作者机构：
[Gao, Ke; Zhang, He; Zhang, Yanmeng] Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Key Lab Pesticides & Chem Biol,Minist Educ, 152 Luoyu Rd, Wuhan, Hubei, Peoples R China.
通讯机构：
[Ke Gao] C;CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, P.R. China
摘要：
The selective reductive N-methylation and N,N-dimethylation of primary amines using CO2 are some of the most significant challenges faced by organic chemists. Herein, we report the highly selective N,N′-diisopropylcarbodiimide-catalyzed methylation of primary amines using 1 atm CO2 under metal-free conditions. Borane–piperazine and borane–trimethylamine complexes were used as reducing agents for the N-methylation and N,N-dimethylation of various aromatic primary amines, respectively, in the presence of CO2. Mechanistic studies suggest that the selectivity of methylation is controlled by the steric effects of amines and boranes.
摘要：
A compact 4-port coplanar waveguide (CPW) fed ultra-wideband (UWB) multiple-input-multiple-output (MIMO) antenna with enhanced isolation is proposed to operate from 3.66 GHz to 16.61 GHz with 127.78% impedance bandwidth. The proposed antenna system consists of 4 orthogonal arrays of monopole antennas improved by four iterations. The UWB characteristic of the antenna is obtained from an improved monopole antenna fed by CPW. The final MIMO antenna is machined on a Rogers 4003C substrate with dimensions of 60 x 60 x 0.3 mm(3). The orthogonal arrangement of antennas brings about the polarization diversity and certain isolation of MIMO antennas. Four rows of orthogonal metasurface elements with via holes and the ring of the backplane further improve the isolation between antenna elements in the MIMO system. The MIMO antenna has an impedance bandwidth of 12.95 GHz with S-11 < -10 dB and good isolation (S-21 =S-41 < -30 dB and S-31 < -20 dB). In particular, S31 is always less than -25 dB at frequencies greater than 6 GHz. The measured results of MIMO antenna agree with the simulated results. The optimized MIMO antenna has excellent performance in many aspects, such as UWB, compact size, omnidirectional radiation, enhanced isolation and high efficiency, which means that it has application potential in UWB wireless communication systems.
摘要：
Enrichment of OVs on oxide semiconductors is an effective strategy to promote their photocatalytic performances but limited by the maximum concentration allowed by lattice thermodynamics. Herein, we report that an In(I) doping strategy, realized by an UV light-induced reduction of a sluggish In(III) precursor, can promote OVs-laden BiOCl by up to 6.5 times for the visible-light sodium pentachlorophenate (PCPNa) degradation. The photocatalysis mechanism study highlighted the In(I) site as an electron transfer site could reduce PCPNa directly, related to the In(I) induced more negative conduction band and faster transfer of electron. Moreover, several monocyclic aromatic organic compounds (AOC) exhibited degradation selectivity over In(I) doped OVs-laden BiOCl (BOVs-In) by an electron reduction path, PCPNa with the lowest negative charge density on the benzene ring has been degraded fastest. Differently, the doped In(I) in BOVs-In mainly triggered the multiring Rhodamine B degradation by promoting the O-center dot(2)- generation not the directly electron reduction path. The electron transfer ability, band structure, and the free energy of O-2 activation over BOVs-In were confirmed by TPV spectra, EPR spectra and DFT calculation. This study illustrates an In(I) doping strategy to couple with OVs engineering for champion photoactivity of BiOCl for AOC degradation under visible light irradiation.
摘要：
The immune checkpoint blockade (ICB) antibody immunotherapy has demonstrated clinical benefits for multiple cancers. However, the efficacy of immunotherapy in tumors is suppressed by deficient tumor immunogenicity and immunosuppressive tumor microenvironments. Pyroptosis, a form of programmed cell death, can release tumor antigens, activate effective tumor immunogenicity, and improve the efficiency of ICB, but efficient pyroptosis for tumor treatment is currently limited. Herein, we show a mild hyperthermia-enhanced pyroptosis-mediated immunotherapy based on hollow carbon nanozyme, which can specifically amplify oxidative stress-triggered pyroptosis and synchronously magnify pyroptosis-mediated anticancer responses in the tumor microenvironment. The hollow carbon sphere modified with iron and copper atoms (HCS-FeCu) with multiple enzyme-mimicking activities has been engineered to induce cell pyroptosis via the radical oxygen species (ROS)-Tom20-Bax-Caspase 3-gasdermin E (GSDME) signaling pathway under light activation. Both in vitro and in vivo antineoplastic results confirm the superiority of HCS-FeCu nanozyme-induced pyroptosis. Moreover, the mild photothermal-activated pyroptosis combining anti-PD-1 can enhance antitumor immunotherapy. Theoretical calculations further indicate that the mild photothermal stimulation generates high-energy electrons and enhances the interaction between the HCS-FeCu surface and adsorbed oxygen, facilitating molecular oxygen activation, which improves the ROS production efficiency. This work presents an approach that effectively transforms immunologically "cold" tumors into "hot" ones, with significant implications for clinical immunotherapy.
