Science China Chemistry最新文献

{"title":"Ag+-induced energy level splitting in Ln-MOFs achieves enhanced Eu3+ emission intensity","authors":"Xiaoyong Zhai,&nbsp;Xijiao Mu,&nbsp;Guoying Tan,&nbsp;Lijuan Liang,&nbsp;Yao Kou,&nbsp;Pingru Su,&nbsp;Chun-Hua Yan,&nbsp;Yu Tang","doi":"10.1007/s11426-024-2386-0","DOIUrl":"10.1007/s11426-024-2386-0","url":null,"abstract":"<div><p>In lanthanide (Ln) complexes, the oversight of f-electrons and inner-shell relativistic interactions has constituted a critical gap, limiting a nuanced understanding and modulation of their luminescent properties. Addressing this issue, our study introduces a pioneering series of Ln-based metal-organic frameworks (Ln-MOFs), designated as Ln-TCPP, utilizing tetraphenylpyrazine-derived ligand and Ln³⁺ ions (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) to modulate luminescence through advanced synthesis and theoretical analysis. We particularly emphasize the enhancement of Eu³⁺ luminescence in Ln-TCPP, where incorporating Ag⁺ ions to replace [(CH₃)₂NH₂]⁺ within the Ln-MOFs plays a pivotal role. Theoretically, by employing time-dependent density functional theory (TD-DFT) with full-electron relativistic effects, we demonstrate that Ag⁺ ions induce a splitting in the energy levels of Eu³⁺. This splitting effectively reduces the rate of non-radiative transitions, significantly amplifying Eu³⁺ emission intensity. Our findings not only fill a long-standing void in understanding the all-electron relativistic interaction between f-electrons in Ln-MOFs luminescence but also establish a new strategy for controlling and optimizing the luminescent efficacy of these materials for potential applications.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 3","pages":"924 - 934"},"PeriodicalIF":10.4,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475245","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":"Tetraphenylethylene-derived organic cages with persistent photogenic radicaloids and efficient photothermal conversion","authors":"Suqiong Yan,&nbsp;Bo Yang,&nbsp;Fanda Feng,&nbsp;Yuan Zhang,&nbsp;Shirong Ban,&nbsp;Hui Ma,&nbsp;Wei Huang","doi":"10.1007/s11426-024-2276-0","DOIUrl":"10.1007/s11426-024-2276-0","url":null,"abstract":"<div><p>Transformation of the electronic spin states has received significant interest in recent years because of its applications in the magnetic information storage materials and optical response switches. However, it can be formidably challenging to use ultraviolet (UV) light as a contactless stimulus to alter the electronic spin states of the supramolecular cages. Inspired by the approach on the radical cation mechanism of the Scholl reaction and the photocyclization reactivity of tetraphenylethylene (TPE) derivatives, we report two photochromic cages (<b>cage-TPE-1</b> and <b>cage-TPE-2</b>) that can be photochemically transformed from electron paramagnetic resonance (EPR)-silent to EPR-active form via UV irradiation due to the photo-induced electron transfer process at the TPE moiety. EPR provided a strong single-electron signal with a <i>g</i> value of 2.003 in <b>cage-TPE-1</b> and <b>cage-TPE-2</b> but no signal was detected for the pristine samples without the UVexposure. The transformation can be monitored by ultraviolet–visible–near-infrared (UV–vis–NIR) and photoluminescence (PL) spectroscopy. The photogenic radical cage intermediate was unstable in solution resulting in the degradation and intramolecular cyclization of the reactive species, while the radicals were found to be stable and persistent in the solid state due to the spin delocalization, the steric protection of confined cavities, and the oxygen isolation. Both theoretical calculations and spectral measurements suggest that the photogenic radical <b>cage-TPE-2</b>^{<b>(•+)</b>} experiences photocyclization on the TPE core. Compared with the close-shell cage, the radical <b>cage-TPE-1</b>^{<b>(•+)</b>} and <b>cage-TPE-2</b>^{<b>(•+)</b>} exhibit better photothermal conversion performance due to the incubated infrared absorption from open-shell electron feature and reduced band gap.