作者机构：
[Furong Guo; Tingjuan Gao] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, China;School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China;[Jiangshan Li] State Key Laboratory of Geomechanics and Geotechnical Engineering, Institute of Rock and Soil Mechanics, Chinese Academy of Sciences, Wuhan 430071, China;[Shiyu Cao] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, China<&wdkj&>State Key Laboratory of Geomechanics and Geotechnical Engineering, Institute of Rock and Soil Mechanics, Chinese Academy of Sciences, Wuhan 430071, China;[Yanbiao Shi; Lizhi Zhang] Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, China<&wdkj&>School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
通讯机构：
[Tingjuan Gao; Lizhi Zhang] K;Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, China<&wdkj&>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, College of Chemistry, Central China Normal University, Wuhan 430079, China
摘要：
Nano zero-valent iron (nZVI) is a promising phosphate adsorbent for advanced phosphate removal. However, the rapid passivation of nZVI and the low activity of adsorption sites seriously limit its phosphate removal performance, accounting for its inapplicability to meet the emission criteria of 0.1 mg P/L phosphate. In this study, we report that the oxalate modification can inhibit the passivation of nZVI and alter the multi-stage phosphate adsorption mechanism by changing the adsorption sites. As expected, the stronger anti-passivation ability of oxalate modified nZVI (OX-nZVI) strongly favored its phosphate adsorption. Interestingly, the oxalate modification endowed the surface Fe(III) sites with the lowest chemisorption energy and the fastest phosphate adsorption ability than the other adsorption sites, by in situ forming a Fe(III)-phosphate-oxalate ternary complex, therefore enabling an advanced phosphate removal process. At an initial phosphate concentration of 1.00 mg P/L, pH of 6.0 and a dosage of 0.3 g/L of adsorbents, OX-nZVI exhibited faster phosphate removal rate (0.11 g/mg/min) and lower residual phosphate level (0.02 mg P/L) than nZVI (0.055 g/mg/min and 0.19 mg P/L). This study sheds light on the importance of site manipulation in the development of high-performance adsorbents, and offers a facile surface modification strategy to prepare superior iron-based materials for advanced phosphate removal.
作者机构：
[Fengjiao Quan; Pengfei Xu; Xiaolan Chen; Wenjuan Shen; Yun He; Jianfen Li] College of Chemical and Environmental Engineering, Wuhan Polytechnic University, Wuhan 430023, China;[Falong Jia] College of Chemistry, Central China Normal University, Wuhan 430079, China;[Guangming Zhan] School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
通讯机构：
[Falong Jia] C;College of Chemistry, Central China Normal University, Wuhan 430079, China
摘要：
Nitrate (NO3–) is a widespread pollutant in high-salt wastewater and causes serious harm to human health. Although electrochemical removal of nitrate has been demonstrated to be a promising treatment method, the development of low-cost electro-catalysts is still challenging. In this work, a phosphate modified iron (P-Fe) cathode was prepared for electrochemical removal of nitrate in high-salt wastewater. The phosphate modification greatly improved the activity of iron, and the removal rate of nitrate on P-Fe was three times higher than that on Fe electrode. Further experiments and density functional theory (DFT) calculations demonstrated that the modification of phosphoric acid improved the stability and the activity of the zero-valent iron electrode effectively for NO3– removal. The nitrate was firstly electrochemically reduced to ammonium, and then reacted with the anodic generated hypochlorite to N2. In this study, a strategy was developed to improve the activity and stability of metal electrode for NO3– removal, which opened up a new field for the efficient reduction of NO3– removal by metal electrode materials.
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024年146(9):6307-6316 ISSN：0002-7863
通讯作者：
Chen, FE;Zhou, H
作者机构：
[Zhao, Fei; Dong, Jianghu; Wang, Wei; Chen, Fen-Er; Yan, Qiongjiao; Xuan, Liangming; Chen, Qinlin; Fan, Rundong; Wang, Haifeng] Wuhan Inst Technol, Pharmaceut Res Inst, Sch Chem Engn & Pharm, Wuhan 430205, Peoples R China.;[Zhou, Hui] Cent China Normal Univ, Coll Chem, Wuhan 430079, Hubei, Peoples R China.;[Chen, Fen-Er] Fudan Univ, Engn Ctr Catalysis & Synth Chiral Mol, Dept Chem, Shanghai 200433, Peoples R China.;[Chen, Fen-Er] Shanghai Engn Ctr Ind Catalysis Chiral Drugs, Shanghai 200433, Peoples R China.
