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A skeletally diverse library of bioactive natural-product-like compounds enabled by late-stage P450-catalyzed oxyfunctionalization 通过后期 P450 催化氧官能化作用,建立一个骨架多样化的生物活性天然产物类化合物库
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.08.003
Andrew R. Bortz , John M. Bennett , Rudi Fasan
Natural products have historically represented a major source of therapeutics and small-molecule probes for interrogating biological systems. Here, we describe the design and implementation of P450-mediated chemoenzymatic diversity-oriented synthesis (CeDOS), a strategy in which selective, regiodivergent P450-catalyzed oxyfunctionalizations are leveraged as key steps for enabling the skeletal rearrangement and diversification of a parent compound. Using this strategy and plant-derived parthenolide as the parent molecule, a structurally diverse library of over 50 unprecedented natural-product-like scaffolds was generated via divergent chemoenzymatic routes. Importantly, several members of this CeDOS library were found to exhibit notable cytotoxicity against human cancer cells as well as diversified anticancer activity profiles. This work demonstrates the power of CeDOS as a strategy for directing the construction and discovery of novel bioactive molecules, and it offers a blueprint for the broader application of this approach toward the creation and exploration of natural-product-like chemical libraries.
天然产物历来是研究生物系统的治疗药物和小分子探针的主要来源。在这里,我们介绍了 P450 介导的化学酶多样性导向合成(CeDOS)的设计和实施,在这种策略中,选择性、区域变异性 P450 催化的氧官能化被用作实现母体化合物骨架重排和多样性的关键步骤。利用这一策略,并以植物提取的马钱子内酯为母体分子,通过不同的化学酶途径生成了一个由 50 多种前所未有的天然产品类支架组成的结构多样的化合物库。重要的是,该 CeDOS 库中的几个成员对人类癌细胞表现出显著的细胞毒性和多样化的抗癌活性。这项工作证明了 CeDOS 作为一种指导构建和发现新型生物活性分子的策略的威力,并为更广泛地应用这种方法来创建和探索类似天然产物的化学库提供了蓝图。
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引用次数: 0
A high-throughput workflow to analyze sequence-conformation relationships and explore hydrophobic patterning in disordered peptoids 分析序列构象关系和探索无序蛋白胨疏水模式的高通量工作流程
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.07.025
Erin C. Day , Supraja S. Chittari , Keila C. Cunha , Roy J. Zhao , James N. Dodds , Delaney C. Davis , Erin S. Baker , Rebecca B. Berlow , Joan-Emma Shea , Rishikesh U. Kulkarni , Abigail S. Knight
Understanding how a macromolecule’s primary sequence governs its conformational landscape is crucial for elucidating its function, yet these design principles are still emerging for macromolecules with intrinsic disorder. Herein, we introduce a high-throughput workflow that implements a practical colorimetric conformational assay, introduces a semi-automated sequencing protocol using matrix-assisted laser desorption/ionization and tandem mass spectrometry (MALDI-MS/MS), and develops a generalizable sequence-structure algorithm. Using a model system of 20mer peptidomimetics containing polar glycine and hydrophobic N-butylglycine residues, we identified nine classifications of conformational disorder and isolated 122 unique sequences across varied compositions and conformations. Conformational distributions of three compositionally identical library sequences were corroborated through atomistic simulations and ion mobility spectrometry coupled with liquid chromatography. A data-driven strategy was developed using existing sequence variables and data-derived “motifs” to inform a machine-learning algorithm toward conformation prediction. This multifaceted approach enhances our understanding of sequence-conformation relationships and offers a powerful tool for accelerating the discovery of materials with conformational control.
