{"title":"Sustainable carbonylative transformation of alkyl iodides to amides via crosslinking of EDA and XAT","authors":"Hefei Yang , Le-Cheng Wang , Xiao-Feng Wu","doi":"10.1016/j.cclet.2025.110843","DOIUrl":"10.1016/j.cclet.2025.110843","url":null,"abstract":"<div><div>The amide moiety plays an important role as a powerful bioactive backbone, and as the synthetic chemistry community moves toward more sp<sup>3</sup>-rich scaffolds, alkyl halides have become the feedstock of choice for obtaining carbonylation products. With the development of photoredox catalysis, several aminocarbonylation systems for alkyl halides were developed which usually require transition metal catalysis. Considering the demands for green sustainable chemical synthesis, here we report a metal-free, exogenous catalyst-free aminocarbonylation reaction of alkyl iodides under atmospheric pressure of carbon monoxide. Through a combination of EDA and XAT strategies, the reaction occurs efficiently under only light irradiation at room temperature.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 9","pages":"Article 110843"},"PeriodicalIF":9.4,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144472013","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}
{"title":"A multi-stimuli responsive [3]rotaxane based on hydrogen-bonded aramide azo-macrocycles","authors":"Zhiyao Yang, Kuirong Fu, Wentao Yu, Along Jia, Xinnan Chen, Yimin Cai, Xiaowei Li, Wen Feng, Lihua Yuan","doi":"10.1016/j.cclet.2025.110842","DOIUrl":"10.1016/j.cclet.2025.110842","url":null,"abstract":"<div><div>A novel [3]rotaxane, featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites, a secondary dialkylammonium (AM) unit and a 4,4′-bipyridinium (BP) unit, has been synthesized. This multi-stimuli-responsive [3]rotaxane exhibits unique molecular motion, with the macrocycles shuttling along the axle in response to acid-base reactions, temperature changes, solvent variations, and light irradiation. The molecular shuttle and reversibility were investigated by <sup>1</sup>H NMR, 2D NOESY, HRESI-MS, and UV-vis spectroscopy. This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness, highlighting its potential for multi-state control over the motion of interlocked rings on an axle. The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 9","pages":"Article 110842"},"PeriodicalIF":9.4,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144472014","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}
Yaojun Li , Yun Li , Shenglong Liao , Yang Li , Shouchun Yin
{"title":"Revolutionizing cancer therapies with organic photovoltaic non-fullerene acceptors: A deep dive into molecular engineering for advanced phototheranostics","authors":"Yaojun Li , Yun Li , Shenglong Liao , Yang Li , Shouchun Yin","doi":"10.1016/j.cclet.2025.110832","DOIUrl":"10.1016/j.cclet.2025.110832","url":null,"abstract":"<div><div>The integration of advanced diagnostic and therapeutic capabilities in oncology has given rise to phototheranostics, a field that combines the precision of imaging with the selectivity of light-activated treatments. Due to their pronounced near-infrared (NIR) absorption, tunable molecular structures, and commendable stability, organic photovoltaic non-fullerene acceptors (NFAs) represent a promising frontier in cancer management. Despite the great potential of NFAs in phototheranostics, there is currently a lack of systematic reviews in this field. This review provides a meticulous examination of the current state of NFAs in the field of phototheranostics, highlighting the strategic approaches to spectral red-shifting that enhance tissue penetration and therapeutic efficacy. It dissects the link between molecular architecture and performance across key therapeutic and diagnostic modalities, including photothermal therapy (PTT), photodynamic therapy (PDT), and fluorescence imaging (FLI). In addition, the review presents a concise analysis of the challenges and milestones in the clinical translation of NFAs, offering insights into the innovations required to overcome existing barriers.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 8","pages":"Article 110832"},"PeriodicalIF":9.4,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144203197","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}
Pei-Pei Liu , Jia-Bin Xing , Yue-Yang Liu , Ke Feng , Hui Wang , Dan-Wei Zhang , Wei Zhou , Gang Zhao , Jiaheng Zhang , Zhan-Ting Li
{"title":"Sulfonatoproxylated cucurbit[7]urils as highly water-soluble and biocompatible excipients for solubilizing poorly soluble drugs and improving the bioavailability of indomethacin","authors":"Pei-Pei Liu , Jia-Bin Xing , Yue-Yang Liu , Ke Feng , Hui Wang , Dan-Wei Zhang , Wei Zhou , Gang Zhao , Jiaheng Zhang , Zhan-Ting Li","doi":"10.1016/j.cclet.2025.110831","DOIUrl":"10.1016/j.cclet.2025.110831","url":null,"abstract":"<div><div>The ongoing development of small molecule drugs underscores the urgent need for novel excipients to formulate poorly soluble drug candidates. Cucurbit[7]uril (CB[7]) possesses high binding affinities for a variety of molecular guests. However, its moderate water solubility limits broader application. Here we report the synthesis of three CB[7] derivatives <strong>M1</strong>-<strong>M3</strong> by modifying an average of 4.2, 5.5, and 5.9 sulfonatopropoxy groups onto their “equator” carbons. Compared to CB[7], their water-solubility increased by at least 26.6-, 23.6-, and 19.2-fold, respectively, while the maximum tolerated doses (MTD) of <strong>M1</strong> and <strong>M2</strong> improved by 2.5- and 2.3-fold. Phase solubility diagram studies demonstrate that <strong>M1</strong> and <strong>M2</strong> significantly enhance the water-solubility of eighteen poorly soluble drugs. <em>In vivo</em> experiments in rat complete Freund's arthritis reveal that <strong>M1</strong> not only improves the anti-inflammatory efficacy of indomethacin by up to 52 %, but also substantially reduces its side effect of gastric ulcer.