust gel in the case of glycine, whereas monodisperse, solid microspheres formed in the case of alanine, phenylalanine, and leucine. The self-assembly pathways of the chiral and achiral BTAs are orthogonal and both microspheres and gel fibers independently assemble in the same medium. Further hierarchical self-assembly results upon addition of lanthanide ions (i.e., Eu(III) and Tb(III) that emit at long wavelengths with long excited-state lifetimes) that crosslink the microspheres through coordination, whereas coordination within the gel led to a change in morphology toward microspheres, as well as the formation of hierarchical superstructures. The chirality of the BTA influences helicity of the assembly and the resulting enantiomeric conformation around the lanthanides, evidenced by circularly polarized luminescence.
苯-1,3,5-三甲酰胺(BTA)的微小结构变化决定了其自组装行为和形态结果。用靠近 BTA 核心的 α- 氨基酸进行官能化(BTA 核心还具有一个末端的terpyridine (typy)单元)会导致甘氨酸形成坚固的凝胶,而丙氨酸、苯丙氨酸和亮氨酸则会形成单分散的固体微球。手性和非手性 BTA 的自组装途径是正交的,微球和凝胶纤维在同一介质中独立组装。加入镧系离子(即 Eu(III)和 Tb(III),它们的发射波长长、激发态寿命长)后,微球通过配位交联,而凝胶中的配位导致形态向微球转变,并形成分层超结构,从而进一步实现分层自组装。BTA 的手性影响了组装的螺旋性以及由此产生的围绕镧系元素的对映体构象,这一点可以通过圆偏振发光得到证明。
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引用次数: 0
Dearomative dimerization of quinolines and their skeletal rearrangement to indoles triggered by single-electron transfer 单电子转移引发的喹啉二聚化及其骨架重排为吲哚的过程
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-16 DOI: 10.1016/j.chempr.2024.09.016
Eugene Yew Kun Tan, Alireza Dehdari, Amirah S. Mat Lani, Derek A. Pratt, Shunsuke Chiba
Dearomatization of two-dimensional planar aromatic feedstocks is an attractive strategy for the introduction of three-dimensional vectors into chemical scaffolds to expand chemical space for drug discovery. Here, we demonstrate the dearomative dimerization and skeletal rearrangement of quinolines under polysulfide anion photocatalysis, in which the additive dictates the reaction courses. In the presence of formate, dearomative dimerization of quinolines is followed by cyclization to form an sp3-rich polyheterocyclic hybrid of a 2,5-methanobenzo[b]azepine and a tetrahydroquinoline in a net-reductive manner. On the other hand, in the presence of triethylamine instead of formate, sequential dimerization and skeletal rearrangement occurs to afford 4-(3-indolylmethyl)quinolines in a redox-neutral manner. These observations enabled the design of a net-reductive skeletal rearrangement of 4-arylquinolines to 3-(arylmethyl)indoles. Detailed mechanistic investigations revealed that this umpolung transformation from electron-deficient quinolines to electron-rich indoles is mediated via a 1,2-aryl migration/ring-contraction sequence, as opposed to the more commonly invoked neophyl-like rearrangement.
二维平面芳香原料的脱芳烃化是一种极具吸引力的策略,可将三维载体引入化学支架,从而拓展药物发现的化学空间。在这里,我们展示了在多硫阴离子光催化作用下,喹啉的脱芳烃二聚化和骨架重排,其中添加剂决定了反应过程。在有甲酸盐存在的情况下,喹啉的脱芳香二聚化反应之后会发生环化反应,以净还原的方式形成富含 sp3 的 2,5-甲基苯并[b]氮杂卓和四氢喹啉的多杂环。另一方面,在有三乙胺而不是甲酸盐的情况下,会发生连续的二聚化和骨架重排,从而以氧化还原中性的方式生成 4-(3-吲哚甲基)喹啉。根据这些观察结果,设计出了一种将 4-芳基喹啉类化合物净还原为 3-(芳基甲基)吲哚类化合物的骨架重排方法。详细的机理研究发现,这种从电子缺乏的喹啉到电子丰富的吲哚的骤变是通过 1,2-芳基迁移/环收缩序列介导的,而不是通常所说的新芳基样重排。
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引用次数: 0
The cyclotriborate trianion 环三硼酸盐三阴离子
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-16 DOI: 10.1016/j.chempr.2024.09.002
Manjur O. Akram, Caleb D. Martin
In this issue of Chem, Kinjo and Feng report the synthesis of a cyclotriborate trianion (B3R63−), a highly charged boron ring system with discrete two-center two-electron bonds. With three contiguous borates, the B33− core of the feature compound defies Coulomb’s law and represents the first homocyclic boron analog of the ubiquitous cyclopropane. The remarkable stability enabled full characterization and opens new vistas in the field of multiply charged boron ions.