了解大分子的主序列如何支配其构象格局对于阐明其功能至关重要,然而这些设计原则对于具有内在无序性的大分子来说仍是崭露头角。在本文中,我们介绍了一种高通量工作流程,它实现了一种实用的比色构象测定法,介绍了一种使用基质辅助激光解吸/电离和串联质谱(MALDI-MS/MS)的半自动测序方案,并开发了一种可通用的序列结构算法。利用含有极性甘氨酸和疏水性 N-丁基甘氨酸残基的 20 聚合物拟肽模型系统,我们确定了九种构象紊乱分类,并分离出 122 个不同组成和构象的独特序列。通过原子模拟和离子迁移谱-液相色谱法,我们证实了三个成分相同的文库序列的构象分布。利用现有序列变量和数据衍生的 "图案 "开发了一种数据驱动策略,为构象预测的机器学习算法提供信息。这种多方面的方法增强了我们对序列-构象关系的理解,为加速发现具有构象控制能力的材料提供了强有力的工具。
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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 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 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
Deuteration of arenes in pharmaceuticals via photoinduced solvated electrons 通过光诱导溶电子使药物中的炔烃发生氘化反应
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.06.029
Yi Tao , Cuihua Jin , Chuanwang Liu , Jiawei Bu , Ling Yue , Xipan Li , Kangjiang Liang , Chengfeng Xia
Deuterium incorporation into pharmaceutical molecules has been recognized as having a positive impact on drug efficacy and safety, allowing improvements in pharmacokinetic and/or toxicity profiles. Due to the high chemical inertness of arenes toward the hydrogen atom and the electron transfer processes, the visible light-induced direct deuteration of aromatic C(sp2)–H bonds via hydrogen isotope exchange remains unexplored. Herein, we report a photochemical deuteration protocol for efficient incorporation of deuterium into arenes in a single step, tolerating manifold functionalities in pharmaceutical compounds. Mechanistic studies provided evidence that solvated electrons were generated by light illumination with a phenolate-type photocatalyst and were involved in deuterium incorporation. This protocol was successfully applied to the late-stage deuteration of pharmaceuticals by photochemical aromatic H/D exchange on arenes.
人们已经认识到,将氘掺入药物分子会对药物疗效和安全性产生积极影响,从而改善药物动力学和/或毒性特征。由于烷烃对氢原子和电子转移过程具有很高的化学惰性,可见光通过氢同位素交换诱导芳香族 C(sp2)-H 键直接氘化的方法仍有待探索。在此,我们报告了一种光化学氘化方案,该方案只需一步就能将氘高效地掺入到烷烃中,并可容忍药物化合物中的多种官能团。机理研究证明,溶解电子是在苯酚型光催化剂的光照下产生的,并参与了氘的掺入。该方案被成功应用于通过光化学芳香族 H/D 交换在烷上对药物进行后期氘化。
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引用次数: 0
Charge delocalization and global aromaticity in a partially fused 12-porphyrin nanoring 部分融合的 12-卟啉纳米中的电荷析出和全局芳香性
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.06.034
Sebastian M. Kopp , Henrik Gotfredsen , Janko Hergenhahn , Arnau Rodríguez-Rubio , Jie-Ren Deng , He Zhu , Wojciech Stawski , Harry L. Anderson
Aromatic and antiaromatic ring currents can reveal global electronic delocalization around the circumference of π-conjugated macrocycles, although these phenomena are poorly understood in large rings. Here, we present the template-directed synthesis of a fully π-conjugated cyclic porphyrin 12-mer consisting of six β,meso,β-edge-fused porphyrin dimers connected by six butadiyne bridges. The lowest energy π-π∗ absorption band of this partially fused nanoring is shifted far into the NIR, confirming strong π-conjugation around the circumference of the macrocycle. Investigation of the oxidized and reduced nanoring-template complex by 1H and 19F NMR spectroscopy demonstrates the presence of coherent global (anti)aromatic ring currents, consistent with DFT calculations. The stronger π-conjugation enables global charge delocalization even at low levels of oxidation or reduction. These findings open new avenues for the engineering of cyclic molecular wires.
芳香族和反芳香族环电流可以揭示π共轭大环圆周上的全局电子析出,但这些现象在大环中却鲜为人知。在这里,我们介绍了一种模板指导合成的全π共轭环卟啉 12-mer,它由六个β、介、β边融合的卟啉二聚体组成,通过六个丁二炔桥连接。这种部分融合的纳米卟啉的最低能量π-π∗吸收带远远偏移到了近红外波段,证实了在大环的圆周上存在很强的π共轭作用。通过 1H 和 19F NMR 光谱对氧化和还原纳米环-模板复合物的研究表明,存在相干的全局(反)芳香环电流,这与 DFT 计算结果一致。即使在低水平的氧化或还原过程中,较强的 π 共轭作用也能实现全局电荷析出。这些发现为环状分子线的工程设计开辟了新的途径。
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引用次数: 0
Advancements in cost-effective direct air capture technology 具有成本效益的直接空气捕获技术的进步
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.09.025
Mihrimah Ozkan, Saeb Besarati, Christopher Gordon, Gaël Gobaille-Shaw, Noah McQueen
Advancements in cost-effective direct air capture (DAC) technology have become critical in addressing climate change, with a particular emphasis on energy and cost reductions. Recent innovations have significantly decreased the energy requirements of DAC systems. In collaboration with experts from industry leaders such as Climeworks, Carbon Capture, Mission Zero, and Heirloom, the latest developments highlight DAC technology’s potential to become a viable and sustainable solution for large-scale CO₂ removal. These advancements include reductions in energy consumption to as low as 1,055 kWh per ton of CO₂ through electrochemical methods and strategic integration of renewable energy sources like geothermal power. Additionally, economies of scale achieved through bulk purchasing and streamlined manufacturing processes have lowered DAC modules’ per-unit cost. Financial incentives and supportive policies, such as the 45Q tax credit in the United States, enhance the economic feasibility of these technologies. These innovations underscore the substantial contributions of DAC technology to global climate change mitigation efforts, making it a promising solution for achieving significant reductions in atmospheric CO₂ levels.
