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Nd@C3N4-photoredox/chlorine dual catalyzed synthesis and evaluation of antitumor activities of 4-alkylated sulfonyl ketimines Nd@C3N4-photoredox/chlorine 双催化合成 4-烷基磺酰基酮亚胺并评估其抗肿瘤活性
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-19 DOI: 10.1016/j.cclet.2024.110568
Hong-Tao Ji , Yu-Han Lu , Yan-Ting Liu , Yu-Lin Huang , Jiang-Feng Tian , Feng Liu , Yan-Yan Zeng , Hai-Yan Yang , Yong-Hong Zhang , Wei-Min He
The first example of Nd@C3N4-photoredox/chlorine dual catalyzed alkylation with unactivated alkanes as the alkyl sources has been developed, which allows for the synthesis of various 4-alkylated cyclic sulfonyl ketimines. In this process, chlorine functions as both a redox and hydrogen atom transfer catalyst. The synergism of the reversible Nd2+/Nd3+ and Cl¯/Cl˙ redox pairs significantly enhances overall photocatalytic efficiency. The in vitro anticancer activity of 4-alkylated products was evaluated by using the CCK8 assay against both human choroidal melanoma (MUM-2B) and lung cancer (A549) cell. Compound 3da showed approximately triple the potency of 5-fluorouracil.
首次开发出以未活化烷烃为烷基源的 Nd@C3N4-photoredox/chlorine 双催化烷基化实例,可用于合成各种 4-烷基环磺酰基酮亚胺。在这一过程中,氯既是氧化还原催化剂,又是氢原子转移催化剂。可逆的 Nd2+/Nd3+ 和 Cl¯/Cl˙ 氧化还原对的协同作用显著提高了整体光催化效率。利用 CCK8 检测法评估了 4-烷基化产物对人类脉络膜黑色素瘤(MUM-2B)和肺癌(A549)细胞的体外抗癌活性。化合物 3da 的效力约为 5-氟尿嘧啶的三倍。
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引用次数: 0
Synthetic Cu(III) from copper plating wastewater for onsite decomplexation of Cu(II)- and Ni(II)-organic complexes 从镀铜废水中合成 Cu(III),用于现场解络合 Cu(II)-和 Ni(II)-有机络合物
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-14 DOI: 10.1016/j.cclet.2024.110549
Junyi Yu , Yin Cheng , Anhong Cai , Xianfeng Huang , Qingrui Zhang
Herein, the Cu(III) synthesized from copper plating effluent was developed for the first time to evaluate the onsite degradation performance of heavy metal complexes in the wastewater, thus achieving the purpose of “treating waste with waste”. The results indicated that synthetic Cu(III) presented the excellent decomplexation performance for Cu(II)/Ni(II)-organic complexes. The removal efficiency of Cu(II)/Ni(II)-EDTA significantly increased with increasing Cu(III) dosage, and the degradation of Cu(II)/Ni(II)-EDTA by synthetic Cu(III) system displayed highly pH-dependent reactivity. The radical quencher experiments confirmed that Cu(III) direct oxidation were mainly involved in the degradation of Cu(II)-EDTA. Additionally, the continuous decarboxylation process was proven to be the main degradation pathway of Cu(II)-EDTA in Cu(III) system. The coexisting substances (SO42−, Cl and fulvic acids) showed little impacts at low level for the removal of Cu(II)/Ni(II)-EDTA, while retarded the degradation of Cu(II)-EDTA slightly at high level, which features high selective oxidation. Encouragingly, it was also effective to remove Cu(II)/Ni(II)-EDTA from in treating actual Cu/Ni-containing wastewater through synthetic Cu(III) treatment.
