首页期刊导航|中国化学会会刊（英文）
期刊信息/Journal information
中国化学会会刊（英文）
中国化学会会刊（英文）
中国化学会会刊（英文）/Journal CCS Chemistry
正式出版
收录年代

    A C54B2 Polycyclic π-System with Bilayer Assembly and Multi-Redox Activity

    Liuzhong YuanJiaxiang GuoYue YangKaiqi Ye...
    876-884页
    查看更多>>摘要：Doping heteroatoms into polycyclic aromatic hydro-carbons(PAHs)is an efficient strategy to achieve fascinating electronic structures and materials.How-ever,nanoscale B-doped PAHs remain very challeng-ing because of the intrinsic instability of the boron atom and the lack of suitable precursors.In this study,we report a C54B2 polycyclic π-system with one em-bedded 1,4-diboron-substituted benzene subunit,which was successfully synthesized from doubly B-doped heptazethrene.This molecule represents not only the largest B-doped PAH by far but also an unprecedented B-doped nanographene.The fully zig-zag-armchair-edged structure creates a planar con-formation,thus leading to its unique bilayer assembly behavior.More importantly,it possesses intriguing electronic structure and optoelectronic properties,such as very broad light absorption that covers 350-750 nm,sharp near-infrared fluorescence with a band width of only 26 nm,and reversible five-step redox capability,all of which are rarely observed for other B-doped PAHs.In addition,this molecule dis-plays distinctive local aromaticity that cannot be reproduced via the reductive manipulation of an all-carbon congener.
      原文链接:
    • NETL
    • NSTL
    • 万方数据

    CASTING:A Potent Supramolecular Strategy to Cytosolically Deliver STING Agonist for Cancer Immunotherapy and SARS-CoV-2 Vaccination

    Jun-Jun WuFang-Yuan ChenBei-Bei HanHong-Qing Zhang...
    885-901页
    查看更多>>摘要：Stimulator of interferon genes,namely STING,an adaptor protein located in the endoplasmic reticulum,has been recog-nized as a shining target for cancer and infection research.However,STING agonists cyclic dinucleotides(CDNs)have shown almost zero efficacy in phase Ⅰ clinical trials as a mono-therapy,likely due to poor cellular permeability and rapid diffusion despite intratumoral injection.These deficiencies further affect other applications of CDNs,such as pandemic SARS-CoV-2 prevention and therapy.Here,we rationally de-sign a supramolecular cytosolic delivery system based on controllable recognition of calixarene,namely CASTING(CAlixarene-STING),to improve CDN druggability,including degradation stability,cellular permeability,and tissue reten-tion.CASTING efficiently enhances the immunostimulatory potency of CDGSF[a chemically modified cyclic di-GMP(CDG)]to generate an immunogenic microenvironment for melanoma regression,anti-PD-1 response rate increase,and durable memory formation against tumor recurrence.More important-ly,CASTING displays a superior adjuvant activity on SARS-CoV-2 recombinant spike/receptor binding domain vaccines,inducing robust and coordinated T-cell and antibody responses against SARS-CoV-2 infection in vivo.Collectively,the CASTING design represents an innovative advancement to facilitate the clinical translational capability of STING agonists.
      原文链接:
    • NETL
    • NSTL
    • 万方数据

    Achieving High-Performance Molecular Rectification through Fast Screening Alkanethiol Carboxylate-Metal Complexes Electroactive Units

