期刊:
Angewandte Chemie - International Edition,2023年135(21):e202301592 ISSN:1433-7851
通讯作者:
Liang-Qiu Lu
作者机构:
[Lu, Liang-Qiu; Rao, Li; Wang, Bao-Cheng; Qu, Bao-Le; Xiao, Wen-Jing; Xiong, Fen-Ya] Cent China Normal Univ, Minist Educ, CCNU Ottawa Joint Res Ctr, Coll Chem,Key Lab Pesticide & Chem Biol, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;[Tan, Ying; Fang, Kai-Xin; Feng, Ying] Tsinghua Univ, Tsinghua Shenzhen Int Grad Sch, State Key Lab Chem Oncogen, Key Lab Chem Biol, Shenzhen, Peoples R China.;[Lu, Liang-Qiu] Chinese Acad Sci, Lanzhou Inst Chem Phys LICP, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China.;[Lu, Liang-Qiu] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China.
通讯机构:
[Liang-Qiu Lu] C;Central China Normal University, CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides and Chemical Biology, 152 Luoyu Road, 430079 Wuhan, Hubei, CHINA
关键词:
antitumor activity;azaheterocycle;aza-ortho-quinone methide;aza-sulfur ylide;transition metal catalysis
摘要:
Metal-polarized aza-ortho-quinone methides (aza-o-QMs) are a unique and efficient handle for azaheterocycle synthesis. Despite great achievements, the potential of these reactive intermediates has not yet been fully exploited, especially the new reaction modes. Herein, we disclosed an unprecedented dearomatization process of metal-polarized aza-o-QMs, affording transient dearomatized spiroaziridine intermediates. Based on this serendipity, we accomplished three sequential dearomatization-rearomatization reactions of benzimidazolines with aza-sulfur ylides, enabling the divergent synthesis of bis-nitrogen heterocycles with high efficiency and flexibility. Moreover, experimental and theoretical studies were performed to explain the proposed mechanisms and observed selectivity. Further cellular evaluation of the dibenzodiazepine products identified a hit compound for new antitumor drugs.
作者机构:
[Zhang, Zhi-Han; Lu, Liang-Qiu; Yu, Xu-Hui; Xiao, Wen-Jing; Shi, De-Qing] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;[Xiao, Wen-Jing] Shanghai Inst Organ Chem, State Key Lab Organometall Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China.
通讯机构:
[De-Qing Shi] K;Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China
摘要:
The asymmetric Michael addition of phosphorus nucleophiles to electron-deficient alkenes is one of the most direct and atom-economical methods to provide chiral organophosphorus compounds with high efficiency in recent years. Herein, we report a cobalt-catalyzed imidazolyl-directed asymmetric phospha-Michael-type reaction of diarylphosphine oxides with electron-deficient alkenes for synthesizing chiral organophosphorus compounds in moderate to good yields and good to excellent enantioselectivities (25 examples, up to 99% yield, and 99% ee). This protocol features broad substrate scope, good functional group tolerance, and mild conditions as well as avoids the release of massive metal wastes and the use of noble transition metal catalysts. The excellent enantioselectivity of the phospha-Michael reaction can be due to the adoption of a novel chiral N4-ligand. Furthermore, the DFT calculation indicates that the bulky 2,4,6-(i-Pr)3C6H2 group of the ligand induces large steric hindrance which blocks the nucleophilic attack from the Si-face.
摘要:
Achieving fast transmembrane transmission of molecules in organisms is a challenging problem. Inspired by the transport of Dopmine (DA) in organisms, the DA transporter (DAT) binds to DA in a way that has a ring recognition (the recognition group is the tryptophan group). Herein, D-Tryptophan-pillar[5]arene (D-Trp-P5) functionalized conical nanochannel is constructed to achieve fast transmission of DA. The D-Trp-P5 functionalized nanochannel enables specific wettability recognition of DA molecules and has great cycle stability. With the controlling of voltage to wettability, the transport flux of DA is up to 499.73 nmol cm(-2) h(-1) at -6 V, 16.88 times higher than that under positive voltages. In response to these results, a high-throughput DA transport device based on controlled electricity-wettability is provided.