通讯机构：
[Zhou, H ] C;[Chen, FE ] W;Wuhan Inst Technol, Pharmaceut Res Inst, Sch Chem Engn & Pharm, Wuhan 430205, Peoples R China.;Cent China Normal Univ, Coll Chem, Wuhan 430079, Hubei, Peoples R China.;Fudan Univ, Engn Ctr Catalysis & Synth Chiral Mol, Dept Chem, Shanghai 200433, Peoples R China.
摘要：
Saturated hydrocarbon bonds are ubiquitous in organic molecules; to date, the selective functionalization of C(sp(3))-H bonds continues to pose a notorious difficulty, thereby garnering significant attention from the synthetic chemistry community. During the past several decades, a wide array of powerful new methodologies has been developed to enantioselectively modify C(sp(3))-H bonds that is successfully applied in asymmetric formation of diverse bonds, including C-C, C-N, and C-O bonds; nevertheless, the asymmetric C(sp(3))-H alkylation is elusive and, therefore, far less explored. In this work, we report a direct and robust strategy to construct highly valuable enantioenriched unnatural α-amino acid (α-AA) cognates and peptides by a copper-catalyzed enantioselective remote C(sp(3))-H alkylation of N-fluorocarboxamides and readily accessible glycine esters under ambient conditions. The key to success lies in the optically active Cu catalyst generated through the coordination of glycine derivatives to enantiopure bisphosphine/Cu(I) species, which is beneficial to the single electronic reduction of N-fluorocarboxamides and the subsequent stereodetermining alkylation. More importantly, all types (primary, secondary, tertiary, and even α-oxy) of δ-C(sp(3))-H bonds could be site- and stereospecifically activated by the kinetically favored 1,5-hydrogen atom transfer (1,5-HAT) step.
期刊：
CHEMISTRY-AN ASIAN JOURNAL,2024年19(2):e202300860- ISSN：1861-4728
通讯作者：
Liu, SH;Hartl, F
作者机构：
[Yang, Xiao Fei; Liu, Sheng Hua; Liu, SH; Zhang, Ming-Xing] Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Zhang, Ming-Xing] Hubei Univ Educ, Coll Chem & Life Sci, Hubei Key Lab Purificat & Applicat Plant Anticanc, Wuhan 430205, Peoples R China.;[Hartl, Frantisek; Hartl, F] Univ Reading, Dept Chem, Reading RG6 6DX, England.
通讯机构：
[Liu, SH ] C;[Hartl, F ] U;Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;Univ Reading, Dept Chem, Reading RG6 6DX, England.
摘要：
The reviewed literature documents that certain metallaaromatics with unconventional photophysical properties, redox and electronic transport properties and magnetism, have potential to be widely used in diverse practical applications, with selected examples of amino acid identification, photothermal effects, functional materials, photodynamic therapy (PDT) in biomedicine, single‐molecule junction conductors, and electron‐transport layer materials (ETLs) in solar cells. Abstract In recent years, the field of organometallic chemistry has made a great progress and diverse types of metallaaromatics have successively been reported. In those studies, incorporation of ligated osmium centers into metallaaromatic systems played a prominent role. The reviewed literature documents that certain metallaaromatics with unconventional photophysical properties, redox and electronic transport properties and magnetism, have potential to be widely used in diverse practical applications, with selected examples of amino acid and fluoride anion identification, photothermal effects, functional materials, photodynamic therapy (PDT) in biomedicine, single‐molecule junction conductors, and electron‐transport layer materials (ETLs) in solar cells.