在本期《化学》杂志上,Kinjo 和 Feng 报告了一种环三硼酸盐三阴离子(B3R63-)的合成,这是一种具有离散双中心双电子键的高电荷硼环系统。由于具有三个连续的硼酸盐,该特征化合物的 B33- 核心违背了库仑定律,代表了无处不在的环丙烷的第一个同环硼类似物。其出色的稳定性使其得以全面表征,并为多电荷硼离子领域开辟了新的前景。
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引用次数: 0
Globally aromatic odd-electron π-magnetic macrocycle 全芳香奇电子π-磁性大环
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-15 DOI: 10.1016/j.chempr.2024.09.015
Federico Villalobos, Jan Berger, Adam Matěj, Reed Nieman, Ana Sánchez-Grande, Diego Soler, Andrés Pinar Solé, Hans Lischka, Mikuláš Matoušek, Jiri Brabec, Libor Veis, Alba Millan, Carlos Sánchez-Sánchez, Araceli G. Campaña, Juan M. Cuerva, Pavel Jelínek
Molecular π-magnets based on single organic molecules have attracted increasing attention for their potential applications in optoelectronics and spintronics. Global aromaticity in conjugated macrocyclic polyradicaloids is still an open question that has only been tackled in molecules with an even number of electrons. Here, we report the on-surface synthesis of a cyclopenta-ring-fused oligo(m-phenylene) macrocycle, 9MC, with an odd number of electrons. The generated polyradicaloid undergoes a surface-induced distortion to a D3h symmetry with a fully delocalized doublet ground state. Interestingly, 9MC exhibits two aromatic annulene-within-an-annulene (AWA) ring currents in the inner and outer rings.
基于单一有机分子的分子π磁体因其在光电子学和自旋电子学中的潜在应用而受到越来越多的关注。共轭大环多核物的全局芳香性仍是一个未决问题,目前只在电子数为偶数的分子中得到解决。在此,我们报告了奇数电子数的环戊环融合低聚(间苯二酚)大环 9MC 的表面合成。生成的多辐射类化合物在表面诱导下畸变为 D3h 对称性,并具有完全去局域化的双基态。有趣的是,9MC 在内环和外环中显示出两个芳香环烯-环内-烯(AWA)环电流。
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引用次数: 0
Nanocellulose: New horizons in organic chemistry and beyond 纳米纤维素:有机化学及其他领域的新视野
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-11 DOI: 10.1016/j.chempr.2024.09.007
Sayad Doobary, Varvara Apostolopoulou-Kalkavoura, Aji P. Mathew, Berit Olofsson
The study of different forms of nanocellulose is a fast-growing field with many advantages. As a biobased polymer, it holds strong promise to replace petrochemical solid supports that need to be phased out. While there are already a plethora of nanocellulose applications, e.g., in the fields of material science, engineering, and water treatment, there is a surprising lack of reports concerning their applications in catalysis and organic chemistry. A crucial property of nanocellulose is its well-defined surface structure, which enables surface modifications to reach useful solid-supported catalysts and reagents. In this perspective, we explore the use of unmodified and modified variants of nanocellulose in organic chemistry. We further propose that the use of mechanochemistry could be a future application to increase the activity and eliminate the requirement for aqueous media due to nanocellulose’s dispersion issues.
对不同形式的纳米纤维素的研究是一个快速发展的领域,具有许多优势。作为一种生物基聚合物,纳米纤维素有望取代亟待淘汰的石化固体支持物。虽然纳米纤维素在材料科学、工程学和水处理等领域的应用已经非常广泛,但有关其在催化和有机化学领域应用的报道却少得令人吃惊。纳米纤维素的一个重要特性是其定义明确的表面结构,这使得通过表面改性可以获得有用的固体支撑催化剂和试剂。从这个角度出发,我们探讨了未改性和改性纳米纤维素在有机化学中的应用。我们进一步提出,由于纳米纤维素的分散问题,使用机械化学可能是未来提高活性和消除对水介质要求的一种应用。
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引用次数: 0
Stimuli-responsive actuation enabled by selective host-guest recognition of urea cage 通过对尿素笼的主客体选择性识别实现刺激响应式驱动
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.09.013
Organic cages, featuring the selective stimuli response and reversible encapsulation of guest molecules, demonstrate a huge potential in guest-triggered actuation. In this issue of Chem, Khashab and co-workers exploited host-guest recognition of organic urea cages with three-dimensional structures to integrate multiple mechanical actuations into a single material for the first time.