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:
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:
[Hao Li] School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China;[Meiqi Li; Xiufan Liu; Hongwei Sun; Chuan Liang; Yaling Li; Bing Zhou; Jincai Zhao] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, Central China Normal University, Wuhan 430079, China;[Cancan Ling; Guangming Zhan; Lizhi Zhang] School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China<&wdkj&>Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, Central China Normal University, Wuhan 430079, China
通讯机构:
[Hao Li; Lizhi Zhang] S;School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China<&wdkj&>Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, Central China Normal University, Wuhan 430079, China<&wdkj&>School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
期刊:
Journal of Colloid and Interface Science,2023年653(Pt A):540-550 ISSN:0021-9797
通讯作者:
Yang, Guohai;Qu, Lu-Lu
作者机构:
[Luo, Siyu; Chen, Yu; Guo, Yuxin; Rong, Chengyu; Gu, Yingqiu] School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou 221116, PR China;[Gao, Wenhui] School of Life Science, Jiangsu Normal University, Xuzhou, 221116, PR China;[Yang, Guohai] School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou 221116, PR China. Electronic address: yangguohai@jsnu.edu.cn;[Xu, Weiqing; Zhu, Chengzhou] National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079, PR China;[Qu, Lu-Lu] School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou 221116, PR China. Electronic address: luluqu@jsnu.edu.cn
通讯机构:
[Qu, Lu-Lu; Yang, Guohai] S;School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou 221116, PR China. Electronic address:
摘要:
Reactive oxygen species (ROS) are ideal alternative antibacterial reagents for rapid and effective sterilization. Although a variety of ROS-based antimicrobial strategies have been developed, many are still limited by their inefficiency. Herein, we report the synthesis of the Ag-MXene nanozyme, which have superior peroxidase-like activity for antibacterial applications. As a result, Ag-MXene nanozyme can efficiently increase the level of intracellular ROS, converting H(2)O(2) into hydroxyl radicals that effectively kill both Gram-negative and Gram-positive bacteria and disrupting the bacterial biofilm formation. Moreover, a sensitive and selective colorimetric biosensor was constructed for assaying cholesterol based on the Ag-MXene's prominent peroxidase-mimicking activity and the cholesterol oxidase cascade reaction. The biosensor exhibits high performance with a linear cholesterol detection range of 2-800μM, and a detection limit of 0.6μM. Ag-MXene nanozyme can be used for the rapid detection of cholesterol in serum without complicated sample pretreatment. Collectively, it is conceivable that the proposed Ag-MXene nanozyme could be used as a biocide and as a cholesterol sensor. This study provides a broad prospect for the rapid detection and sterilization of MXene nanozymes in the biomedical field.
作者机构:
[Shen, Baojie; Qi, Yinghua; Chen, Disong; Li, Rui] Cent China Normal Univ, Coll Chem, Lab Mass Spectrometry, Wuhan 430079, Hubei, Peoples R China.;[Zhong, Hongying; Zhong, HY] Guangxi Univ, Coll Life Sci & Technol, Ctr Instrumental Anal, Nanning 530004, Guangxi, Peoples R China.;[Gao, Anji] Chinese Acad Sci, Innovat Acad Precis Measurement Sci & Technol, Wuhan 430071, Peoples R China.;[Gao, Anji] Univ Chinese Acad Sci, Beijing 100049, Peoples R China.
通讯机构:
[Zhong, HY ] G;Guangxi Univ, Coll Life Sci & Technol, Ctr Instrumental Anal, Nanning 530004, Guangxi, Peoples R China.
关键词:
Anaerobic oxidization;Hot electrons;Ligand-bridged electron transfer;Mass spectrometry;Plasmonic nanoreactors
摘要:
The light induced hot-electron on plasmonic nanostructures has been recognized as a breakthrough discovery for photovoltaic and photocatalytic applications. With mass spectrometry, we demonstrate the dynamics of hot electron transfers of anaerobic oxidization reactions on Au decorated TiO2 plasmonic nanoparticles, which were coated on the inner surface of a flask. Those nanoparticles were covered by continuously renewed liquid droplets of solvent and reactants that were transported through a Venturi jet mixer with auto-spray. In addition to intensive mass transfer in such droplet-based nanoreactors, as well as strong adsorption of reactants and rapid desorption of products on materials surfaces, the localized surface plasmon resonance (LSPR) excitation upon visible light illumination, by which accumulated energies of plasmons are transferred to electrons in the conduction band of the material, attributes to the efficient photocatalytic transformation. Mass spectrometric detection of intermediate radical anions and negative ions with stable isotope labeling unambiguously identifies that highly energetic hot electrons can escape from the plasmonic nanostructures, be collected by adsorbed molecules, and initiate bond cleavages. It was demonstrated that losses of two H atoms result in the anaerobic oxidization of each benzyl alcohol molecule to a benzyl aldehyde molecule in the absence of molecular oxygen with more than 90 % yields. The well recyclable plasmonic nanoreactors implicate the injection of transferred electrons eventually back to electronically depleted Au+ positive ions. Bridged by adsorbed molecules, electrons were repeatedly circulated back and forth in plasmonic nanoreactors, where the collected light was eventually converted into chemical energy.