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 2","pages":"661 - 669"},"PeriodicalIF":10.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446479","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":"pH-responsive AIE nanogels for synergistic chemo-photodynamic cancer therapy with imaging guidance","authors":"Yilin Zhu,&nbsp;Liping Zhang,&nbsp;Rongyuan Zhang,&nbsp;Chenghan He,&nbsp;Han Yang,&nbsp;Yong Liu,&nbsp;Ryan T. K. Kwok,&nbsp;Jacky W. Y. Lam,&nbsp;Jianwei Sun,&nbsp;Jing Feng,&nbsp;Zheng Zhao,&nbsp;Cuiping Yao,&nbsp;Ben Zhong Tang","doi":"10.1007/s11426-024-2379-x","DOIUrl":"10.1007/s11426-024-2379-x","url":null,"abstract":"<div><p>Photodynamic therapy (PDT) is a promising cancer treatment that uses photosensitizers (PSs) to generate cytotoxic reactive oxygen species (ROS) under light, but improving its efficacy is crucial for clinical applications. To address this, we propose a smart nanoplatform (P@BAO-DOX) for synergistic chemo-photodynamic therapy, featuring efficient PDT, controllable drug release, and fluorescence imaging guidance. We designed an aggregation-induced emission (AIE)-based PS (BAO) with effective ROS generation and NIR-II fluorescence. Additionally, BAO as a PS and doxorubicin (DOX) as a chemo drug were encapsulated in pH-responsive nanogels (PNA) to obtain P@BAO-DOX nanogels. Upon uptake by tumor cells, the nanogel releases drugs in acidic conditions, leading to cell death. White light irradiation further triggers BAO to produce substantial ROS, enhancing phototoxicity and synergistic chemo-PDT cancer therapy. Thus, P@BAO-DOX nanogels, as a smart nanoplatform, offer precise drug release and efficient ROS generation for imaging-guided chemo-PDT synergistic therapy, showing promise in advancing cancer treatment.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 4","pages":"1445 - 1455"},"PeriodicalIF":10.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11426-024-2379-x.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716656","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"New Co-MOF adsorption material with pharynx-shaped channel and large cavity for record ethylene and propylene purification","authors":"Lin Zhang,&nbsp;Jia-Qi Ma,&nbsp;Yi-Zhao Guo,&nbsp;Xiu-Yuan Li,&nbsp;Lei Hou,&nbsp;Yao-Yu Wang,&nbsp;Zhonghua Zhu","doi":"10.1007/s11426-024-2271-2","DOIUrl":"10.1007/s11426-024-2271-2","url":null,"abstract":"<div><p>Ethylene (C₂H₄) and propylene (C₃H₆) produced by methanol to olefin (MTO) technology are important chemical raw materials. However, the purification and separation between C₂H₄ and C₃H₆ mixtures is very challenging. Herein, a novel microporous metal-organic framework (MOF) adsorbent Co₂(OATA)(DPA) was fabricated through mixed linkers of 5,5′-(oxalylbis(azanediyl))diisophthalic acid (H₄OATA) and V-shaped di(pyridin-4-yl)amine (DPA) with –NHCO– and –NH– functional groups, which was endowed with ideal small pore size, large cavity, and interesting C₃H₆ trap constructed by four sets of –NH– groups. Under 298 K and a crucial low pressure (0.05 bar) for the separation in microporous materials, the MOF shows ultra-high C₃H₆ preferential adsorption (97.8 cm³ g⁻¹) and considerable C₃H₆/C₂H₄ selectivity (about 22), representing an advanced material for the reported porous materials with C₃H₆/C₂H₄ separation function. The studies of single crystal X-ray diffraction and simulations showed that the customized pore limitation in the MOF provided stronger multiple attractive interactions with C₃H₆, leading to significant adsorption selectivity in the process of competing adsorption for C₃H₆ and C₂H₄. In one separation step, the MOF generated highly pure C₂H₄ (⩾99.9%) and C₃H₆ (⩾99.6%) products respectively from C₂H₄/C₃H₆ mixtures at different ratios, pressures, and temperatures.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 3","pages":"967 - 973"},"PeriodicalIF":10.