    Lixian TianAiqing FanXi YuWenping Hu...
    902-914页
    查看更多>>摘要：Achieving high performance in molecular scale diode devices remains a formidable challenge due to the complexity of the charge transport process and the difficulty in device structure modulation.Herein,we demonstrated a low-cost and fast screening strategy to search for proper electroactive units and construct high performance self-assembled monolayer(SAM)-based molecular diodes.The strategy is based on off-the-shelf carboxylate-terminated alkane thiols and simple carboxylate-metal ion complexes,struc-tures denoted as Au-S-(CH2)n-1COO-Mm+(Cn+Mm+),where n=11,12,13,14,16,18,and Mm+=Ca2+,Mn2+,Fe2+,Fe3+,Co2+,Ni2+,Cu2+,and Zn2+,as the library of functional SAM layers on gold substrate.Combing the fast screening measurements using a eutectic indium-gallium alloy top contact(EGain),C18+Ca2+and C18+Zn2+structures were found to afford record high rectification ratio(RR)＞700 at±1.5 V.Theoreti-cal analysis based on a single level tunneling model shows that the C18+Ca2+and C18+Zn2+devices possessed an optimized combination of asymmetric voltage division,energy offset,and coupling of car-boxylate-metal complexes with the electrode.This newly developed method represents a general strat-egy for fast,inexpensive,and effective exploration of the functional metal complex chemical space,and can largely accelerate the development of practical high performance molecular diode devices.
      原文链接:
    • NETL
    • NSTL
    • 万方数据

    A Smart Molecule Showing Spin Crossover Responsive Aggregation-Induced Emission

    Cheng YiYin-Shan MengLiang ZhaoNian-Tao Yao...
    915-924页
    查看更多>>摘要：The utilization of spin crossover(SCO)to modulate the luminescence properties in smart multifunction-al materials and multichannel sensors is promising.However,it is challenging to build a strong coupling between SCO and luminescence in one system.Herein,we present a mononuclear compound[Fe(tpe-abpt)2(SeCN)2]·4DMF(1·4DMF,tpe-abpt:(4-(1,1,2,2-tetraphenylethene))-N-(3,5-bis(pyridin-2-yl)-4H-1,2,4-triazol-4yl)methanimine)showing aggre-gation-induced emission(AIE)and thermally induced SCO properties.Variable-temperature single-crystal structural analysis reveals that SCO changes the num-ber of pathways and strength of intermolecular inter-actions,resulting in deactivation of nonradiative decay and significant enhancement of luminescence.The photoluminescence(PL)intensity of 1.4DMF exhibited a fivefold increase upon the spin transition from the low-spin to the high-spin states.In contrast with the current strategy of controlling the Förster resonance energy transfer(FRET)process by utilizing SCO to tune the overlap degree between the emission band of the luminophore and UV-vis absorption band of high-spin and low-spin states,we developed a new approach to tune the intermolecular interactions between AIE luminogens(AIEgens)by utilizing a sub-tle SCO-induced structural transformation,therefore leading to effective coupling between SCO and lumi-nescence and a significant change in luminescence upon SCO.Our results provide a rational strategy to build smart multifunctionalized materials with remark-ably synergetic SCO and luminescence.
      原文链接:
    • NETL
    • NSTL
    • 万方数据
    • 维普

    Diselenide as a Dual Functional Mechanophore Capable of Stress Self-Reporting and Self-Strengthening in Polyurethane Elastomers

    Xiaopei LiFan YangYiran LiCheng Liu...
    925-933页
    查看更多>>摘要：Unlike biological materials that can sense mechanical force and actively remodel locally,synthetic polymers typically break down under stress.Molecular-level responses to damage with both stress-reporting and self-strengthening functions are significant yet diffi-cult to realize for synthetic polymers.To overcome this challenge,chemo-mechanical coupling into poly-mers that can simultaneously ameliorate mechanical,optical,or other functional properties of a polymer combined with mechanical treatment will offer a new principle for materials design.Here,we report a kind of elastomer in which destructive forces are chan-nelled into productive and bond-forming reactions by using diselenide(Se-Se)as a mechanophore.Polyure-thane has been functionalized with labile Se-Se bonds,whose mechanical activation generates seleno radicals that trigger radical transfer and cross-linking reactions in situ.These reactions are activated effi-ciently in a mechanical way by compression in bulk materials.The resulting covalent networks possess turn-on mechano-fluorescence and increased moduli,which provide the functions of stress reporting,mechano-healing,and mechano-remodeling for the deformed film.This study not only illuminates the mechano-responsive nature of Se-Se bonds in the bulk state but also paves the way for the development of new stress-responsive materials.
      原文链接:
    • NETL
    • NSTL
    • 万方数据
    • 维普