作者机构:
[Qin, Ying; Tang, Yinjun; Zhu, Chengzhou; Li, Jinli; Jiao, Lei; Gu, Wenling; Fang, Qie; Liu, Mingwang; Wu, Yu] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Wen, Jing; Hu, Liuyong] Wuhan Inst Technol, Hubei Engn Technol Res Ctr Optoelect & New Energy, Hubei Key Lab Plasma Chem & Adv Mat, Wuhan 430205, Peoples R China.;[Zheng, Lirong; Cui, Xiaowen] Chinese Acad Sci, Inst High Energy Phys, Beijing 100049, Peoples R China.;[Guo, Shaojun] Peking Univ, Sch Mat Sci & Engn, Beijing 100871, Peoples R China.
通讯机构:
[Chengzhou Zhu] N;[Liuyong Hu] H;[Shaojun Guo] S;National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan, 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, China<&wdkj&>School of Materials Science and Engineering, Peking University, Beijing, China
摘要:
Carrier migration path and driving forces are two crucial factors for charge separation of heterojunction with efficient photoelectric response from the thermodynamic and kinetic perspectives, respectively. Constructing the S-scheme heterojunction and achieving an efficient migration path for space charge separation have aroused great interest, while a thorough insight into tuning interfacial band bending for S-scheme heterojunction is absent. Herein, we report a class of Zn atom-doped CeO2/g-C3N4 heterostructure for achieving a new carrier migration path conversion from inferior type-II to advanced S-scheme. Zn-dependent volcano-type plot for Zn-CeO2 is established to tune the Fermi level of CeO2. The built-in electric field for carrier flow dynamics strengthens when coupling with g-C3N4, which significantly boosts the photoelectric response. Based on the intrinsic enzymelike activity of Zn-CeO2, we further demonstrate that the Zn-CeO2/g-C3N4 S-scheme heterojunction can be explored for constructing a sensitive nanozymatic photoelectrochemical biosensor for the detection of acetylcholinesterase.
摘要:
Mimicking the structure of natural enzymes for designing advanced alternatives provides great opportunities to address the bottleneck of enzyme-involved chemiluminescence (CL). Herein, according to theoretical calculations, we found that an endogenous axial ligand of M-N-C single-atom nanozymes (SAzymes), originating from OH- spontaneously bonding to the metal center in an alkaline medium, can self-adaptively change its strength to facilitate intermediate steps. Furthermore, the lowest energy barrier of the rate-determining step and the strongest affinity and fastest electron transfer with luminol anion endow Co-N-C with the highest peroxidase-like activity. Guided by the theoretical calculations, a series of M-N-C SAzymes (M=Fe, Co, Ni) were synthesized to boost CL, where Co-N-C SAzymes with superior catalytic activity and high selective generation of O(2)(center dot-)were validated. As a proof-of-concept, Co-N-C SAzymes were employed for sensitive detection of acetylcholinesterase and organophosphorus pesticide.
作者机构:
[Gao, Ying; Ouyang, Qianxi; Duan, Fangfang; Chang, Jinling; Peng, Xiaogang; Gan, Yutian; Ruan, Hanli] Huazhong Univ Sci & Technol, Tongji Med Coll, Sch Pharm, Hubei Key Lab Nat Med Chem & Resource Evaluat, Wuhan 430030, Peoples R China.;[Meng, Xianggao] Cent China Normal Univ, Coll Chem, Wuhan 430079, Peoples R China.