摘要：
Cancer cells need a greater supply of glucose mainly due to their aerobic glycolysis, known as the Warburg effect. Glucose transport by glucose transporter 1 (GLUT1) is the rate-limiting step for glucose uptake, making it a potential cancer therapeutic target. However, GLUT1 is widely expressed and performs crucial functions in a variety of cells, and its indiscriminate inhibition will cause serious side effects. In this study, we designed and synthesized a photocaged GLUT1 inhibitor WZB117-PPG to suppress the growth of cancer cells in a spatiotemporally controllable manner. WZB117-PPG exhibited remarkable photolysis efficiency and substantial cytotoxicity toward cancer cells under visible light illumination with minimal side effects, ensuring its safety as a potential cancer therapy. Furthermore, our quantitative proteomics data delineated a comprehensive portrait of responses in cancer cells under glucose deprivation, underlining the mechanism of cell death via necrosis rather than apoptosis. We reason that our study provides a potentially reliable cancer treatment strategy and can be used as a spatiotemporally controllable trigger for studying nutrient deprivation-related stress responses.
作者机构：
[Guan, Rui; Sun, Yao; Li, Junrong; Liu, Guorong] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Yan, Mingzhe] Huazhong Univ Sci & Technol, Wuhan Jinyintan Hosp, Tongji Med Coll, Wuhan 430023, Peoples R China.;[Cheng, Jing] Wuhan Univ Sci & Technol, Sch Publ Hlth, Wuhan 430072, Peoples R China.;[Zhan, Jianbo] Hubei Prov Ctr Dis Control & Prevent, Inst Hlth Inspect & Testing, Wuhan 430072, Peoples R China.;[Wuethrich, Alain; Trau, Matt; Wuethrich, A] Univ Queensland, Australian Inst Bioengn & Nanotechnol, Ctr Personalized Nanomed, Brisbane, Qld 4072, Australia.
通讯机构：
[Wuethrich, A ] U;[Sun, Y ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;Univ Queensland, Australian Inst Bioengn & Nanotechnol, Ctr Personalized Nanomed, Brisbane, Qld 4072, Australia.
摘要：
The molecular detection of multiple respiratory viruses provides evidence for the rational use of drugs and effective health management. Herein, we developed and tested the clinical performance of an electrohydrodynamic-driven nanobox-on-mirror platform (E-NoM) for the parallel, accurate, and sensitive detection of four respiratory viral antigens. The E-NoM platform uses gold-silver alloy nanoboxes as the core material with the deposition of a silver layer as a shell on the core surfaces to amplify and enable a reproducible Raman signal readout that facilitates accurate detection. Additionally, the E-NoM platform employs gold microelectrode arrays as the mirror with electrohydrodynamics to manipulate the fluid flow and enhance molecular interactions for an improved biosensing response. The presence of viral antigens binds the nanobox-based core-shell nanostructure on the gold microelectrode and creates the nanocavity with extremely strong "hot spots" to benefit sensitive analysis. Significantly, in a large clinical cohort with 227 patients, the designed E-NoM platform demonstrates the capability of screening respiratory infection with achieved clinical specificity, sensitivity, and accuracy of 100.0, 96.48, and 96.91%, respectively. It is anticipated that the E-NoM platform can find a position in clinical usage for respiratory disease diagnosis.
作者机构：
[Li, Qian; Yan, Qiang; Yan, Q; Li, Yuntao] Zhejiang Univ, Huzhou Cent Hosp, Affiliated Huzhou Hosp, Dept Gen Surg,Sch Med, Huzhou 313000, Peoples R China.;[Li, Qian; Sun, Yao; Zhao, Fang] 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.;[Zhang, ZP; Zhang, Zhipeng] Hubei Univ Sci & Technol, Xianning Med Coll, Coll Pharm, Xianning 437100, Peoples R China.
通讯机构：
[Zhang, ZP ] H;[Sun, Y ] C;[Yan, Q ] Z;Zhejiang Univ, Huzhou Cent Hosp, Affiliated Huzhou Hosp, Dept Gen Surg,Sch Med, Huzhou 313000, Peoples R China.;Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
Bacterial infections can lead to the development of large-scale outbreaks of diseases that pose a serious threat to human life and health. Also, conventional antibiotics are prone to producing resistance and allergic reactions, and their therapeutic effect is dramatically diminished when bacterial communities form biofilms. Fortunately, well-designed supramolecular coordination complexes (SCCs) have been used as antibacterials or anti-biofilms in recent years. SCCs can kill bacteria by directly engaging with the bacterial surface through electrostatic interactions or by penetrating the bacterial membrane through the auxiliary effect of cell-penetrating peptides. Furthermore, scientists have engineered fluorescent SCCs that can produce reactive oxygen species (ROS) to eliminate bacteria when exposed to laser irradiation, and they also demonstrate outstanding performance in in vivo imaging, enabling integrated diagnosis and treatment. In this review, we summarize the design strategy and applications of SCCs in antibacterials or anti-biofilms and provide an outlook on future research.