作者机构：
[Lei, Shuang-Gui; Wu, An-Xin; Zhou, You; Chen, Ting; Yu, Zhi-Cheng; Wu, Yan-Dong; Wang, Li-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Gao, Meng] South China Univ Technol, Natl Engn Res Ctr Tissue Restorat & Reconstruct, Sch Mat Sci & Engn, Key Lab Biomed Mat & Engn,Minist Educ, Guangzhou 510006, Peoples R China.
通讯机构：
[Wu, AX ] C;[Gao, M ] S;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;South China Univ Technol, Natl Engn Res Ctr Tissue Restorat & Reconstruct, Sch Mat Sci & Engn, Key Lab Biomed Mat & Engn,Minist Educ, Guangzhou 510006, Peoples R China.
摘要：
An unprecedented dual alpha,beta-C(sp(2))-H functionalization/bicyclization strategy of o-hydroxyphenyl enaminones for the preparation of chromeno[2,3-b]pyrrol-4(1H)-ones has been established. The multi-component cascade reaction achieves dual alpha,beta-C(sp(2))-H functionalization of o-hydroxyphenyl enaminones to construct C2,C3-disubstituted chromenes for the first time, along with intramolecular cascade cyclization between two functional groups to construct four new bonds and two rings in one pot. Moreover, the products have polarity sensitivity and feature aggregation-induced emission (AIE) characteristics after simple modifications, which is promising for bioimaging and theranostic applications.
摘要：
The synthesis of chiral endocyclic allenes, especially the medium-sized ones, remains a challenge in allene chemistry due to unfavorable tension and difficult stereocontrol. Herein, an efficient protocol for the construction of chiral nine-membered endocyclic allenes via palladium-catalyzed asymmetric cycloaddition/Cope rearrangement relay of vinyl carbonates with activated enynes is highlighted. This process provides rapid access to a variety of chiral nine-membered endocyclic allenes in good yields with excellent enantioselectivities. In particular, a chiral P,S-ligand shows good performance on stereoinduction, generating central and axial chirality in a single transformation, which is rationalized by DFT calculations and by a proposed transition state.
1 Introduction
2 Pd-Catalyzed Asymmetric Cycloaddition/Cope Rearrangement Relay
3 Plausible Mechanism and Stereochemical Outcome
4 Conclusion and Outlook
通讯作者：
Prof. Liuyong Hu<&wdkj&>Prof. Wenling Gu<&wdkj&>Prof. Chengzhou Zhu<&wdkj&>Prof. Liuyong Hu Prof. Liuyong Hu Prof. Liuyong Hu<&wdkj&>Prof. Wenling Gu Prof. Wenling Gu Prof. Wenling Gu<&wdkj&>Prof. Chengzhou Zhu Prof. Chengzhou Zhu Prof. Chengzhou Zhu
作者机构：
[Mengzhen Xi; Zhichao Wu; Zhen Luo; Ling Ling; Weiqing Xu; Hengjia Wang; Qie Fang; Prof. Wenling Gu; Prof. Chengzhou Zhu; Mengzhen Xi Mengzhen Xi Mengzhen Xi; Zhichao Wu Zhichao Wu Zhichao Wu; Zhen Luo Zhen Luo Zhen Luo; Ling Ling Ling Ling Ling Ling; Weiqing Xu Weiqing Xu Weiqing Xu; Hengjia Wang Hengjia Wang Hengjia Wang; Qie Fang Qie Fang Qie Fang; Prof. Wenling Gu Prof. Wenling Gu Prof. Wenling Gu; Prof. Chengzhou Zhu Prof. Chengzhou Zhu Prof. Chengzhou Zhu] National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan, 430079 P. R. China;[Prof. Liuyong Hu; Prof. Liuyong Hu Prof. Liuyong Hu Prof. Liuyong Hu] Hubei Key Laboratory of Plasma Chemistry and Advanced Materials, Hubei Engineering Technology Research Center of Optoelectronic and New Energy Materials, Wuhan Institute of Technology, Wuhan, 430205 P. R. China;[Runshi Xiao; Runshi Xiao Runshi Xiao Runshi Xiao] National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan, 430079 P. R. China<&wdkj&>Hubei Key Laboratory of Plasma Chemistry and Advanced Materials, Hubei Engineering Technology Research Center of Optoelectronic and New Energy Materials, Wuhan Institute of Technology, Wuhan, 430205 P. R. China
通讯机构：
