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Hyperforatone A, the 1,8-seco rearranged polycyclic polyprenylated acylphloroglucinol with a unique bicyclo[5.4.0]undecane core from Hypericum perforatum
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-20 DOI: 10.1016/j.cclet.2024.110478
Wu-Yang Liu , Xin-Xiang Lei , Wen-Ji Wang , Jun-Mian Tian , Yu-Qi Gao , Jin-Ming Gao
Hyperforatone A (1), the 1,8-seco rearranged polycyclic polyprenylated acylphloroglucinol, possessed an unusual bicyclo[5.4.0]undecane skeleton bearing a 5/7/6/5 ring system, and two known biosynthetically related precursors (2 and 3) were isolated from Hypericum perforatum (St. John's wort). The structure and absolute configuration were unambiguously confirmed by a combination of comprehensive spectroscopic data, computational methods including residual dipolar couplings (RDCs), and X-ray crystallography. Density functional theory (DFT) calculations revealed that the cationic cyclization reaction was key to proposed formation mechanism for hyperforatone A. Furthermore, in vitro and in vivo experiments demonstrated that compound 1 was a potential anti-neuroinflammatory agent.
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引用次数: 0
Film thickness effect on 2D lead-free hybrid double perovskite properties: Band gap, photocurrent and stability
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-20 DOI: 10.1016/j.cclet.2024.110477
Mohamed Saber Lassoued , Faizan Ahmad , Yanzhen Zheng
Lead-free hybrid double perovskites (LFHDPs) have received a lot of attention due to their environmental friendliness and promising attributes. However, studying the effect of film thickness on LFHDPs optoelectronic properties has not yet been investigated. Herein, we synthesized two new Ruddlesden–Popper LFHDPs, namely (C5H12N)4AgBiI8 (CAB-1) and (C6H14N)4AgBiI8 (CAB-2) using cyclopentylamine and cyclohexylamine as monoamine ligands. Indeed, these two Ag(I)-Bi(III) LFHDPs form smooth and uniform films ranging in thickness from 250 nm to 1 μm, with preferred orientations. Notably, the studies on the optical properties showed that the direct band gap value decreased from 2.17 eV to 1.91 eV for CAB-1 and from 2.05 eV to 1.86 eV for CAB-2 with increasing thickness. Accordingly, photo-current response using a xenon lamp revealed a significant difference of over 1000 nA between light and dark conditions for 1 μm-thickness films, suggesting potential for light harvesting. Other than that, thicker films of CAB-1 and CAB-2 exhibit high stability for 90 days in a relatively humid environment (RH of 55 %), paving the way for promising optoelectronic applications.
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引用次数: 0
Constant-potential simulation of electrocatalytic N2 reduction over atomic metal-N-graphene catalysts
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-19 DOI: 10.1016/j.cclet.2024.110476
Sanmei Wang , Yong Zhou , Hengxin Fang , Chunyang Nie , Chang Q Sun , Biao Wang
Charge-neutral method (CNM) is extensively used in investigating the performance of catalysts and the mechanism of N2 electrochemical reduction (NRR). However, disparities remain between the predicted potentials required for NRR by the CNM methods and those observed experimentally, as the CNM method neglects the charge effect from the electrode potential. To address this issue, we employed the constant electrode potential (CEP) method to screen atomic transition metal-N-graphene (M1/N-graphene) as NRR electrocatalysts and systematically investigated the underlying catalytic mechanism. Among eight types of M1/N-graphene (M1 = Mo, W, Fe, Re, Ni, Co, V, Cr), W1/N-graphene emerges as the most promising NRR electrocatalyst with a limiting potential as low as −0.13 V. Additionally, the W1/N-graphene system consistently maintains a positive charge during the reaction due to its Fermi level being higher than that of the electrode. These results better match with the actual circumstances compared to those calculated by conventional CNM method. Thus, our work not only develops a promising electrocatalyst for NRR but also deepens the understanding of the intrinsic electrocatalytic mechanism.