通讯机构:
[Hanli Ruan] S;School of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Hubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation, Wuhan 430030, People’s Republic of China
期刊:
Trends in Biochemical Sciences,2023年48(6):539-552 ISSN:0968-0004
通讯作者:
Hao, Ge-Fei;Yang, GF;Hao, GF
作者机构:
[Yang, Guang-Fu; Wang, Zhi-Zheng; Yang, GF; Shi, Xing-Xing; Huang, Guang-Yi; Hao, Ge-Fei] Cent China Normal Univ, Natl Key Lab Green Pesticide, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.;[Hao, Ge-Fei] Guizhou Univ, Ctr R&D Fine Chem, Natl Key Lab Green Pesticide, Key Lab Green Pesticide & Agr BioEngn,Minist Educ, Guiyang 550025, Peoples R China.
通讯机构:
[Hao, GF ] G;[Yang, GF ; Hao, GF] C;Cent China Normal Univ, Natl Key Lab Green Pesticide, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.;Guizhou Univ, Ctr R&D Fine Chem, Natl Key Lab Green Pesticide, Key Lab Green Pesticide & Agr BioEngn,Minist Educ, Guiyang 550025, Peoples R China.
关键词:
PPI modulator;fragment evolution;fragment screening;hot spot;structure-based drug design
摘要:
Protein-protein interactions (PPIs) have important roles in various cellular processes, but are commonly described as 'undruggable' therapeutic targets due to their large, flat, featureless interfaces. Fragment-based drug discovery (FBDD) has achieved great success in modulating PPIs, with more than ten compounds in clinical trials. Here, we highlight the progress of FBDD in modulating PPIs for therapeutic development. Targeting hot spots that have essential roles in both fragment binding and PPIs provides a shortcut for the development of PPI modulators via FBDD. We highlight successful cases of cracking the 'undruggable' problems of PPIs using fragment-based approaches. We also introduce new technologies and future trends. Thus, we hope that this review will provide useful guidance for drug discovery targeting PPIs.
关键词:
In-situ remediation dynamics;Petroleum contaminants;Raman spectroscopy and microscopy;Soil and groundwater
摘要:
The mechanistic study of soil and groundwater remediation in petroleum contaminated lands significantly demands rapid qualitative and quantitative identification of petroleum substances. However, most traditional detection methods cannot provide the on-site or in-situ information of petroleum compositions and contents simultaneously even with multi-spot sampling and complex sample preparation. In this work, we developed a strategy for the on-site detection of petroleum compositions and in-situ monitoring of petroleum contents in soil and groundwater using dual-excitation Raman spectroscopy and microscopy. The detection time was 0.5h for the Extraction-Raman spectroscopy method and one minute for the Fiber-Raman spectroscopy method. The limit of detection was 94ppm for the soil samples and 0.46ppm for the groundwater samples. Meanwhile, the petroleum changes at the soil-groundwater interface were successfully observed by Raman microscopy during the in-situ chemical oxidation remediation processes. The results revealed that hydrogen peroxide oxidation released petroleum from the interior to the surface of soil particles and then to groundwater during the remediation process, while persulfate oxidation only degraded petroleum on the soil surface and in groundwater. This Raman spectroscopic and microscopic method can shed light on the petroleum degradation mechanism in contaminated lands, and facilitate the selection of suitable soil and groundwater remediation plans.
通讯机构:
[Shi-Yu Liu; Xianwang Wang] D;Department of Biochemistry and Molecular Biology, Center for Molecular Medicine, Health Science Center, Yangtze University, Jingzhou, Hubei, 434023, PR China<&wdkj&>Department of Laboratory Medicine, Health Science Center, Yangtze University, Jingzhou, Hubei, 434023, PR China<&wdkj&>Department of Biochemistry and Molecular Biology, Center for Molecular Medicine, Health Science Center, Yangtze University, Jingzhou, Hubei, 434023, PR China
摘要:
Early diagnosis of cancer is an efficient strategy to prevent tumor progression and improve the survival rate of patients. However, to discovery of reliable tumor-specific biomarkers remains a great challenge. Leukotriene A4 hydrolase (LTA(4)H) is a bifunctional zinc metalloenzyme with epoxide hydrolase activity and aminopeptidase activity, which plays important roles in allergic and inflammatory reactions and showed strong relevance with carcinoma progression. We thus sought to investigate the possibility of application LTA(4)H activity detection in cancer diagnosis. To achieve this, we herein develop an enzyme activated fluorescent probe for LTA(4)H activity sensing by incorporating the specific recognition unit of LTA(4)H with a red-emitting fluorophore. The acquired probe (named as ADMAB) showed high sensitivity and specificity toward LTA(4)H in vitro. By further application of ADMAB in living cells, significantly elevated LTA(4)H activity in cancer cell lines was observed when compared with normal cell lines and in vivo tracing A549 tumor in nude mice was also realized by ADMAB. Meanwhile, the wound-healing assay further revealed the importance of LTA(4)H in tumor metastasis. Moreover, the LTA(4)H activity in human serum sample was successfully detected by ADMAB and significantly elevated LTA(4)H activity in patients diagnosed with cancer was firstly found, which demonstrated ADMAB to be a useful tool for cancer diagnosis and LTA(4)H related biological study.