[Prof. Liuyong Hu; Prof. Liuyong Hu Prof. Liuyong Hu Prof. Liuyong Hu] H;[Prof. Wenling Gu; Prof. Chengzhou Zhu; Prof. Wenling Gu Prof. Wenling Gu Prof. Wenling Gu; Prof. Chengzhou Zhu Prof. Chengzhou Zhu Prof. Chengzhou Zhu] N;National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan, 430079 P. R. China<&wdkj&>Hubei Key Laboratory of Plasma Chemistry and Advanced Materials, Hubei Engineering Technology Research Center of Optoelectronic and New Energy Materials, Wuhan Institute of Technology, Wuhan, 430205 P. R. China
摘要：
In conventional luminol electrochemiluminescence (ECL) systems, hydrogen peroxide and dissolved oxygen are employed as typical co-reactants to produce reactive oxygen species (ROS) for efficient ECL emission. However, the self-decomposition of hydrogen peroxide and limited solubility of oxygen in water inevitably restrict the detection accuracy and luminous efficiency of luminol ECL system. Inspired by ROS-mediated ECL mechanism, for the first time, we used cobalt-iron layered double hydroxide as co-reaction accelerator to efficiently activate water to generate ROS for enhancing luminol emission. Experimental investigations verify the formation of hydroxyl and superoxide radicals in the process of electrochemical water oxidation, which subsequently react with luminol anion radicals to trigger strong ECL signals. Finally, the detection of alkaline phosphatase has been successfully achieved with impressive sensitivity and reproducibility for practical sample analysis.
作者机构：
[Zhu, Xinrui; Jia, Shuwen; Li, Dongfeng; Li, DF] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.
通讯机构：
[Li, DF ] C;Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.
摘要：
A key challenge in the design of magnetic molecules with intramolecular charge transfer behavior is to obtain reversible magnetic bistability triggered by external stimuli. Here, we show that two dinuclear metal complexes, [(bbp)Fe(CN)3Mn(Py5Me2)]center dot 2.5CH3OH (4) and [(bbp)Fe(CN)3Ni(Py5Me2)]center dot 2.5CH3OH (5) (Py5Me2 = 2,6-bis(1,1-di(pyridine-2-yl)ethyl)pyridine, H2bbp = 2,6-bis(benzimidazole-2-yl)pyridine), were self-assembly synthesized by (Bu4N)2[(bbp)FeIII(CN)3] and [Mn(Py5Me2)(OH2)](ClO4)2 or [Ni(Py5Me2)(OH2)](ClO4)2, respectively. Complexes 4 and 5 exhibited intramolecular metal-to-metal charge transfer with the addition of acids or bases in solution by UV-visible spectrophotometric measurements and electrochemistry studies, and concomitant switching of the {FeIII(mu-CN)MnII/NiII} state to the {FeII(mu-CN)MnIII/NiIII} state. The possibility of external stimulus induced intra-molecular metal-to-metal charge transfer by protonation in [(bbp)Fe(CN)3Mn(Py5Me2)]center dot 2.5CH3OH and [(bbp)Fe(CN)3Ni(Py5Me2)]center dot 2.5CH3OH molecules was investigated.
摘要：
Catalytic oxidation technology is currently considered as a feasible approach to degrade and mineralize volatile organic compounds (VOCs). However, it is still challenging to realize efficient removal of VOCs through catalytic oxidation at room temperature. In our study, a novel flow-through electrocatalytic reactor was designed, composed of porous solid-electrolyte, gas-permeable titanium sub-oxides/titanium-foam (TiSO/Ti-foam) as anode and platinum coated titanium foam (Pt/Ti-foam) as cathode. This device could oxidize nearly 100% of benzene (10 ppm) to carbon dioxide at a current density of 1.2 mA/cm2 under room temperature. More importantly, the device maintained excellent stability over 1000 h. Mechanism of benzene mineralization was discussed. Hydroxyl radicals generated on the TiSO/Ti-foam anode played a crucial role in the oxidation of benzene. This study provides a promising prototype of the electrochemical air purifier, and may find its application in domestic and industrial air pollution control.