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 9","pages":"Article 110831"},"PeriodicalIF":9.4,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144480602","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}
Sheng Tang , Mingyue Liao , Weihai Sun , Jihuai Wu , Jiamin Lu , Yiming Xie
{"title":"Optimizing CsPbBr3 perovskite solar cell interface and performance through tetraphenylethene derivatives","authors":"Sheng Tang , Mingyue Liao , Weihai Sun , Jihuai Wu , Jiamin Lu , Yiming Xie","doi":"10.1016/j.cclet.2025.110838","DOIUrl":"10.1016/j.cclet.2025.110838","url":null,"abstract":"<div><div>Recently, CsPbBr<sub>3</sub> perovskite solar cells (PSCs) have garnered attention due to cost-effectiveness and reliability. However, hole transport limitations lead to charge recombination and lower power conversion efficiency (PCE). Defects in the CsPbBr<sub>3</sub> layer, poor hole transport at the interface with carbon electrodes, and energy level differences hinder performance. Optimizing the perovskite layer using electron-donating organic molecules containing -NH<sub>2</sub> groups enhances efficiency and stability by passivating defects and modulating lattice structure. In this work, tetra(4-aminophenyl)ethylene (TPE) and tetra(4-aminobiphenyl)ethylene (TPE-Ph) were employed to optimize the CsPbBr<sub>3</sub>/carbon electrode interface. Their strong electron-donating properties and amino groups facilitate hole transfer and defect passivation, boosting PCE to 9.38% and enhancing stability.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 6","pages":"Article 110838"},"PeriodicalIF":9.4,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143704216","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}
Lei Zhang , Chenyang Kou , Kun Ni , Yiwen Chen , Tongchuan Zhang , Baoliang Zhang
{"title":"Microenvironment regulation of copper sites by chelating hydrophobic polymer for electrosynthesis of ethylene","authors":"Lei Zhang , Chenyang Kou , Kun Ni , Yiwen Chen , Tongchuan Zhang , Baoliang Zhang","doi":"10.1016/j.cclet.2025.110836","DOIUrl":"10.1016/j.cclet.2025.110836","url":null,"abstract":"<div><div>Molecular catalysts can effectively steer the electrocatalytic acetylene semihydrogenation into ethylene, but realizing high Faradaic efficiency (FE) at industrial current densities remains a challenge. Herein, we report a ligand engineering strategy that utilizes polymeric <em>N</em>‑heterocyclic carbene (NHC) as a hydrophobic ligand to modulate the microenvironment of Cu sites. This polymeric NHC imparts appropriate hydrophobic properties for the chelated Cu sites, thereby moderating the H<sub>2</sub>O transport and enabling easy access of acetylene. Consequently, the polymeric NHC chelated Cu exhibits an FE<sub>ethylene</sub> of ∼97% at a current density of 500 mA/cm<sup>2</sup> in a flow cell. Particularly in a zero-gap reactor, the FE<sub>ethylene</sub> consistently exceeds 86% across current densities from 100 mA/cm<sup>2</sup> to 400 mA/cm<sup>2</sup>, reaching an optimal FE<sub>ethylene</sub> of 98% at 200 mA/cm<sup>2</sup> and achieving durable operation for 155 h at 100 mA/cm<sup>2</sup>. This work provides a promising paradigm to regulate the microenvironment of molecular catalysts for improving electrocatalytic performances under industrial current densities.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 6","pages":"Article 110836"},"PeriodicalIF":9.4,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143704211","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}
{"title":"Highly regioselective electrochemical oxidative 2,1-azolization of alkenes with azoles and nucleophiles","authors":"Yaqi Deng, Jian Xue, Xiang Wu, Shunying Liu","doi":"10.1016/j.cclet.2025.110822","DOIUrl":"10.1016/j.cclet.2025.110822","url":null,"abstract":"<div><div>The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds. The existing approach is extensively promoted by using C/X-centered radicals and N-nucleophiles to conduct 1,2-difunctional amination/azolization of alkenes. In contrast, 2,1-difunctional amination/azolization of alkenes by using nitrogen-centered radicals (NCRs) and nucleophiles still remains rarely underexplored. It is possibly due to the highly active electron properties of NCRs and the relatively poor nucleophilicity of aromatic NCRs to be trapped by arylalkenes. Herein, we demonstrate an unprecedented 2,1-hydroxazolization reactions of arylalkenes through electrochemically enabled addition of NCRs from azoles and nucleophiles (NuH) in high yields and with high regioselectivity. This conversion is characterized by the fact that neither metal catalysts nor external chemical oxidants are required. This electrochemical oxidation synthesis method can also be applied for a broad range of NuH including pyridine hydrofluoride, ammonia, water, alcohols, and acids which enables the formation of C-N and C–X (X = F/N/O) bonds in one-pot fashion to furnish efficient fluoroamination, diamination and oxoamination of alkenes.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 9","pages":"Article 110822"},"PeriodicalIF":9.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144365379","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}
