Chinese Journal of Chemistry最新文献

{"title":"Rare-Earth Doping Induced Pinning Effect with Enhanced Chemo-Mechanical Stability in Ni-Rich Cathodes for Lithium-Ion Batteries","authors":"Bin Zhang,&nbsp;Hongyun Zhang,&nbsp;Yuefeng Su,&nbsp;Jinyang Dong,&nbsp;Kang Yan,&nbsp;Jinzhong Liu,&nbsp;Yun Lu,&nbsp;Haoyu Wang,&nbsp;Chengzhi Wang,&nbsp;Feng Wu,&nbsp;Lai Chen","doi":"10.1002/cjoc.202401071","DOIUrl":"https://doi.org/10.1002/cjoc.202401071","url":null,"abstract":"<div>\u0000 \u0000 <p>The nickel-rich layered ternary cathode material (NCM) has been extensively studied due to its high specific capacity and low cost. Nevertheless, with the increase of Ni content, the unstable structure of NCM material has gradually become prominent. Residual alkali on the surface and Li⁺/Ni²⁺ mixing before cycling, phase change, transition metal ions dissolution, microcracking, and other issues during the cycle, are the primary causes for the fast capacity fading of Ni-rich materials. In this study, Sc³⁺ is doped into the LiNi_0.8Co_0.1Mn_0.1O₂ material, which has been demonstrated to impede the Li⁺/Ni²⁺ mixing, while simultaneously increasing the layer spacing. This results in the stabilization of the material structure and an enhancement of both the cycling stability and the rate performance. Notably, single-particle force testing and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging further demonstrate reduced stress accumulation and mitigated chemo-mechanical failure. This study underscores the efficacy of a minor addition of multifunctional rare-earth doping in enhancing the chemo-mechanical stability of Ni-rich cathodes, offering a straightforward and comprehensive solution to optimize the design and performance of energy storage cathodes.\u0000\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 8","pages":"889-896"},"PeriodicalIF":5.5,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629774","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":"Construction of 1,3-Diboryl Allenes from gem-Iododiboron Compounds via Intermolecular Boryl Group Transfer†","authors":"Ming Li,&nbsp;Yi Wei,&nbsp;Du Chen,&nbsp;Peng-Fei Ning,&nbsp;Yi-Fei Yang,&nbsp;Xiao-Yu Xie,&nbsp;Chao Liu,&nbsp;Kai Hong","doi":"10.1002/cjoc.202400840","DOIUrl":"https://doi.org/10.1002/cjoc.202400840","url":null,"abstract":"<div>\u0000 \u0000 <p>Allenylboronates are valuable synthetic building blocks and have garnered significant interest. However, their 1,3-diboyl substituted analogs have not been reported. Herein, we disclosed a novel method for creating 1,3-diboyl allenes from <i>gem</i>-iododiboron compounds and alkynyl Grignard reagents. The starting materials are initially converted into the corresponding propargylic <i>gem</i>-bis(boronates), which then undergo an intermolecular boryl group transfer to afford 1,3-diboyl allenes, as confirmed by mechanistic studies. This method features good tolerance to steric hindrance and is compatible with a wide variety of functional groups.\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 8","pages":"949-955"},"PeriodicalIF":5.5,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629775","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":"Synthesis of Dendronized Polymers via a “m+n” Grafting-onto Strategy with Reaction-Enhanced Reactivity of Intermediates (RERI) Mechanism","authors":"Yingqing Zhou,&nbsp;Yanping Xu,&nbsp;Xiuzhe Yin,&nbsp;Wangmeng Hou,&nbsp;Zhijia Liu,&nbsp;Yi Shi,&nbsp;Yongming Chen","doi":"10.1002/cjoc.202401233","DOIUrl":"https://doi.org/10.1002/cjoc.202401233","url":null,"abstract":"<div>\u0000 \u0000 <p>Dendronized polymers (DenPols) with tunable shape and surface property have been recognized as a type of promising unimolecular nanomaterials. However, it still has lacked a rapid and efficient approach to the facile synthesis of DenPols with high-generation and well-defined structures. Herein, we report a “<i>m+n”</i> grafting-onto strategy combined with the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction with reaction-enhanced reactivity of intermediates (RERI) mechanism for synthesizing DenPols G_{<i>m</i>+<i>n</i>} by attaching <i>n</i>-generation dendrons (G_<i>n</i>) onto the <i>m</i>-generation DenPols G_<i>m</i>. In this “<i>m+n</i>” grafting-onto strategy, the DenPols G_<i>m</i> (<i>m</i> = 1, 2) bearing 1,3-triazido branches on the repeating unit were capable of RERI effect that guaranteed the CuAAC reaction in an extremely efficient way with ultrafast kinetics to synthesize third-, fourth- and fifth-generation DenPols (G₁₊₂, G₁₊₃, G₁₊₄, G₂₊₂, and G₂₊₃) with near quantitative grafting density and narrow distribution. Moreover, these resultant DenPols G_{<i>m</i>+<i>n</i>} had more terminal groups per repeating unit due to the three branches of 1,3-triazido structure, exhibiting valuable potential opportunities for molecular surface engineering. The development of this “<i>m</i>+<i>n</i>” grafting-onto strategy with RERI mechanism not only presents a new avenue for ultrafast preparing DenPols but also holds great promise for preparing unimolecular materials with more functional terminal groups.