具有成本效益的直接空气捕集(DAC)技术的进步已成为应对气候变化的关键,其中特别强调能源和成本的降低。最近的创新大大降低了 DAC 系统的能源需求。通过与来自 Climeworks、Carbon Capture、Mission Zero 和 Heirloom 等行业领导者的专家合作,最新进展凸显了 DAC 技术成为大规模二氧化碳去除的可行且可持续的解决方案的潜力。这些进步包括通过电化学方法和地热能等可再生能源的战略整合,将能耗降低到每吨二氧化碳 1,055 千瓦时。此外,通过批量采购和简化制造流程实现的规模经济降低了 DAC 模块的单位成本。财政激励和支持政策(如美国的 45Q 税收抵免)提高了这些技术的经济可行性。这些创新凸显了 DAC 技术对全球气候变化减缓工作的巨大贡献,使其成为实现大幅降低大气中 CO₂ 水平的一个前景广阔的解决方案。
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引用次数: 0
Dynamic vertical triplet energies: Understanding and predicting triplet energy transfer 动态垂直三重能:了解和预测三重能传递
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.07.001
Mihai V. Popescu , Robert S. Paton
A computational approach for modeling and predicting triplet energy sensitization of organic molecules is described, which involves sampling the instantaneous, vertical energy gaps over molecular vibrational motions. This approach provides new theoretical support for the hot-band mechanism of energy transfer, in which the energy difference between donor and acceptor can be lessened by geometric distortions. We demonstrate excellent predictive performance against experimental triplet energies, with R2 = 0.97 and a mean absolute error (MAE) of 1.7 kcal/mol, for a collection of 24 small organic molecules, whereas a static, adiabatic description performs significantly worse (R2 = 0.51, MAE = 9.5 kcal/mol). Using this approach, it is possible to quantitatively predict the correct E/Z-isomerism of alkenes under energy transfer, for which adiabatic calculations predict the wrong outcome.
本文介绍了一种用于模拟和预测有机分子三重能敏化的计算方法,该方法涉及对分子振动运动的瞬时垂直能隙进行采样。这种方法为能量转移的热带机制提供了新的理论支持,在这种机制中,供体和受体之间的能量差可以通过几何畸变而减小。我们对 24 种小有机分子的实验三重态能量进行了出色的预测,R2 = 0.97,平均绝对误差(MAE)为 1.7 kcal/mol,而静态绝热描述的结果要差得多(R2 = 0.51,MAE = 9.5 kcal/mol)。利用这种方法,可以定量预测烯烃在能量转移情况下正确的 E/Z 异构体,而绝热计算预测的结果是错误的。
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引用次数: 0
Cooperative hydrogenation catalysis at a constrained gallylene-nickel(0) interface 受约束的镓-镍(0)界面上的协同氢化催化作用
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-13 DOI: 10.1016/j.chempr.2024.10.016
Till L. Kalkuhl, Israel Fernández, Terrance J. Hadlington
The discovery of unique mechanisms in 3d metal catalysis is of paramount importance in utilizing these Earth-abundant metals in place of scarce precious metals. Inspired by the Horiuti-Polanyi mechanism at play in heterogeneous hydrogenation catalysts, we describe a bimetallic molecular catalyst that can selectively semi-hydrogenate alkynes via a ligand-to-substrate hydride transfer mechanism. This mimics established heterogeneous mechanisms in which remote surface-bound hydride ligands undergo a similar reactive process. This is achieved through the development of a chelate-constrained gallium(I) ligand, which operates in concert with nickel(0) to (reversibly) cleave H2, generating a [GaNi] 1,2-dihydride complex that is found to be the resting state in the catalytic process. This discovery takes steps toward utilizing non-innocent low-valent group 13 centers in effective cooperative catalysis, opening new mechanistic pathways that may aid in employing Earth-abundant metals in key catalytic transformations.