{"title":"Constant-potential simulation of electrocatalytic N2 reduction over atomic metal-N-graphene catalysts","authors":"Sanmei Wang ,&nbsp;Yong Zhou ,&nbsp;Hengxin Fang ,&nbsp;Chunyang Nie ,&nbsp;Chang Q Sun ,&nbsp;Biao Wang","doi":"10.1016/j.cclet.2024.110476","DOIUrl":"10.1016/j.cclet.2024.110476","url":null,"abstract":"<div><div>Charge-neutral method (CNM) is extensively used in investigating the performance of catalysts and the mechanism of N<sub>2</sub> electrochemical reduction (NRR). However, disparities remain between the predicted potentials required for NRR by the CNM methods and those observed experimentally, as the CNM method neglects the charge effect from the electrode potential. To address this issue, we employed the constant electrode potential (CEP) method to screen atomic transition metal-N-graphene (M<sub>1</sub>/N-graphene) as NRR electrocatalysts and systematically investigated the underlying catalytic mechanism. Among eight types of M<sub>1</sub>/N-graphene (M<sub>1</sub> = Mo, W, Fe, Re, Ni, Co, V, Cr), W<sub>1</sub>/N-graphene emerges as the most promising NRR electrocatalyst with a limiting potential as low as −0.13 V. Additionally, the W<sub>1</sub>/N-graphene system consistently maintains a positive charge during the reaction due to its Fermi level being higher than that of the electrode. These results better match with the actual circumstances compared to those calculated by conventional CNM method. Thus, our work not only develops a promising electrocatalyst for NRR but also deepens the understanding of the intrinsic electrocatalytic mechanism.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 3","pages":"Article 110476"},"PeriodicalIF":9.4,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143356835","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}
引用次数: 0
Recent advances in semi-heterogenous photocatalysis in organic synthesis 有机合成中半同源光催化技术的最新进展
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-18 DOI: 10.1016/j.cclet.2024.110469
Jia-Cheng Hou , Wei Cai , Hong-Tao Ji , Li-Juan Ou , Wei-Min He
Semi-heterogeneous photocatalysis has emerged as a powerful and productive platform in organic chemistry, which provides mild and eco-friendly conditions for a diverse range of bond-forming reactions. The synergy of homogeneous catalysts and heterogeneous catalysts inherits their main advantages, such as higher activities, easy separation and superior recyclability. In this review, we summarize the recent advances in recyclable semi-heterogenous protocols for the light promoted bond-forming reactions and identify directions for future research according to the different photocatalysts/metal/redox catalysts involved. Notably, this review is not a comprehensive description of reported literature but aim to highlight and illustrate key concepts, strategies, reaction model, reaction conditions and mechanisms.
半均相光催化技术已成为有机化学领域一个强大而富有成效的平台,它为各种成键反应提供了温和而环保的条件。均相催化剂和异相催化剂的协同作用继承了它们的主要优点,如更高的活性、易于分离和卓越的可回收性。在本综述中,我们总结了用于光促进成键反应的可回收半异质方案的最新进展,并根据所涉及的不同光催化剂/金属/氧化还原催化剂确定了未来的研究方向。值得注意的是,本综述并非对已报道文献的全面描述,而是旨在强调和说明关键概念、策略、反应模型、反应条件和机理。
{"title":"Recent advances in semi-heterogenous photocatalysis in organic synthesis","authors":"Jia-Cheng Hou ,&nbsp;Wei Cai ,&nbsp;Hong-Tao Ji ,&nbsp;Li-Juan Ou ,&nbsp;Wei-Min He","doi":"10.1016/j.cclet.2024.110469","DOIUrl":"10.1016/j.cclet.2024.110469","url":null,"abstract":"<div><div>Semi-heterogeneous photocatalysis has emerged as a powerful and productive platform in organic chemistry, which provides mild and eco-friendly conditions for a diverse range of bond-forming reactions. The synergy of homogeneous catalysts and heterogeneous catalysts inherits their main advantages, such as higher activities, easy separation and superior recyclability. In this review, we summarize the recent advances in recyclable semi-heterogenous protocols for the light promoted bond-forming reactions and identify directions for future research according to the different photocatalysts/metal/redox catalysts involved. Notably, this review is not a comprehensive description of reported literature but aim to highlight and illustrate key concepts, strategies, reaction model, reaction conditions and mechanisms.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 2","pages":"Article 110469"},"PeriodicalIF":9.4,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657003","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}
引用次数: 0
Corrigendum to ‘Fluorescence immunoassay based on alkaline phosphatase-induced in situ generation of fluorescent non-conjugated polymer dots’ [Chinese Chemical Letters 34 (2023) 107672] 基于碱性磷酸酶诱导原位生成荧光非共轭聚合物点的荧光免疫测定"[中国化学快报 34 (2023) 107672]勘误表
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-17 DOI: 10.1016/j.cclet.2024.109881
Donghui Wu , Qilin Zhao , Jian Sun , Xiurong Yang
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引用次数: 0
Sp1-hybridized linear and cyclic carbon chain
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-16 DOI: 10.1016/j.cclet.2024.110466
Huiju Cao, Lei Shi
Carbon materials have long been a subject of study, offering diverse properties based on their hybridized structures. Except sp2-hybridized graphene and carbon nanotubes, the focus on sp1-hybridized carbon chains has garnered significant interest due to its unique predicted properties, despite limitations in research and development stemming from its high reactivity. This comprehensive review summaries recent advancements in synthetic methodologies and characterization of the sp1-hybridized carbon chains, encompassing linear carbon chains and cyclo[n]carbons. The review traces significant milestones in synthesis and offers a thorough overview of various properties on linear and cyclic carbon chains, from their initial discovery to recent development. The advancing synthetic methods have led to practical breakthroughs, transitioning theoretical concepts into tangible carbon-chain materials. However, challenges persist in achieving controlled and scalable preparation due to the high reactivity associated with sp1-hybridization. Future research prospects focus on fundamental studies, such as exploring the transition length from polyyne to carbyne and experimentally determining the properties of single carbon chains. This review underscores both the progress made and the compelling avenues for future exploration in the dynamic field of sp1-hybridized carbon chains.