Bowen Song , Chenxu Shi , Yinghao Qu , Hongjun Liu , Hui Yang , Xiaoming Wu , Xijun Liu
{"title":"The electrical properties and charge transport mechanism of MXenes","authors":"Bowen Song , Chenxu Shi , Yinghao Qu , Hongjun Liu , Hui Yang , Xiaoming Wu , Xijun Liu","doi":"10.1016/j.cclet.2025.110823","DOIUrl":"10.1016/j.cclet.2025.110823","url":null,"abstract":"","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 6","pages":"Article 110823"},"PeriodicalIF":9.4,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143838029","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}
{"title":"Developing color-tunable long afterglow anti-counterfeiting materials using cucurbit[6]uril and classical aggregation-caused quenching compounds through multiple non-covalent interactions","authors":"Xingyue Yuan, Li Wu, Qiuyu Peng, Yanyan Tang, Mingxu Wang, Yuhang Wei, Zhu Tao, Xin Xiao","doi":"10.1016/j.cclet.2025.110821","DOIUrl":"10.1016/j.cclet.2025.110821","url":null,"abstract":"<div><div>This investigation focuses on the utilization of cucurbit[6]uril (Q[6]) as the host compound for the development of long-lasting afterglow materials. By strategically manipulating the outer surface interactions of Q[6], classical aggregation-caused quenching (ACQ) compounds such as fluorescein sodium (FluNa) and calcein sodium (CalNa) were transformed into afterglow materials with varying colors and durations upon exposure to ultraviolet light. This transformation was facilitated through a host-guest doping method combined with coordination with metal ions. Even at a reduced doping concentration of 5 × 10<sup>–5</sup> wt%, the materials exhibit remarkable afterglow properties, lasting up to 2s, with a phosphorescence lifetime of up to 150 ms. Moreover, by adjusting the concentration of the guest compound, the persistent luminescence color of the materials could be easily transitioned from orange to yellow and subsequently to green. These findings suggest that the developed afterglow materials hold significant potential for multi-level anti-counterfeiting and information encryption applications when exposed to ultraviolet light. The supramolecular assembly strategy, which relies on the outer surface interactions of cucurbit[<em>n</em>]uril, offers a simpler and more efficient approach to crafting multi-color luminescent materials. Additionally, this method opens avenues for enhancing the application potential of aggregation-caused quenching (ACQ) compounds in various technological domains.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 9","pages":"Article 110821"},"PeriodicalIF":9.4,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144335733","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}
Cui-Ting Yang , Dan-Dan Wang , Shuai Chen , Jian-Mei Yang , Jun-Nan He , Jun-Hui Zhang , Xiao-Qing Liu , Jin Zhang , Lei Zhang , Yan Zhao
{"title":"A chiral supramolecular nanocatcher prepared by d-biotin-pillar[5]arene for the selective capture and targeted delivery of oxaliplatin enantiomers","authors":"Cui-Ting Yang , Dan-Dan Wang , Shuai Chen , Jian-Mei Yang , Jun-Nan He , Jun-Hui Zhang , Xiao-Qing Liu , Jin Zhang , Lei Zhang , Yan Zhao","doi":"10.1016/j.cclet.2025.110820","DOIUrl":"10.1016/j.cclet.2025.110820","url":null,"abstract":"<div><div>Chiral anticancer drugs are the subject of ongoing research due to their optical characterization and pharmacological effects. Achieving a single enantiomer of a chiral anticancer drug is arduous, but it can significantly improve its pharmacokinetics for tumor therapy. Here, the chiral nanocatchers, known as <span>d</span>-biotin-P5⊃MCC NCs, were designed and prepared based on host-guest self-assembly between <span>d</span>-biotin anchored pillar[5]arene (<span>d</span>-biotin-P5) and myristoyl chloride choline (MCC). <span>d</span>-Biotin-P5⊃MCC NCs featuring the chiral separation and enzyme-induced disassemble were evaluated for their ability to selectively capture and subsequently target the release of (<em>R,R</em>)-OXA enantiomers into tumor cells. Furthermore, the use of <span>d</span>-biotin-P5⊃MCC NCs has demonstrated a significant enhancement in the intracellular uptake of OXA, with the drug being efficiently released to MCF-7 breast cancer cells. This has led to a superior inhibitory effect on MCF-7 cells when compared to free OXA, while also reducing the cytotoxicity of the drug in HEK 293 human embryonic kidney cells. This research not only paves a promising way for the fabrication of chiral supramolecular nanocarriers but also holds the potential to improve the processes of chiral drug separation and targeted therapy.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 9","pages":"Article 110820"},"PeriodicalIF":9.4,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144365380","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}