通讯机构：
[Wu, DY ] X;Xiamen Univ, State Key Lab Phys Chem Solid Surface, Collaborat Innovat Ctr Chem Energy Mat, Xiamen 361005, Peoples R China.;Xiamen Univ, Coll Chem & Chem Engn, Dept Chem, Xiamen 361005, Peoples R China.
摘要：
Stereoelectronic effects in single-molecule junctions have been widely utilized to achieve a molecular switch, but high-efficiency and reproducible switching remain challenging. Here, we demonstrate that there are three stable intramolecular conformations in the 9,10-diphenyl-9,10-methanoanthracen-11-one (DPMAO) systems due to steric effect. Interestingly, different electronic coupling approaches including weak coupling (through-space), decoupling, and strong coupling (through-bond) between two terminal benzene rings are accomplished in the three stable conformations, respectively. Theoretical calculations show that the molecular conductance of three stable conformations differs by more than 1 order of magnitude. Furthermore, the populations of the three stable conformations are highly dependent on the solvent effect and the external electric field. Therefore, an excellent molecular switch can be achieved using the DPMAO molecule junctions and external stimuli. Our findings reveal that modulating intramolecular electronic coupling approaches may be a useful manner to enable molecular switches with high switching ratios. This opens up a new route for building high-efficiency molecular switches in single-molecular junctions.
通讯作者：
Prof. Chengzhou Zhu<&wdkj&>Prof. Chengzhou Zhu Prof. Chengzhou Zhu Prof. Chengzhou Zhu
作者机构：
[Dr. Xiaoli Cai; Dr. Xiaoli Cai Dr. Xiaoli Cai Dr. Xiaoli Cai] Department of Nutrition, Hygiene and Toxicology, School of Public Health, Medical College, Wuhan University of Science and Technology, 430065 Wuhan, P. R. China;[Weiqing Xu; Yu Wu; Yuling Xu; Prof. Wenling Gu; Prof. Chengzhou Zhu; Weiqing Xu Weiqing Xu Weiqing Xu; Yu Wu Yu Wu Yu Wu; Yuling Xu Yuling Xu Yuling Xu; Prof. Wenling Gu Prof. Wenling Gu Prof. Wenling Gu; Prof. Chengzhou Zhu Prof. Chengzhou Zhu Prof. Chengzhou Zhu] National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, 430079 Wuhan, P. R. China
通讯机构：
[Prof. Chengzhou Zhu; Prof. Chengzhou Zhu Prof. Chengzhou Zhu Prof. Chengzhou Zhu] N;National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, 430079 Wuhan, P. R. China
摘要：
Enzymatic catalysis with high efficiency allows them a great prospect in metabolite monitoring in living cells. However, complex tumor microenvironments, such as acidity, H2O2, and hypoxia, are bound to disturb catalytic reactions for misleading results. Here, we report a spatially compartmentalized artificial organelle to correct intratumoral glucose analysis, where the zeolitic imidazolate framework-8 immobilized glucose oxidase-horseradish peroxidase cascade core and catalase-directed shell act as signal transduction and guarding rooms respectively. The acid-digested core and stable shell provide appropriate spaces to boost biocatalytic efficiency with good tolerability. Notably, the endogenous H2O2 is in situ decomposed to O2 by catalase, which not only overcomes the interference in signal output but also alleviates the hypoxic states to maximize glucose oxidation. The marked protective effect and biocompatibility render artificial organelles to correct the signal transduction for dynamic monitoring glucose in vitro and in vivo, achieving our goal of accurate intratumoral metabolite analysis.
作者机构：
[Tang, Yuchen; Gao, Tingjuan; Zheng, Xingxing] Cent China Normal Univ, Coll Chem, China Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.
通讯机构：
[Tang, YC; Gao, TJ ] C;Cent China Normal Univ, Coll Chem, China Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.
摘要：
High-throughput assays play an important role in the fields of drug discovery, genetic analysis, and clinical diagnostics. Although super-capacity coding strategies may facilitate labeling and detecting large numbers of targets in a single assay, practically, the constructed large-capacity codes have to be decoded with complicated procedures or are lack of survivability under the required reaction conditions. This challenge results in either inaccurate or insufficient decoding outputs. Here, we identified chemical-resistant Raman compounds to build a combinatorial coding system for the high-throughput screening of cell-targeting ligands from a focused 8-mer cyclic peptide library. The accurate in situ decoding results proved the signal, synthetic, and functional orthogonality for this Raman coding strategy. The orthogonal Raman codes allowed for a rapid identification of 63 positive hits at one time, evidencing a high-throughput-out capability in the screening process. We anticipate this orthogonal Raman coding strategy being generalized to enable efficient high-throughput-out screening of more useful ligands for cell targeting and drug discovery.