有机笼具有选择性刺激响应和客体分子可逆封装的特点,在客体触发致动方面展现出巨大的潜力。在本期《化学》杂志上,Khashab 及其合作者利用具有三维结构的有机脲笼的主客识别功能,首次将多种机械致动功能集成到了单一材料中。
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引用次数: 0
The tension-activated carbon–carbon bond 张力激活的碳-碳键
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.05.012
Mechanical force drives distinct chemical reactions; yet, its vectoral nature results in complicated coupling with reaction trajectories. Here, we utilize a physical organic model inspired by the classical Morse potential and its differential forms to identify effective force constant (keff) and reaction energy (ΔE) as key molecular features that govern mechanochemical kinetics. Through a comprehensive experimental and computational investigation with four norborn-2-en-7-one (NEO) mechanophores, we establish the relationship between these features and the force-dependent energetic changes along the reaction pathways. We show that the complex kinetic behavior of the tensioned bonds is generally and quantitatively predicted by a simple multivariate linear regression based on the two easily computed features with a straightforward workflow. These results demonstrate a general mechanistic framework for mechanochemical reactions under tensile force and provide a highly accessible tool for the large-scale computational screening in the design of mechanophores.
机械力驱动着不同的化学反应;然而,其矢量性质导致了与反应轨迹的复杂耦合。在此,我们利用受经典莫尔斯电势及其微分形式启发的物理有机模型,确定有效力常数(keff)和反应能量(ΔE)是支配机械化学动力学的关键分子特征。通过对四种降冰片-2-烯-7-酮(NEO)机械分子进行全面的实验和计算研究,我们确定了这些特征与反应路径上的力依赖性能量变化之间的关系。我们的研究表明,张力键的复杂动力学行为一般可以通过简单的多元线性回归进行定量预测,而多元线性回归是基于两个易于计算的特征,工作流程简单明了。这些结果展示了拉伸力作用下机械化学反应的一般机械框架,并为机械分子设计中的大规模计算筛选提供了一个非常容易获得的工具。
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引用次数: 0
Anion-derived contact ion pairing as a unifying principle for electrolyte design 阴离子衍生接触离子配对作为电解质设计的统一原则
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.07.031
Enabling new electrochemical technologies requires systems that can operate under ever-more demanding conditions, and progress in energy storage applications reveals tantalizing opportunities to reimagine electrolyte design for performance at extreme potentials. A common thread among these innovations is the formation of significant populations of contact ion pairs (CIPs) in the electrolyte, regardless of the specific cation chemistry or solvent system. The examples summarized in this review suggest that a set of general electrolyte design rules likely exists, where the purposeful selection of anion chemistry can yield CIP structures with tunable control over reaction thermodynamics, kinetics, and interphase chemistry. Identifying the relevant descriptors for high-performance, anion-derived CIP structures can be achieved utilizing a combined experimental and computational approach, aided by machine learning and artificial intelligence, to more rapidly survey the vast combinatorial space available and to enable a new generation of electrolytes for decarbonized electrochemical processes at scale.
新型电化学技术的应用要求系统能够在要求越来越高的条件下运行,而储能应用方面的进展则为重新设计电解质以实现极端电位下的性能提供了诱人的机会。这些创新的一个共同点是在电解质中形成大量接触离子对(CIPs),而与具体的阳离子化学或溶剂系统无关。本综述中总结的例子表明,可能存在一套通用的电解质设计规则,有目的地选择阴离子化学性质可以产生可调节控制反应热力学、动力学和相间化学性质的 CIP 结构。利用实验和计算相结合的方法,并在机器学习和人工智能的辅助下,可以确定高性能阴离子衍生 CIP 结构的相关描述符,从而更迅速地调查现有的巨大组合空间,并为脱碳电化学过程大规模生产新一代电解质。
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引用次数: 0
Arylative difunctionalization of olefins using easily accessed organobismuth (V) reagents 使用易于获取的有机铋 (V) 试剂对烯烃进行芳基化反官能度处理
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-10 DOI: 10.1016/j.chempr.2024.09.014
In this issue of Chem, Li and Rawal present an exciting new application of Ar3BiCl2 as convenient reagents for arylative difunctionalization of alkenes using visible or near-visible light. Unburdened by air and moisture sensitivity, the method affords rapid and facile azido-, cyano-, and chloro-arylation of a bevy of functionalized alkenes.
在本期《化学》杂志上,Li 和 Rawal 介绍了 Ar3BiCl2 作为方便的试剂在利用可见光或近视光对烯烃进行芳基二官能化时的一种令人兴奋的新应用。该方法不受空气和湿度的影响,能快速、简便地对多种官能化烯进行叠氮、氰和氯芳基化反应。
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引用次数: 0
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