{"title":"Sp1-hybridized linear and cyclic carbon chain","authors":"Huiju Cao,&nbsp;Lei Shi","doi":"10.1016/j.cclet.2024.110466","DOIUrl":"10.1016/j.cclet.2024.110466","url":null,"abstract":"<div><div>Carbon materials have long been a subject of study, offering diverse properties based on their hybridized structures. Except sp<sup>2</sup>-hybridized graphene and carbon nanotubes, the focus on sp<sup>1</sup>-hybridized carbon chains has garnered significant interest due to its unique predicted properties, despite limitations in research and development stemming from its high reactivity. This comprehensive review summaries recent advancements in synthetic methodologies and characterization of the sp<sup>1</sup>-hybridized carbon chains, encompassing linear carbon chains and cyclo[<em>n</em>]carbons. The review traces significant milestones in synthesis and offers a thorough overview of various properties on linear and cyclic carbon chains, from their initial discovery to recent development. The advancing synthetic methods have led to practical breakthroughs, transitioning theoretical concepts into tangible carbon-chain materials. However, challenges persist in achieving controlled and scalable preparation due to the high reactivity associated with sp<sup>1</sup>-hybridization. Future research prospects focus on fundamental studies, such as exploring the transition length from polyyne to carbyne and experimentally determining the properties of single carbon chains. This review underscores both the progress made and the compelling avenues for future exploration in the dynamic field of sp<sup>1</sup>-hybridized carbon chains.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 4","pages":"Article 110466"},"PeriodicalIF":9.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143098170","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}
引用次数: 0
Swelling and erosion assisted sustained release of tea polyphenol from antibacterial ultrahigh molecular weight polyethylene for joint replacement 抗菌超高分子量聚乙烯中茶多酚的膨胀和侵蚀辅助持续释放,用于关节置换术
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-15 DOI: 10.1016/j.cclet.2024.110468
Yue Ren , Kang Li , Yi-Zi Wang , Shao-Peng Zhao , Shu-Min Pan , Haojie Fu , Mengfan Jing , Yaming Wang , Fengyuan Yang , Chuntai Liu
The considerable hazard posed by periprosthetic joint infections underlines the urgent need for the rapid advancement of in-situ drug delivery systems within joint materials. However, the pursuit of sustained antibacterial efficacy remains a formidable challenge. In this context, we proposed a novel strategy that leverages swelling and erosion mechanisms to facilitate drug release of drug-loaded ultrahigh molecular weight polyethylene (UHMWPE), thereby ensuring its long-lasting antibacterial performance. Polyethylene oxide (PEO), a hydrophilic polymer with fast hydrating ability and high swelling capacity, was incorporated in UHMWPE alongside the antibacterial tea polyphenol (epigallocatechin gallate, EGCG as representative). The swelling of PEO enhanced water infiltration into the matrix, while the erosion of PEO balanced the release of the encapsulated EGCG, resulting in a steady release. The behavior was supported by the EGCG release profiles and the corresponding fitted release kinetic models. As demonstrated by segmented antibacterial assessments, the antibacterial efficiency was enhanced 2 to 3 times in the PEO/EGCG/UHMWPE composite compared to that of EGCG/UHMWPE. Additionally, the PEO/EGCG/UHMWPE composite exhibited favorable biocompatibility and mechanical performance, making it a potential candidate for the development of drug-releasing joint implants to combat prosthetic bacterial infections.