本文首次开发了由镀铜废水合成的 Cu(III),用于评估废水中重金属络合物的现场降解性能,从而达到 "以废治废 "的目的。结果表明,合成的 Cu(III) 对 Cu(II)/Ni(II)- 有机络合物具有优异的解络合性能。随着 Cu(III) 用量的增加,Cu(II)/Ni(II)-EDTA 的去除率显著提高,而合成 Cu(III) 体系对 Cu(II)/Ni(II)-EDTA 的降解具有高度的 pH 依赖性。自由基淬灭剂实验证实,Cu(III) 直接氧化作用是 Cu(II)-EDTA 降解的主要原因。此外,连续脱羧过程被证明是 Cu(III)体系中 Cu(II)-EDTA 的主要降解途径。共存物质(SO42-、Cl- 和富勒酸)在低浓度时对 Cu(II)/Ni(II)-EDTA 的去除影响不大,而在高浓度时则略微延缓了 Cu(II)-EDTA 的降解,这说明其具有高选择性氧化的特点。令人鼓舞的是,在通过合成 Cu(III) 处理实际含铜/镍废水时,它也能有效去除 Cu(II)/Ni(II)-EDTA 中的 Cu(II)/Ni(II)-EDTA。
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引用次数: 0
“Super-heterojunctioned” thermoelectric polymers "超级热结 "热电聚合物
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-30 DOI: 10.1016/j.cclet.2024.110523
Hanying Li , Wee-Liat Ong
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引用次数: 0
Oxygen vacancies-rich molybdenum tungsten oxide nanowires as a highly active nitrogen fixation electrocatalyst 富氧空位钼钨氧化物纳米线作为高活性固氮电催化剂
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-26 DOI: 10.1016/j.cclet.2024.110491
Jincheng Zhang , Mengjie Sun , Jiali Ren , Rui Zhang, Min Ma, Qingzhong Xue, Jian Tian
Herein, vacancy engineering is utilized reasonably to explore molybdenum tungsten oxide nanowires (W4MoO3 NWs) rich in O-vacancies as an advanced electrochemical nitrogen reduction reaction (eNRR) electrocatalyst, realizing further enhancement of NRR performance. In 0.1 mol/L Na2SO4, W4MoO3 NWs rich in O vacancies (CTAB-D-W4MoO3) achieve a large NH3 yield of 60.77 µg h-1 mg-1cat. at -0.70 V vs. RHE and a high faradaic efficiency of 56.42 % at -0.60 V, much superior to the W4MoO3 NWs deficient in oxygen vacancies (20.26 µg h-1 mg-1cat. and 17.1 % at -0.70 V vs. RHE). Meanwhile, W4MoO3 NWs rich in O-vacancies also show high electrochemical stability. Density functional theory (DFT) calculations present that O vacancies in CTAB-D-W4MoO3 reduce the energy barrier formed by the intermediate of *N-NH, facilitate the activation and further hydrogenation of *N-N, promote the NRR process, and improve NRR activity.
本文合理利用空位工程技术,探索将富含 O 空位的钼钨氧化物纳米线(W4MoO3 NWs)作为先进的电化学氮还原反应(eNRR)电催化剂,实现氮还原反应性能的进一步提高。在 0.1 mol/L Na2SO4 中,富含 O 空位的 W4MoO3 NWs(CTAB-D-W4MoO3)在 -0.70 V 对 RHE 时的 NH3 产率高达 60.77 µg h-1 mg-1cat.,在 -0.60 V 时的远化效率高达 56.42 %,远优于缺乏氧空位的 W4MoO3 NWs(在 -0.70 V 对 RHE 时的产率为 20.26 µg h-1 mg-1cat.)同时,富含氧空位的 W4MoO3 NWs 也表现出很高的电化学稳定性。密度泛函理论(DFT)计算表明,CTAB-D-W4MoO3 中的 O 空位降低了 *N-NH 中间体形成的能障,有利于 *N-N 的活化和进一步氢化,促进了 NRR 过程,提高了 NRR 活性。
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引用次数: 0
Polyvinyl alcohol fiber with enhanced strength and modulus and intense cyan fluorescence based on covalently functionalized graphene quantum dots 基于共价官能化石墨烯量子点的具有更高强度和模量以及更强青色荧光的聚乙烯醇纤维
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-26 DOI: 10.1016/j.cclet.2024.110510
Manman Ou, Yunjian Zhu, Jiahao Liu, Zhaoxuan Liu, Jianjun Wang, Jun Sun, Chuanxiang Qin, Lixing Dai
In this study, we proposed a novel and efficient way to strengthen polyvinyl alcohol (PVA) fiber using graphene quantum dots (GQDs). PVA molecular chains were grafted onto the surface of GQDs through Friedel-Crafts alkylation reaction to obtain functionalized GQDs (f-GQDs), and PVA/f-GQDs composite fiber was successfully prepared by wet spinning and post-treatment. The tensile strength and Young's modulus of the composite fiber reached up to 1229.24 MPa and 35.36 GPa which were approximately twice and 4 times those of the pure PVA fiber, respectively. Moreover, the composite fiber was demonstrated excellent resistance to solvents. In addition, the PVA/f-GQDs composite fiber showed intense and uniform cyan fluorescence, meanwhile, it could maintain stable solid-state fluorescence in acid and alkali solutions and particularly after long-term immersion in water (1 month). This study proposes a promising route for obtaining high-performance conventional fibers with some new functions.