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475165","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":"Room-temperature polarization and spin switching via electron transfer in a valence tautomer","authors":"Zhen Liu,&nbsp;Xiao-Yi Zhang,&nbsp;Zhi-Rui Li,&nbsp;Han Xu,&nbsp;Hai-Xia Zhao,&nbsp;La-Sheng Long,&nbsp;Lan-Sun Zheng","doi":"10.1007/s11426-024-2288-1","DOIUrl":"10.1007/s11426-024-2288-1","url":null,"abstract":"<div><p>Achieving simultaneous polarization and spin switching at room temperature is essential for advanced multi-state storage and control applications, particularly in magnetoelectrics and electron spintronics, yet such materials are exceedingly rare. Based on polar molecular valence tautomerism of Co^III(3,5-DBcat)(3,5-DBsq)(<i>trans</i>-4-stypy)₂ (<b>1</b>), room-temperature spin and polarization switching was achieved via electron transfer. Notably, the ferroelectric polarization and spin switching in <b>1</b> are modulated by both temperature and light. The successful implementation of room-temperature polarization and spin switching in <b>1</b> signifies an important advancement toward practical applications.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 3","pages":"961 - 966"},"PeriodicalIF":10.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475164","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":"Size-selective hybridization chain reaction for accurate signal amplification in living cancer cells","authors":"Ting Chen,&nbsp;Xiaojiao Wang,&nbsp;Rongrong Gao,&nbsp;Meihe Yuan,&nbsp;Mei Chen,&nbsp;Xiao-Bing Zhang,&nbsp;Guoliang Ke","doi":"10.1007/s11426-024-2294-x","DOIUrl":"10.1007/s11426-024-2294-x","url":null,"abstract":"<div><p>Accurate signal amplification in living cells is highly important in biomedical research and medical diagnostics. Benefiting from its enzyme-free, efficient isothermal signal amplification ability, hybridization chain reaction (HCR) plays an important role in intracellular signal amplification; however, HCR fails the accurate signal amplification in the situation when the properties of some biological targets and analogues are too similar. Particularly, their signal amplification accuracy for mature miRNAs is unsatisfactory due to the signal interference of precursor microRNAs (abbreviated as pre-miRNAs), which also contain the sequence of mature miRNAs. Herein, we develop the first example of size-selective hybridization chain reaction probe for accurate signal amplification, which achieved accurate and sensitive biosensing of mature miRNAs in living cancer cells. Our probe, termed as qTcage, consists of a DNA nanocage for size-selective responsive to mature miRNAs, as well as a quadrivalent tetrahedral DNA structure for HCR signal amplification. Benefiting from the size-selectivity of DNA nanocage, shorter mature miRNAs (19–23 nt) rather than longer pre-miRNAs (60–70 nt) could enter the cavity to release triggers strand, which activates HCR reaction for fluorescence signal recovery. The probe efficiently reduces signal interference of pre-miRNAs and improves the imaging sensitivity for intracellular mature miRNAs, which was successfully applied for mature miRNAs imaging during drug treatment. Overall, this strategy provides the hybridization chain reaction with the feature of size-selective ability, which holds promise for further accurate signal amplification in biological processes study and clinical diagnostics.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"67 12","pages":"4259 - 4266"},"PeriodicalIF":10.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142758036","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":"Fostering a growing chemistry community: the 2024 emerging investigator issue of Science China Chemistry","authors":"Li-Jun Wan","doi":"10.1007/s11426-024-2414-x","DOIUrl":"10.1007/s11426-024-2414-x","url":null,"abstract":"","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"67 12","pages":"3897 - 3905"},"PeriodicalIF":10.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142758035","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":"Potential dependence in electrocatalysis: a theoretical perspective","authors":"Leyu Liu,&nbsp;Zhaoming Xia,&nbsp;Zeyu Wang,&nbsp;Yinjuan Chen,&nbsp;Hai Xiao","doi":"10.1007/s11426-024-2402-2","DOIUrl":"10.1007/s11426-024-2402-2","url":null,"abstract":"<div><div><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 1","pages":"21 - 25"},"PeriodicalIF":10.