发现 3d 金属催化的独特机制对于利用这些地球上丰富的金属来替代稀缺的贵金属至关重要。受异相氢化催化剂中 Horiuti-Polanyi 机制的启发,我们描述了一种双金属分子催化剂,它可以通过配体到底物的氢化物转移机制选择性地半氢化炔烃。这模仿了已建立的异质机制,其中远距离表面结合的氢化物配体也经历了类似的反应过程。这是通过开发一种受螯合物约束的镓(I)配体实现的,该配体与镍(0)协同(可逆地)裂解 H2,生成[GaNi] 1,2-二酸酐复合物,该复合物被发现是催化过程中的静止状态。这一发现为利用非无辜的低价 13 族中心进行有效的合作催化迈出了一步,开辟了新的机理途径,可能有助于在关键的催化转化过程中使用地球上富集的金属。
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引用次数: 0
De novo luciferases enable multiplexed bioluminescence imaging 新荧光素酶实现了多重生物发光成像
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-12 DOI: 10.1016/j.chempr.2024.10.013
Julie Yi-Hsuan Chen, Qing Shi, Xue Peng, Jean de Dieu Habimana, James Wang, William Sobolewski, Andy Hsien-Wei Yeh
We leverage AI-powered de novo protein design to create a new generation of luciferase catalysts, termed the neoLux series, which exhibit superior properties over native luciferases. These features include compact size, robust stability, cofactor independence, efficient cellular expression, higher catalytic efficiency, and unique substrate orthogonality, marking a significant advancement beyond the limitations of native luciferases. Additionally, we computationally designed highly efficient neoLux-fluorescent protein Förster resonance energy transfer (FRET) fusions capable of simultaneous multi-parametric imaging in cellulo and in vivo. Our pioneering approach has created a unified luminescent toolkit to allow for multi-colored tracking of cancer heterogeneity in vivo, paving the way for complex biological discovery.
我们利用人工智能驱动的从头蛋白质设计,创造出新一代荧光素酶催化剂(称为 neoLux 系列),与原生荧光素酶相比,它们具有更优越的特性。这些特性包括体积小巧、稳定性强、不依赖于辅助因子、细胞表达效率高、催化效率高以及独特的底物正交性,标志着超越原生荧光素酶限制的重大进步。此外,我们通过计算设计了高效的新荧光蛋白佛斯特共振能量转移(FRET)融合体,能够在细胞内和体内同时进行多参数成像。我们的开创性方法创建了一个统一的发光工具包,可在体内对癌症异质性进行多色追踪,为复杂的生物学发现铺平了道路。
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引用次数: 0
One-pot catalytic conversion of polyethylene wastes to gasoline through a dual-catalyst system 通过双催化剂系统将聚乙烯废料一锅催化转化为汽油
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-06 DOI: 10.1016/j.chempr.2024.10.007
Wanying Han, Longfei Lin, Ziyu Cen, Yubin Ke, Qian Xu, Junfa Zhu, Xuelei Mei, Zhanghui Xia, Xinrui Zheng, Yaqin Wang, Yani Liu, Mingyuan He, Haihong Wu, Buxing Han
Chemical upcycling of polyethylene (PE) waste presents a viable and promising approach to address the issues of plastic waste accumulation. However, developing cost-effective and efficient routes for converting PE waste into value-added products remains a challenging task. Here, we report a one-pot, dual-catalyst system for efficient conversion of PE into gasoline without the need for noble-metal catalysts, external hydrogen, or solvents. A gasoline yield of up to 87% is achieved over a dual-catalyst system comprising WZr-KIT-6 and HZSM-5 at 240°C. The WZr-KIT-6 catalyst facilitated the activation and pre-cracking of PE chains into unsaturated oligomers over Si-O-Zr and W-O(H)-Zr sites. These unsaturated oligomers, characterized by increased mobility and reactivity, were subsequently converted into C4–C12 gasoline-range compounds through β-scission, isomerization, and hydride transfer over HZSM-5. The synergistic reaction mechanism over mesoporous and microporous materials was crucial for enhancing the efficiency and selectivity of PE conversion.
聚乙烯(PE)废料的化学升级再循环是解决塑料废料堆积问题的一种可行且前景广阔的方法。然而,开发具有成本效益且高效的途径将聚乙烯废料转化为增值产品仍是一项具有挑战性的任务。在此,我们报告了一种无需贵金属催化剂、外部氢气或溶剂即可将聚乙烯高效转化为汽油的单锅双催化剂系统。由 WZr-KIT-6 和 HZSM-5 组成的双催化剂系统可在 240°C 的温度下实现高达 87% 的汽油收率。WZr-KIT-6 催化剂可促进聚乙烯链在 Si-O-Zr 和 W-O(H)-Zr 位点上活化并预裂解为不饱和低聚物。这些不饱和低聚物具有更高的流动性和反应活性,随后在 HZSM-5 上通过 β 裂解、异构化和氢化物转移转化为 C4-C12 汽油范围的化合物。介孔和微孔材料上的协同反应机制对于提高聚乙烯转化的效率和选择性至关重要。
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引用次数: 0
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