    Pressure-Induced Intermetallic Charge Transfer and Semiconductor-Metal Transition in Two-Dimensional AgRuO3

    Chuanhui ZhuJinjin YangPengfei ShanMei-Huan Zhao...
    934-946页
    查看更多>>摘要：The intricate correlation between charge degrees of freedom and physical properties is a fascinating area of research in solid state chemistry and condensed matter physics.Herein,we report on the pressure-induced successive charge transfer and accompanied resistive evolution in honeycomb layered ruthenate AgRuO3.Structural revisiting and spectroscopic anal-yses affirm the ilmenite type R-3 structure with mixed valence cations as Ag+1/+2Ru+4/+5O3 at ambient pres-sure.In-situ pressure-and temperature-dependent resistance variation reveals a successive insulator-metal-insulator transition upon pressing,accompa-nied by unprecedented charge transfer between Ag and Ru under applied pressure,and a further structur-al phase transition in the insulator region at higher pressure.These phenomena are also corroborated by in-situ pressure-dependent Raman spectra,syn-chrotron X-ray diffraction,bond valence sums,and electronic structure calculations,emphasizing the dominated rare Ag2+,and near zero thermal expansion in the ab-plane in the metallic zone mostly due to the Jahn-Teller effect of d9-Ag2+.The multiple electronic instabilities in AgRuO3 may offer new possibilities toward novel and unconventionally physical and chemical behaviors in strongly correlated honeycomb lattices.
      原文链接:
    • NETL
    • NSTL
    • 万方数据

    Dual Rolling Circle Amplification-Assisted Single-Particle Fluorescence Profiling of Exosome Heterogeneity for Discriminating Lung Adenocarcinoma from Pulmonary Nodules

    Yan ZhouHaoxiang LiMin HouJianjun He...
    947-957页
    查看更多>>摘要：Exosomes secreted by tumor cells carry abundant molecular biomarkers that reflect the status of their originating cells.These tumor-derived exosomes(TDEs)have emerged as attractive diagnostic tar-gets.However,the identification and characteriza-tion of highly heterogeneous TDEs remain practically challenging.Here,we report a dual rolling circle amplification(DRCA)-assisted approach for the se-lective encapsulation of single TDEs for fluorescence microscopic and flow cytometric analysis.TDEs have been targeted by aptamers that recognized their surface tumor marker and exosomal marker CD63,following DRCA that produced entangling polymeric DNA chains,resulting in facile particle enlargement that allows single-particle fluorescence profiling of exosome heterogeneity.We have demonstrated the use of a dual-marker positive ratio for exosome dif-ferentiation and applied division and multiplication operations for normalized and magnified marker het-erogeneity analysis.We further applied this assay to distinguish lung adenocarcinoma and pulmonary nodule patients and found an accuracy of 90％.We anticipate promising transformations of this straight-forward assay into clinically implantable diagnostic methods.
      原文链接:
    • NETL
    • NSTL
    • 万方数据

    C-H…S Hydrogen Bond Assisted Supramolecular Encapsulation of Fullerenes with Nanobelts