作者机构:
[Cai, Fei; Cai, F; Zhang, Zhipeng] Hubei Univ Sci & Technol, Xianning Med Coll, Xianning 437000, Peoples R China.;[Ye, Huan; Sun, Yao] Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Ye, Huan] Guangxi Univ, Sch Light Ind & Food Engn, Nanning 530004, Peoples R China.
通讯机构:
[Sun, Y ] C;[Cai, F ] H;Hubei Univ Sci & Technol, Xianning Med Coll, Xianning 437000, Peoples R China.;Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要:
Recently, metal-based drugs have attracted relentless interest in the biomedical field. However, their short excitation/emission wavelengths and unsatisfactory therapeutic efficiency limit their biological applications in vivo. Currently, the second near-infrared window (NIR-II, 1000-1700 nm) provides more accurate imaging and therapeutic options. Thus, there has been a constant focus on developing multifunctional NIR metal agents for imaging and therapy that have deeper tissue penetration. Fortunately, supramolecular coordination complexes (SCCs) formed by the coordination-driven self-assembly of NIR-II emissive ligands can address the above issues. Importantly, metal receptors with chemotherapeutic properties in SCCs can bind to luminescent ligands, thus becoming a versatile therapeutic platform for chemotherapy, imaging and phototherapy. In this context, we systematically summarize the evolution of NIR-II emissive SCCs for biomedical applications and discuss future challenges and prospects.
作者机构:
[Xu, Weiqing; Fang, Qie; Tang, Yinjun; Zhu, Chengzhou; Wei, Xiaoqian; Zhu, CZ; Luo, Xin; Gu, Wenling; Wang, Hengjia] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Hu, Liuyong] Wuhan Inst Technol, Hubei Engn Technol Res Ctr Optoelect & New Energy, Hubei Key Lab Plasma Chem & Adv Mat, Wuhan 430205, Peoples R China.
通讯机构:
[Zhu, CZ ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要:
Developing functional nanomaterials for nonenzymatic glucose electrochemical sensing platforms is vital and challenging from the perspective of pathology and physiology. Accurate identification of active sites and thorough investigation of catalytic mechanisms are critical prerequisites for the design of advanced catalysts for electrochemical sensing. Herein, Cu aerogels are synthesized as a model system for sensitive nonenzymatic glucose sensing. The resultant Cu aerogels exhibit good catalytic activity for glucose electrooxidation with high sensitivity and a low detection limit. Significantly, in situ electrochemical investigations and Raman characterizations reveal the catalytic mechanism of Cu-based nonenzymatic glucose sensing. During the electrocatalytic oxidation of glucose, Cu(I) is electrochemically oxidized to generate Cu(II), and the resultant Cu(II) is spontaneously reduced back to Cu(I) by glucose, achieving the sustained Cu(I)/Cu(II) redox cycles. This study provides profound insights into the catalytic mechanism for nonenzymatic glucose sensing, which provides great potential guidance for a rational design of advanced catalysts in the future.
期刊:
Chemical Engineering Journal,2023年477:147085 ISSN:1385-8947
通讯作者:
Yu, Q;Sun, Y
作者机构:
[Li, Qiangwang; Zhu, Hongda; Zhou, Yujing; Zhang, Qin; Yu, Q; Yu, Qi; Liu, Mingxing] Hubei Univ Technol, Sch Food & Biol Engn, Natl Ctr Cellular Regulat & Mol Pharmaceut 111, Key Lab Fermentat Engn,Minist Educ,Hubei Key Lab I, Wuhan 430068, Peoples R China.;[Tu, Le; Sun, Yao] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticides, Wuhan 430079, Peoples R China.;[Tu, Le] Soochow Univ, Key Lab Adv Opt Mfg Technol Jiangsu Prov, Suzhou 215006, Peoples R China.