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 7","pages":"805-813"},"PeriodicalIF":5.5,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143521749","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":"Artificial Cell Wall: From Maintenance of Cell Viability to Boosting New Cellular Functionalities†","authors":"Haoxiang Yuan,&nbsp;Xin Qiao,&nbsp;Shangsong Li,&nbsp;Xiaoman Liu,&nbsp;Xin Huang","doi":"10.1002/cjoc.202400995","DOIUrl":"https://doi.org/10.1002/cjoc.202400995","url":null,"abstract":"&lt;div&gt;\u0000 \u0000 &lt;section&gt;\u0000 \u0000 &lt;h3&gt; Comprehensive Summary&lt;/h3&gt;\u0000 \u0000 &lt;p&gt;Artificial cell wall (ACW) referring to active functional cellular nano-coatings is capable of providing more cell-shell synergic and cooperative properties than conventional single cell nanoencapsulation (SCNE). With the development of SCNE, the issues of cytocompatibility, degradability, &lt;i&gt;etc&lt;/i&gt;., have already been improved successively. However, the further emphasis on the cooperativity between the cell itself and its shell is still missing and paying more attention on the functions of cellular hybrids. Recent research proved that the construction of nano-coating on cells not only needs to satisfy the functionalization of the single cells, but also is necessary to empower cells to interact with other cells and environments. This indicates that SCNEs on cells are tending to be more “active” to participate in the metabolic process of cells and gradually develop to the stage of ACWs. This review provided a reasonable description of artificial cell wall, and the realization of this concept requires cooperativity, self-adaption and fluxionality. Then, the methodologies of constructing ACWs were discussed. Finally, the applications were summarized accompanied by the potential outlook in the given fields.&lt;/p&gt;\u0000 \u0000 &lt;p&gt;\u0000 &lt;/p&gt;\u0000 &lt;/section&gt;\u0000 \u0000 &lt;section&gt;\u0000 \u0000 &lt;h3&gt; Key Scientists&lt;/h3&gt;\u0000 \u0000 &lt;p&gt;Within recent ten years, fabricating a biocompatible nano-coating on the surface of cells for cyto-protection rapidly developed. For example, Rawil F. Fakhrullin and Yuri M. Lvov developed a ‘layer-by-layer’ strategy to construct ‘face-lifting’ on the surface of micro-organisms. Afterwards, Choi introduced the concept of ‘artificial spore’ which is thin and tough biocompatible cell encapsulations. At the same time, Tsukruk summarized the functions of hydrogel-based ‘artificial spore’ in terms of cyto-protection in 2013. In 2016, Tang reported that the strategy of biomimetic mineralization can be used to improve and modify the metabolism processes of cells. More advanced, Qu and Hawker separately developed a way to introduce manganese dioxide nanozymes and &lt;i&gt;in-situ&lt;/i&gt;-grafting polymers on the surface of cells to realize the responsive effects towards the artificial regulation in 2017. In 2018, Huang showed a way to generate a type of heritable artificial cell wall based on &lt;i&gt;in situ&lt;/i&gt; self-assembly of coacervate micro-droplets around yeast cells. In 2019, Jeffrey reported that nanoparticles can be adopted to construct exoskeletons outside the cells which can endow new functions and forming ‘supracells’. Choi put forward the concepts of ‘active shell’ and ‘dynamic shell’ which indicated that the research of cellular nanoencapsulations was beginning to transition to control the fate of cells. Huang introduced a reasonable strategy in constructing","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 6","pages":"715-728"},"PeriodicalIF":5.5,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143424320","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":"1-Methylpyridine-2(1H)-thione Photocatalyzed Giese Reaction with N-Hydroxyphthalimide Esters via Single Electron Transfer","authors":"Lanting Li,&nbsp;Yuzhuo Wang,&nbsp;Li