摘要：
Pyroptosis has garnered significant interest due to its involvement in cancer progression and potential to trigger inflammation and host immune responses. While many efforts have been made to induce pyroptosis using chemotherapeutic agents, these approaches often result in off-target effects, drug resistance, and unwanted systemic toxicity. Furthermore, the non-specific activation of pyroptosis could lead to pro-inflammatory death, creating a microenvironment that potentially heightens the chances of cancer proliferation and metastasis. To solve these limitations, photon-evoking pyroptosis engineering has emerged as a promising approach due to its precise spatiotemporal control, non-invasiveness, and reduced side effects. In this context, this work provides an overview of recent advancements in the molecular mechanisms of pyroptosis, and explore various effective strategies associated with different mode of photon-evoked pyroptosis based on the pyroptosis pathway. Thereafter, we put forth our perspectives on the challenges and prospects of utilizing photon-evoked pyroptosis in anticancer therapy.
期刊：
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY,2024年72(8):3884-3893 ISSN：0021-8561
通讯作者：
Lin, Hong-Yan;Wang, DW
作者机构：
[Ye, Bao-Qing; Yang, Guang-Fu; Cai, Zhuo-Mei; Chen, Li-Jun; Wang, Da-Wei; Dong, Jin; Huang, Guang-Yi; Lin, Hong-Yan; Lin, HY] Cent China Normal Univ, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Ye, Bao-Qing; Yang, Guang-Fu; Cai, Zhuo-Mei; Chen, Li-Jun; Wang, Da-Wei; Dong, Jin; Huang, Guang-Yi; Lin, Hong-Yan; Lin, HY] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Wuhan 430079, Peoples R China.
通讯机构：
[Wang, DW ; Lin, HY] C;Cent China Normal Univ, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Wuhan 430079, Peoples R China.
摘要：
4-Hydroxyphenylpyruvate dioxygenase (HPPD, EC 1.13.11.27) is one of the most valuable herbicide targets due to its unique biological functions. In search of HPPD inhibitors with promising biological performance, we designed and synthesized a series of novel tetrazolamide-benzimidazol-2-ones using a structure-based drug design strategy. Among the synthesized compounds, 1-(2-chlorobenzyl)-3-methyl-N-(1-methyl-1H-tetrazol-5-yl)-2-oxo-2,3-dihydro-1H-benzo[d]imidazole-4-carboxamide, <bold>25</bold>, IC50 = 10 nM, was identified to be the most outstanding HPPD inhibitor, which showed more than 36-fold increased Arabidopsis thaliana HPPD (AtHPPD) inhibition potency than mesotrione (IC50 = 363 nM). Our AtHPPD-<bold>25</bold> complex indicated that one nitrogen atom on the tetrazole ring and the oxygen atom on the amide group formed a classical bidentate chelation interaction with the metal ion, the benzimidazol-2-one ring created a tight pi-pi stacking interaction with Phe381 and Phe424, and some hydrophobic interactions were also found between the ortho-Cl-benzyl group and surrounding residues. Compound <bold>32</bold> showed more than 80% inhibition against all four tested weeds at 150 g ai/ha by the postemergence application. Our results indicated that the tetrazolamide-benzimidazol-2-one scaffold may be a new lead structure for herbicide discovery.
通讯机构：
[Pan, FF ] C;[Dong, XY ] H;Henan Polytech Univ, Coll Chem & Chem Engn, Jiaozuo 454000, Peoples R China.;Zhengzhou Univ, Coll Chem, Zhengzhou 450001, Peoples R China.;Cent China Normal Univ, Coll Chem, Wuhan 430079, Peoples R China.