通讯机构:
[Sun, Y ] C;[Yu, Q ] H;Hubei Univ Technol, Sch Food & Biol Engn, Natl Ctr Cellular Regulat & Mol Pharmaceut 111, Key Lab Fermentat Engn,Minist Educ,Hubei Key Lab I, Wuhan 430068, Peoples R China.;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticides, Wuhan 430079, Peoples R China.
关键词:
Cancer immunotherapy;Pyroptosis;NIR-II Fluorescence imaging;Nanoreservoir;Mitochondrial dysfunction
摘要:
The therapeutic efficacy of immunotherapy for most solid tumors is unsatisfactory due to the "immune-cold" nature. As a form of lytic pro-inflammatory programmed cell death, pyroptosis can release abundant immuno-genic damage-associated molecular patterns to extracellular milieu, exhibiting self-cascade amplifying capacity for cancer immunotherapy. However, the activation of the caspase-3-mediated pyroptosis is difficult because mRNA hypermethylation induces the down-regulated GSDME expression. Herein, an integrated strategy to elicit dual pyroptosis pathways is introduced based on calcium sulfide-based nanoreservoirs (denoted as CSSG). CSSG are degraded in the aggravated acidic tumor microenvironment (TME) triggered by the surface GOx participating oxidation and result in the avalanching generation of H2S and Ca2+, which elevate oxidative pressure and induce mitochondrial respiration inhibition. Moreover, the sudden surge in H2S evokes GSDMD mediated pyroptosis through "DUSP6/ERK/NLRP3/caspase-1" signaling pathway, which synergistically reinforces the performance of the Ca2+ overloading initiating GSDME-mediated pyroptosis. CSSG elicit robust pyroptotic cell death to effec-tively stimulate tumor immunogenicity, and promote an impressive antitumor immunity with effective elimi-nation of primary and distant tumors. Collectively, this work establishes TME-associated degradable nanomaterials to introduce dual pyroptosis pathways simultaneously and has a promising prospect in optimizing cancer immunotherapy.
作者机构:
[Li, Chaoxiong; Zheng, Chunyang; Wang, Dunjia; Sun, Xuancheng] Hubei Normal Univ, Coll Chem & Chem Engn, Hubei Key Lab Pollutant Anal & Reuse Technol, Huangshi 435002, Peoples R China.;[Meng, Xianggao] Cent China Normal Univ, Coll Chem, Wuhan 430079, Peoples R China.
通讯机构:
[Meng, XG ] C;[Zheng, CY ] H;Hubei Normal Univ, Coll Chem & Chem Engn, Hubei Key Lab Pollutant Anal & Reuse Technol, Huangshi 435002, Peoples R China.;Cent China Normal Univ, Coll Chem, Wuhan 430079, Peoples R China.
摘要:
The development of luminescent metal-organic frameworks for effective sensing and monitoring of environmental pollutants is of great significance for human health and environmental protection. In this work, a novel water-stable Zn(II)-based luminescent coordination polymer, namely {[Zn(BBDF)(ATP)]·2DMF·3H(2)O}(n) ((BBDF = 2,7-bis(1H-benzimidazol-1-yl)-9,9-dimethyl-9H-fluorene) and H(2)ATP = 2-aminoterephthalic acid), was designed and obtained using the mixed-ligand method. Structural analysis indicated that 1 presents a two-fold interpenetrated two-dimensional layer structure with one dimensional (1D) channels along the a axis. Intriguingly, the uncoordinated -NH(2) group was danged onto the pore walls of 1. Remarkably, compound 1 shows good aqueous stability at different pH values of 3-13 and exhibits a fluorescence turn-off sensing behavior for Hg(2+), Cr(2)O(7)(2-), CrO(4)(2-), and antibiotics (NFZ, NFT) in aqueous solution with high selectivity and sensitivity. The limits of detection (LOD) are 0.12 μM (Hg(2+)), 0.17 μM (Cr(2)O(7)(2-)), 0.21 μM (CrO(4)(2-)), 0.098 μM (NFZ), and 0.14 μM (NFT). The luminescence quenching mechanism analysis by experiment and theoretical calculation revealed that the competitive absorption and the photoinduced electron transfer process are largely responsible for the sensing of the two antibiotics, while the weak interaction contributes to the selective luminescence quenching for Hg(2+).