摘要：
The comprehensive understanding of contaminant interfacial behavior strongly depends on the in situ characterization technique, which is still a great challenge. In this study, we constructed a device integrated with open-circuit potentialand attenuated total reflectance Fourier transform infrared (OCP-ATR-FTIR) spectroscopy to simultaneously monitor the electrochemical and infrared spectral information on the interfacial reaction for the process analysis, taking the competitive adsorption of hexavalent chromium (Cr(VI)) and oxalate on hematite nanocubes (HNC) as an example. The synchronous OCP and infrared results revealed that Cr(VI) interacted with HNC via bidentate binuclear inner-sphere coordination, accompanied by electron transfer from HNC to Cr(VI), while oxalate was adsorbed on HNC through bidentate mononuclear side-on inner-sphere coordination with electron transfer from HNC to oxalate, and also outer-sphere coordination with negative charge accumulation. When oxalate was added to HNC with preadsorbed Cr(VI), oxalate would occupy the inner-sphere adsorption sites and thus cause the detaching of preadsorbed Cr(VI) from HNC. This study provides a promising in situ characterization technique for real-time interfacial reaction monitoring and also sheds light on the competitive adsorption mechanism of oxalate and Cr(VI) on the mineral surface.
通讯机构：
[Qiu, S ] Z;[Li, JR; Sun, Y ] C;[Xiong, XX ] W;Zhejiang Univ, Huzhou Cent Hosp, Affiliated Huzhou Hosp, Dept Neurosurg,Sch Med, Huzhou 313000, Peoples R China.;Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticides, Wuhan 430079, Peoples R China.
关键词：
Metallacycles;metallacages;Near-infrared biochannel;In vivo imaging;Theranostic
摘要：
In the past decade, the metallacycles/metallacages have attracted unremitting interest in biomedical fields, yet visual tracking of their in vivo delivery, targeting ability, biodistribution and therapeutic evaluation are still hampered by their short emission wavelengths. More recently, the near-infrared biochannel (NIR, 0.7-1.7 & mu;m) especially the NIR-II region (1.0-1.7 & mu;m) provides deeper tissue penetration and higher contrast than traditional UV-Vis region for in vivo imaging. In this context, we provide a comprehensive and systematic insight into the development of NIR metallacycles/metallacages for biomedical applications. Finally, we also discuss the challenges and prospects of NIR metallacycles/metallacages for future biomedical research and clinical translation.
作者：
Song, Yongjun;Yu, Renyou;Meng, Xianwen;He, Lei
期刊：
Dyes and Pigments,2023年208:110876 ISSN：0143-7208
通讯作者：
He, Lei(helei@ccnu.edu.cn)
作者机构：
[Song, Yongjun; Meng, Xianwen; He, Lei; Yu, Renyou] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ,Hubei Int Sci & Technol Cooperat Base, Wuhan 430079, Peoples R China.;[He, Lei] South China Univ Technol, State Key Lab Luminescent Mat & Devices, Guangzhou 510640, Peoples R China.
通讯机构：
[Lei He] K;Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, College of Chemistry, Central China Normal University, Wuhan, 430079, PR China<&wdkj&>State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, PR China
摘要：
A sensitive extraction and instrumental method was established to detect topramezone and its metabolite (M670H05) in maize and animal-origin foods. Two years of field experiments were carried out to study the dissipation dynamics of topramezone in maize straw, and their residue levels of actual samples collected from the supermarket were determined. They were extracted using liquid-liquid extraction (LLE), and ultra-high-performance liquid chromatography-tandem mass spectrometry was used for detection. The limit of quantification was 0.005 mg kg(-1). Recoveries ranged between 73.8% and 109.9% at 3 spiking levels with intraday relative standard deviation (RSD) <= 17.7% and the inter-day <= 18.1%, which meets the requirements of SANTE/12682/2019. Dissipation dynamics experiment showed that, the deposition of topramezone in maize straw in Jilin were <0.005-0.62 mg kg(-1)with 28 days after application. And the residue level of market samples were all less than 0.005 mg kg(-1), much lower than the MRLs (range from 0.01 to 0.8 mg kg(-1)) set by European Union, United States Food and Drug Administration, China, and Canada. This method was effective to analyse the residues of topramezone and M670H05.