假体周围关节感染带来的巨大危害凸显了在关节材料中快速开发原位给药系统的迫切性。然而,追求持续的抗菌效果仍然是一项艰巨的挑战。在此背景下,我们提出了一种新策略,利用膨胀和侵蚀机制促进药物负载的超高分子量聚乙烯(UHMWPE)的药物释放,从而确保其持久的抗菌性能。聚氧化乙烯(PEO)是一种具有快速水合能力和高溶胀能力的亲水性聚合物,它与抗菌茶多酚(表没食子儿茶素没食子酸酯,以 EGCG 为代表)一起被加入到超高分子量聚乙烯中。PEO 的溶胀增强了水对基质的渗透,而 PEO 的侵蚀平衡了封装 EGCG 的释放,从而实现了稳定释放。EGCG 的释放曲线和相应的拟合释放动力学模型都支持这种行为。分段抗菌评估表明,与 EGCG/UHMWPE 相比,PEO/EGCG/UHMWPE 复合材料的抗菌效率提高了 2 到 3 倍。此外,PEO/EGCG/UHMWPE 复合材料还表现出良好的生物相容性和机械性能,使其成为开发药物释放关节植入物的潜在候选材料,以对抗假体细菌感染。
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引用次数: 0
Structuring MoO3-polyoxometalate hybrid superstructures to boost electrocatalytic hydrogen evolution reaction 构建 MoO3-聚氧化金属酸盐混合超结构,促进电催化氢气进化反应
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-15 DOI: 10.1016/j.cclet.2024.110467
Bowen Li, Ting Wang, Ming Xu, Yuqi Wang, Zhaoxing Li, Mei Liu, Wenjing Zhang, Ming Feng
Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H2 production by electrochemical water splitting, but it remains a great challenge. Herein, we reported two kinds of MoO3-polyoxometalate hybrid nanobelt superstructures (MoO3-POM HNSs, POM = PW12O40 and SiW12O40) using a simple hydrothermal method. Such superstructure with highly uniform nanoparticles as building blocks can expose more surface atoms and emanate increased specific surface area. The incorporated POMs generated abundant oxygen vacancies, improved the electronic mobility, and modulated the surface electronic structure of MoO3, allowing to optimize the H* adsorption/desorption and dehydrogenation kinetics of catalyst. Notably, the as-prepared MoO3-PW12O40 HNSs electrodes not only displayed the low overpotentials of 108 mV at 10 mA/cm2 current density in 0.5 mol/L H2SO4 electrolyte but also displayed excellent long-term stability. The hydrogen evolution reaction (HER) performance of MoO3-POM superstructures is significantly better than that of corresponding bulk materials MoO3@PW12O40 and MoO3@SiW12O40, and the overpotentials are about 8.3 and 4.9 times lower than that of single MoO3. This work opens an avenue for designing highly surface-exposed catalysts for electrocatalytic H2 production and other electrochemical applications.
提高催化剂的表面原子利用效率对于电化学水分离大规模生产 H2 极其重要,但这仍然是一个巨大的挑战。在此,我们采用简单的水热法报道了两种 MoO3 聚氧化铝杂化纳米带上层结构(MoO3-POM HNSs,POM = PW12O40 和 SiW12O40)。这种以高度均匀的纳米颗粒为构件的超结构可以暴露出更多的表面原子,并增加比表面积。加入的 POM 产生了大量的氧空位,提高了电子迁移率,并调节了 MoO3 的表面电子结构,从而优化了催化剂的 H* 吸附/解吸和脱氢动力学。值得注意的是,制备的 MoO3-PW12O40 HNSs 电极不仅在 0.5 mol/L H2SO4 电解液中以 10 mA/cm2 的电流密度显示出 108 mV 的低过电位,而且显示出优异的长期稳定性。MoO3-POM 超结构的氢进化反应(HER)性能明显优于相应的块体材料 MoO3@PW12O40 和 MoO3@SiW12O40,其过电位分别是单一 MoO3 的 8.3 倍和 4.9 倍。这项工作为设计用于电催化制取 H2 及其他电化学应用的高表面暴露催化剂开辟了一条途径。
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引用次数: 0
Small molecule chemical scaffolds in plant growth regulators for the development of agrochemicals
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-14 DOI: 10.1016/j.cclet.2024.110462
Ali Dai , Zhiguo Zheng , Liusheng Duan , Jian Wu , Weiming Tan
Agrochemicals, especially plant growth regulators (PGRs), are extensively used to modulate endogenous phytohormone signals in small quantities, significantly influencing plant growth and development. Plant hormones typically exhibit diverse chemical structures, with common examples including indole rings, terpenoid frameworks, adenine motifs, cyclic lactones, cyclopentanones, and steroidal compounds, which are extensively employed in pesticides. This article explores the interactions and biological activities of small molecules on proteins, enzymes, and other reactive sites involved in the biosynthesis, metabolism, transport, and signal transduction pathways of various plant hormones. Additionally, it analyzes the structure-activity relationships (SARs) of pesticides incorporating these structural motifs to elucidate the relationship between active fragments, pharmacophores, and targets, highlighting the characteristics of potent small molecules and their derivatives. This comprehensive review aims to provide novel perspectives for the development and design of pesticides, offering valuable insights for researchers in the field.
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引用次数: 0
EDA-complexes-enabled photochemical synthesis of α-amino acids with imines and tetrabutylammonium oxalate 用亚胺和草酸四丁基铵光化学合成α-氨基酸的 EDA 复合物
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-14 DOI: 10.1016/j.cclet.2024.110446
Min-Hang Zhou, Jun Jiang, Wei-Min He
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引用次数: 0
期刊
Chinese Chemical Letters
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