在这项研究中,我们提出了一种利用石墨烯量子点(GQDs)增强聚乙烯醇(PVA)纤维的新型高效方法。通过 Friedel-Crafts 烷基化反应将 PVA 分子链接枝到 GQDs 表面,得到功能化 GQDs(f-GQDs),并通过湿法纺丝和后处理成功制备了 PVA/f-GQDs 复合纤维。复合纤维的拉伸强度和杨氏模量分别达到 1229.24 MPa 和 35.36 GPa,约为纯 PVA 纤维的 2 倍和 4 倍。此外,复合纤维还具有优异的耐溶剂性。此外,PVA/f-GQDs 复合纤维显示出强烈而均匀的青色荧光,同时在酸碱溶液中,尤其是在水中长期浸泡(1 个月)后,仍能保持稳定的固态荧光。这项研究为获得具有某些新功能的高性能传统纤维提供了一条可行的途径。
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引用次数: 0
Engineered iron-based metal-organic frameworks nanoplatforms for cancer theranostics: A mini review 用于癌症治疗的铁基金属有机框架纳米平台:微型综述
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-25 DOI: 10.1016/j.cclet.2024.110501
Yunlong Li , Xinyu Zhang , Shuang Liu , Chunsheng Li , Qiang Wang , Jin Ye , Yong Lu , Jiating Xu
Up to now, numerous emerging methods of cancer treatment including chemodynamic therapy, photothermal therapy, photodynamic therapy, sonodynamic therapy, immunotherapy and chemotherapy have rapidly entered a new stage of development. However, the single treatment mode is often constrained by the complex tumor microenvironment. Recently, the nanomaterials and nanomedicine have emerged as promising avenues to overcome the limitation in cancer theranostics. Especially, metal-organic frameworks (MOFs) have gained considerable interests in cancer therapy because of their customizable morphologies, easy functionalization, large specific surface area, and good biocompatibility. Among these MOFs, iron-based MOFs (Fe-MOFs) are particularly promising for cancer treatment due to their properties as nano-photosensitizers, peroxidase-like activity, bioimaging contrast capabilities, and biodegradability. Utilizing their structural regularity and synthetic tunability, Fe-MOFs can be engineered to incorporate organic molecules or other inorganic nanoparticles, thereby creating multifunctional nanoplatforms for single or combined theranostic modes. Herein, the minireview focuses on the recent advancements of the Fe-MOFs-based nanoplatforms for self-enhanced imaging and treatment at tumor sites. Furthermore, the clinical research development of Fe-MOFs-based nanoplatforms is discussed, addressing key challenges and innovations for the future. Our review aims to provide novice researchers with a foundational understanding of advanced cancer theranostic modes and promote their clinical applications through the modification of Fe-MOFs.
迄今为止,包括化学动力疗法、光热疗法、光动力疗法、声动力疗法、免疫疗法和化疗在内的众多新兴癌症治疗方法已迅速进入新的发展阶段。然而,单一的治疗模式往往受制于复杂的肿瘤微环境。近来,纳米材料和纳米医学的出现为克服肿瘤治疗学的局限性提供了很好的途径。特别是金属有机框架(MOFs),由于其形态可定制、易于功能化、比表面积大、生物相容性好等特点,在癌症治疗中获得了极大的关注。在这些 MOFs 中,铁基 MOFs(Fe-MOFs)因其具有纳米光敏剂、过氧化物酶样活性、生物成像对比能力和生物可降解性等特性,在癌症治疗中尤其具有广阔的前景。利用其结构的规则性和合成可调性,Fe-MOFs 可与有机分子或其他无机纳米粒子结合,从而创造出单一或组合治疗模式的多功能纳米平台。在此,小编将重点介绍基于 Fe-MOFs 的纳米平台在肿瘤部位自我增强成像和治疗方面的最新进展。此外,还讨论了基于 Fe-MOFs 的纳米平台的临床研究发展,探讨了未来的主要挑战和创新。我们的综述旨在让新手研究人员对先进的癌症治疗模式有一个基础性的了解,并通过对 Fe-MOFs 的改性促进其临床应用。
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引用次数: 0
High quantum yield yellow emission carbon dots for the construction of blue light blocking films 用于构建蓝光阻挡薄膜的高量子产率黄色发射碳点
IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-24 DOI: 10.1016/j.cclet.2024.110497
Liwen Wang , Boyang Wang , Siyu Lu , Shubo Lv , Xiaoli Qu
White light illumination is essential in daily life, however, the substantial amount of blue light it contains can damage human eyes. Therefore, it is important to block this high-energy blue light to protect visual health. In this study, yellow-emitting carbon dots (CDs) with a quantum yield exceeding 94 % were synthesized using citric acid and urea. These CDs effectively absorb blue light. By incorporating them into polystyrene, multiple films termed CDs-based blue light blocking films (CBFs) were developed, each offering different levels of blue light absorption. These CBFs exhibited excellent transparency and efficient blue light filtering capabilities. This study highlights the potential of high quantum yield CDs, which specifically absorb blue light, as foundational materials for developing light-blocking solutions against high-energy short-wavelength light.
白光照明在日常生活中必不可少,但其中含有的大量蓝光会对人眼造成伤害。因此,阻挡这种高能蓝光以保护视力健康非常重要。本研究利用柠檬酸和尿素合成了量子产率超过 94% 的黄色发光碳点(CD)。这些碳点能有效吸收蓝光。通过将它们与聚苯乙烯结合,开发出了多种薄膜,称为基于 CD 的蓝光阻隔薄膜(CBF),每种薄膜都具有不同程度的蓝光吸收能力。这些 CBF 具有出色的透明度和高效的蓝光过滤能力。这项研究凸显了高量子产率 CD(专门吸收蓝光)作为开发阻挡高能短波光解决方案的基础材料的潜力。
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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。
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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
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
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Chinese Chemical Letters
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