Yuan,&nbsp;Xinjun Tang","doi":"10.1002/cjoc.202401238","DOIUrl":"https://doi.org/10.1002/cjoc.202401238","url":null,"abstract":"<div>\u0000 \u0000 <p>We have developed a series of 1-methylpyridine-2(1<i>H</i>)-thione (MPT) analogues to be used as organocatalysts. The MPT catalysts are easily prepared and bench-stable. In our previous work, we found that the ground-state MPT catalyst could act as a nucleophile to generate primary radicals via an S_N2 pathway. However, this reaction was limited to benzyl radicals. Herein, we reported a new catalytic property of the MPT catalyst. The photoexcited MPT catalyst (<i>E</i>(MPT^·+/MPT*) = –1.60 V vs. Ag/AgCl in MeCN) could reduce NHPI esters through a single electron transfer process. Various carbon radicals, including benzyl radical, as well as primary, secondary and tertiary alkyl radicals, could be generated easily. Notably, amino acids, peptide, pharmaceuticals, and other biologically active molecules could be modified by using this methodology showing the potential synthetic utility of this method.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 8","pages":"911-915"},"PeriodicalIF":5.5,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629850","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":"Space Charge Improved Poly(Aryl Ether Sulfone) Composite Membrane for Osmotic Energy Conversion","authors":"Jundong Zhong,&nbsp;Hongyan Qi,&nbsp;Tingting Xu,&nbsp;Weibo Sun,&nbsp;Zhe Zhao,&nbsp;Haibo Zhang,&nbsp;Xuanbo Zhu,&nbsp;Zhenhua Jiang","doi":"10.1002/cjoc.202401024","DOIUrl":"https://doi.org/10.1002/cjoc.202401024","url":null,"abstract":"<div>\u0000 \u0000 <p>The ion-selective porous membrane is the key component in osmotic energy conversion, and optimizing its permeability and selectivity is crucial for improving output performance. Here, to construct a permeability and selectivity synergistically enhanced osmotic energy generator, the surface and space charge synergistically enhanced 3D composite membrane is prepared by inserting sulfonated hydrogels into the 3D ion channels with tunable surface charge. The membrane's selectivity is improved from 0.66 to 0.94 by increasing the charge density on the membrane surface and the spatial charge density of the membrane. The experimental and simulation results showed that the synergistic enhancement of the spatial and surface charges significantly improved the electrostatic interactions between the ions and the ion channels, which led to the enhancement of selectivity, net ionic fluxes, and output performance. The space charge improved composite membrane presents an advanced power density of about 6.4 W·m^–2 under a 50-fold concentration gradient, which is nearly 2 times that of the phase inversion membrane without hydrogels. Our study provides a promising solution for constructing high-performance osmotic energy generators.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 7","pages":"814-822"},"PeriodicalIF":5.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143521835","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":"Aggregation-Dependent Polymer Photochromism via Double Intramolecular Hydrogen Bonds from Excited State Intramolecular Proton Transfer","authors":"Jingyuan Zhou,&nbsp;Huan Hu,&nbsp;Mingzhi Chen,&nbsp;Yongjie Li,&nbsp;Xin Cheng,&nbsp;Zhimin Ma,&nbsp;Shui Hu,&nbsp;Zhiyong Ma","doi":"10.1002/cjoc.202401035","DOIUrl":"https://doi.org/10.1002/cjoc.202401035","url":null,"abstract":"<div>\u0000 \u0000 <p>Excited-state intramolecular proton transfer (ESIPT) involves photochemical tautomerization between two excited states (E* and K*) <i>via</i> intramolecular proton transfer. Developing polymer photochromism based on the photochemical tautomerization of organic ESIPT molecules has been rarely reported. We report the ESIPT molecule <b>HBT-2OH</b> exhibits concentration-dependent photochromic behavior in a polyurethane (PU) network. At low concentrations, <b>HBT-2OH</b> primarily exists in the <i>trans</i>-enol configuration without intramolecular OH···N hydrogen bonds in PU, emitting blue fluorescence at ~464 nm (enol emission). Upon UV irradiation, the dihedral angle between the proton donor and acceptor twists to form an intramolecular OH···N H-bond, converting <i>trans</i>-enol to <i>cis</i>-enol and resulting in ESIPT with pale yellow fluorescence at ~603 nm (keto emission). The photochromic effect of <b>HBT-2OH@PU</b> diminishes at high concentrations due to that aggregation favors the <i>cis</i>-enol form. Control molecules <b>HBT, HBO-2OH</b>, and <b>HBI-2OH</b> show no photochromism in PU, confirming that ethanolyl branches and intramolecular OH···S hydrogen bonds stabilize the <i>trans</i>-enol configuration of <b>HBT-2OH</b>. Incorporating these molecules into PMMA and PCL networks demonstrates that increased free volume and smaller aggregates enhance photochromism by reducing resistance to dihedral angle twisting. Density functional theory (DFT) calculations further confirm stable intramolecular heteroatomic hydrogen bonds (OH···S) exist in <b>HBT-2OH</b>. This study offers new theoretical insights and opens avenues for research on polymer based photochromic materials.