    Jialin XieXia LiZhenglin DuYandie Liu...
    958-970页
    查看更多>>摘要：Hydrogen-bonded capsules have been widely employed as supramolecular hosts for organic mo-lecular guests.Encapsulation of fullerenes by cap-sules is relatively scarce,especially those that utilize sulfur atoms as hydrogen-bond acceptors.Herein,we describe,in both solution and solid state,a bowl-shaped nanobelt[8]cyclophenoxathiin 1a and its tetra-methylated derivative 1b that can form C-H…S hydrogen-bonded capsules induced by complexation with suitable fullerenes.1a strongly encapsulates C60,C70,or 6,6-phenyl-C61-butyric acid methyl ester(PC61BM)to form a 2∶1 ternary complex featuring 16 equatorial(sp2)C-H…S hydrogen bonds.A pseudorotaxane structure was further obtained for the complex of 1a with PC61BM.Conversely,a 1∶1 inclusion complex was observed for binding C60 or PC61BM with 1b indicating the reduced tendency to form capsules by introducing methyl groups into the belt.Surprisingly,the capsule-like structure was retained for the 1∶2 complex of C70 with 1b as ob-served by the presence of multiple(sp3)C-H…S hy-drogen bonds.The strong binding affinity and tailorable complexation mode enable further appli-cations of nanobelts in fullerene chemistry.
      原文链接:
    • NETL
    • NSTL
    • 万方数据

    Controlled Growth Interface of Charge Transfer Salts of Nickel-7,7,8,8-Tetracyanoquinodimethane on Surface of Graphdiyne

    Yuxin LiuYang GaoFeng HeYurui Xue...
    971-981页
    查看更多>>摘要：Here we report an in situ assembly growth method that controls the growth of NiTCNQ on the surface of graphdiyne(GDY).The catalytic system of donor-acceptor-donor(GDY/TCNQ/Ni)structure with multiple charge transfer(CT)was achieved by con-trolling the growth of NiTCNQ on the surface of GDY.Significantly,a controlled double layer interface of GDY/TCNQ/Ni was formed.This system implemen-ted simultaneously the two elements we expected(1)an incomplete CT,and(2)the infinite distribution of active sites originating from highly asymmetric sur-face charge distribution.The high conductivity and typical semiconductor characteristics of the catalyst endows it with high catalytic activity.We found that an electrolytic cell consisting of the CT salt as a catalyst provided a 1.40 V ultra-small cell voltage up to 10 mA cm-2 and the outer GDY film effectively prevented the corrosion of the catalyst.Our study is the first to introduce CT complexes to a novel cata-lytic material platform for high selectivity of cata-lysts,and undoubtedly demonstrates the high selectivity,stability,and activity of such catalytic systems,which provides a new space for the devel-opment of novel conceptual catalysts.
      原文链接:
    • NETL
    • NSTL
    • 万方数据

    Inherently Chiral 6,7-Diphenyldibenzo[e,g][1,4]diazocine:Enantioselective Synthesis and Application as a Ligand Platform

    Yu LuoXilong WangWeiming HuYan Peng...
    982-993页
    查看更多>>摘要：Inherently chiral 6,7-diphenyldibenzo[e,g][1,4]diazo-cine(DDD)has been synthesized enantioselectively for the first time via chiral phosphoric acid(CPA)-catalyzed cyclocondensation of readily available[1,1'-biphenyl]-2,2'-diamine(1a)and benzil(2a)in 82％yield,with 98％ee under mild reaction conditions.The strategy could also be applied to racemic biaryl dia-mines through kinetic resolution.The unexpectedly high interconversion energy barriers between the enantiomers(ΔG=39.5 kcal/mol)and the chemical stability rendered DDD an ideal platform for develop-ing new chiral ligands and catalysts.Unique inherently chiral DDD-based phosphoramidites,phosphoric acid,mono-and diphosphine ligands were prepared from optically pure diphenol derivative DDDOL as a common precursor.Preliminary asymmetric reactions catalyzed by Pd or Rh in the presence of newly devel-oped ligands exhibited comparable or even better enantioselectivities than the corresponding BINOL-or SPINOL-derived ligands.Density functional theory calculation revealed the origin of the enantioselectiv-ity during the process.
      原文链接:
    • NETL
    • NSTL
    • 万方数据