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925612","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":"Ultrathin nickel sulfide nanosheets for sulfur ion electrooxidation assisted acetonitrile electroreduction","authors":"Xiao-Hui Wang,&nbsp;Ze-Nong Zhang,&nbsp;Na Li,&nbsp;Xuan Ai,&nbsp;Xue Xiao,&nbsp;Yu Chen,&nbsp;Shu-Ni Li","doi":"10.1007/s11426-024-2279-2","DOIUrl":"10.1007/s11426-024-2279-2","url":null,"abstract":"<div><p>Electrochemical reduction of acetonitrile (ACN) to ethylamine (ETA) is a new strategy for producing high-value chemicals. Herein, the ultrathin nickel sulfide nanosheets (Ni_<i>x</i>S_<i>y</i> NSs) anchored on nickel foam (NF) nanohybrid (Ni_<i>x</i>S_<i>y</i> NSs/NF) were designed as an efficient bifunctional electrocatalyst for the waste conversion. Owing to the introduction of the S element, the ultrathin nanosheet structure, and the three-dimensional architecture, Ni_<i>x</i>S_<i>y</i> NSs/NF simultaneously reveals excellent electrocatalytic activity for both electrochemical ACN reduction reaction (EACNRR) at the cathode and electrochemical sulfur ion (S²⁻) oxidation reaction (ESOR) at the anode. For the EACNRR, Ni_<i>x</i>S_<i>y</i> NSs/NF exhibits a Faradaic efficiency of 95.5% and the ETA yield of 923.1 mmol h⁻¹ g⁻¹ at −0.05 V potential. For the ESOR, the S²⁻ ion is oxidized to the value-added S₈ product, in which the oxidation potential is only 0.16 V at 50 mA cm⁻². Consequently, the assembled Ni_<i>x</i>S_<i>y</i> NSs/NF∥Ni_<i>x</i>S_<i>y</i> NSs/NF electrolytic cell is successfully established for the ESOR-assisted EACNRR system that only needs a cell voltage of 0.32 V to reach the 50 mA cm⁻² current density. This work provides an effective and energy-saving strategy for the co-production of value-added chemicals from pollutants.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 3","pages":"951 - 960"},"PeriodicalIF":10.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475163","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":"Breaking the concentration quenching limit of lanthanide emitter through multi-coupling of confined quasi-0D & 2D energy migration","authors":"Yuanchao Lei,&nbsp;Shanshan Zhou,&nbsp;Jianxi Ke,&nbsp;Licheng Yu,&nbsp;Youchao Wei,&nbsp;Yongsheng Liu,&nbsp;Maochun Hong","doi":"10.1007/s11426-024-2319-9","DOIUrl":"10.1007/s11426-024-2319-9","url":null,"abstract":"<div><p>The widespread applications of lanthanide-doped materials have fuelled a growing demand for precise control over the luminescence characteristics of these materials. However, the limitation imposed by concentration quenching remains a major obstacle in achieving efficient luminescence from lanthanide-doped materials. Herein, a novel strategy utilizing Sc₂O₃:Ln³⁺ microflowers to enable confined energy migration in both microscopic quasi-zero-dimensional (0D) and mesoscopic two-dimensional (2D) multi-coupling systems is proposed to overcome the concentration quenching limit of lanthanide emitters and achieve a remarkable doping amount of 48.14% on a single particle without resorting to complex core/multishell structure. Mechanistic studies reveal that the multi-confinement structure effectively restricts the range of energy migration and significantly reduces excitation energy migration to defects. Based on these highly doped Sc₂O₃ microflowers, full spectrum and power-dependent tunable multi-color lanthanide emission in a single particle is successfully achieved. Furthermore, the 2D-encoded patterns derived from these microflowers hold great promise for anti-counterfeiting applications. Our findings emphasize the multi-coupling of confined quasi-0D &amp; 2D energy migration within a well-designed structure, providing valuable insights into concentration quenching mechanisms. This also opens up new opportunities for multi-level anti-counterfeiting systems and information security.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 4","pages":"1372 - 1382"},"PeriodicalIF":10.4,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716951","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}