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 8","pages":"879-888"},"PeriodicalIF":5.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629783","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":"Photoinduced Metal-/Additive-Free Difluoromethylation of N-Heteroaromatics†","authors":"Congjun Zhu,&nbsp;Yangyang Shen,&nbsp;Tao Guo,&nbsp;Qing Yang,&nbsp;Dongpu Zhao,&nbsp;Huiqing Yang,&nbsp;Jin Xie","doi":"10.1002/cjoc.202401153","DOIUrl":"https://doi.org/10.1002/cjoc.202401153","url":null,"abstract":"<div>\u0000 \u0000 <p>Herein, we report a photo-induced, metal-/additive-free protocol for the difluoromethylation of <i>N</i>-heteroaromatics with [bis(difluoroacetoxy)iodo]benzene as the difluoromethylation reagent. The protocol affords difluoromethylated <i>N</i>-heteroaromatics in moderate to good yield (up to 91%). The transformation is compatible with a wide range of substrates and has good tolerance towards various functional groups. Moreover, the synthetic value of this method is further demonstrated by applications in gram-scale synthesis and the late-stage functionalization of biologically important molecules.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 8","pages":"905-910"},"PeriodicalIF":5.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629785","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":"Electrochemical N–H Methylsulfoxidation of Sulfoximines with DMSO","authors":"Qing-Ru Zhu,&nbsp;Gen Liu,&nbsp;Yongxiang Wang,&nbsp;Zhubing Xiao,&nbsp;Hui Gao,&nbsp;Pei-Long Wang","doi":"10.1002/cjoc.202401029","DOIUrl":"https://doi.org/10.1002/cjoc.202401029","url":null,"abstract":"<div>\u0000 \u0000 <p>The N–H methylsulfoxidation of sulfoximines using DMSO as a methylsulfinyl source, induced by electrochemistry, has been developed. This method is the first example of an electrochemical reaction in which DMSO serves as a methylsulfinyl source. Unlike previous electrochemical reactions involving DMSO as a substrate, which exclusively proceed via radical mechanisms, this reaction follows an S-cation pathway. A wide range of <i>N</i>-methylsulfinyl sulfoximines were successfully obtained.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 8","pages":"897-904"},"PeriodicalIF":5.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629784","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":"Dual-Chromophore Fluorescent Probe: Multi-Stimuli Sensing and Visual Discrimination","authors":"Min Qiao,&nbsp;Yuheng Huang,&nbsp;Xiaolin Zhu,&nbsp;Liping Ding,&nbsp;Yu Fang","doi":"10.1002/cjoc.202401058","DOIUrl":"https://doi.org/10.1002/cjoc.202401058","url":null,"abstract":"<div>\u0000 \u0000 <p>The advancement of multifunctional fluorescent probes for monitoring diverse environmental parameters is of paramount importance. In this study, we engineered dual-chromophore fluorescent probe, <b>DBT</b>, that responds to multiple stimuli by integrating functional groups with unique characteristics. Notably, the probe <b>DBT</b> exhibits pronounced bimodal emission under specific conditions, with its fluorescence shifting between red and blue in response to alterations in solvent composition, humidity levels, and temperature variations. Significantly, <b>DBT</b> facilitates the differentiation and visual identification of eight solvents, and permits the quantitative detection of trace water content in organic solvents. Additionally, it allows for the visual detection of gasoline. These findings herald the development of single-molecule fluorescent materials capable of responding to multiple stimulus, paving the way for simultaneous multi-stimuli detection and discrimination in various applications.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 8","pages":"871-878"},"PeriodicalIF":5.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629754","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}