摘要：
Materials exhibiting X-ray-induced photochromism have consistently piqued the interest of researchers. Exploring the photochromic properties of such materials is valuable for understanding the structural changes and electron transfer processes that occur under high energy radiation, such as X-ray irradiation. Here, a crystalline silver(I) nanocluster synthesized from tert-butylacetylene silver was found to have the ability to exhibit color and photoluminescence changes upon exposure to X-ray radiation. The responsive behavior was observed across a wide temperature range of 100-300 K, with the ability to respond particularly well to soft X-rays (lambda > 1 & Aring;) and exhibit light responsiveness to hard X-rays (lambda < 1 & Aring;). By combining experimental findings including X-ray diffraction, X-ray photoelectron spectroscopy, electron spin resonance, etc. with theoretical calculations, we have proposed that X-ray irradiation induces electron transfer from chloride (Cl-) located in the center of the silver(I) nanocluster to the surrounding Ag-14 in the skeleton. This represents the first documented example in which electron transfer induced by X-ray excitation has been observed, accompanied by a photochromism process, in silver nanoclusters. This study contributes to our understanding of X-ray-induced photochromism and the electron transfer process in silver cluster compounds. It also provides valuable insights and potential design strategies for applications such as photochromism, photoluminescence color change, and photoenergy conversion.
期刊：
JOURNAL OF NATURAL PRODUCTS,2024年 ISSN：0163-3864
通讯作者：
Ruan, HL
作者机构：
[Ruan, Han-Li; Xie, Zuo-Ye; Chang, Jin-Ling; Peng, Xiao-Gang; Ruan, HL; Gan, Yu-Tian; Zhou, Yin-Hui] Huazhong Univ Sci & Technol, Tongji Med Coll, Sch Pharm, Hubei Key Lab Nat Med Chem & Resource Evaluat, Wuhan 430030, Peoples R China.;[Gan, Yu-Tian] Xiangyang Hosp Tradit Chinese Med, Xiangyang 441000, Peoples R China.;[Meng, Xianggao] Cent China Normal Univ, Coll Chem, Wuhan 430079, Peoples R China.;[Li, Shu-Ming] Philipps Univ Marburg, Fachbereich Pharm, Inst Pharmazeut Biol & Biotechnol, D-35037 Marburg, Germany.
通讯机构：
[Ruan, HL ] H;Huazhong Univ Sci & Technol, Tongji Med Coll, Sch Pharm, Hubei Key Lab Nat Med Chem & Resource Evaluat, Wuhan 430030, Peoples R China.
摘要：
Ten new (1-10) and nine known (11-19) austocystins, along with four known anthraquinones (20-23), were isolated from the culture of Aspergillus ustus NRRL 5856 by bioactivity-guided fractionation. The structures of the new compounds were elucidated by spectroscopic data analysis, X-ray crystallographic study, the modified Mosher's method, [Rh(2)(OCOCF3)(4)]-induced ECD spectral analysis, and comparison of the experimental ECD spectra with those of the similar analogues. Compounds 1-8 represent the first examples of austocystins with a C-4' oxygenated substitution. The absolute configuration of 1″-hydroxy austocystin D (11) was determined by single-crystal X-ray diffraction and consideration of its biosynthetic origin. Compounds 5, 9, and 11 exhibited significant inhibitory effects against the proliferation of ConA-induced T cells with IC(50) values of 1.1, 1.0, and 0.93 μM, respectively. Furthermore, these compounds suppressed the expression of IL-6 in a dose-dependent manner. Compounds 10-12 and 14 showed pronounced cytotoxicities against MCF-7 with IC(50) values of 3.9, 1.3, 0.46, and 2.3 μM, respectively.
期刊：
Green Synthesis and Catalysis,2024年 ISSN：2666-5549
通讯作者：
Long Wang<&wdkj&>Qing-Qing Yang
作者机构：
[Zheng-Wei Wu; Han-Han Kong] College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002, China;[Yong Wei; Wen-Chao Zhou] Yichang Humanwell Pharmaceutical Co., Ltd., 19 Dalian Road, Yichang 443008, China;Hubei Three Gorges Labratory, Yichang 443007, China;[Liang-Qiu Lu] CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China;[Long Wang; Qing-Qing Yang] College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002, China<&wdkj&>Hubei Three Gorges Labratory, Yichang 443007, China
通讯机构：
[Long Wang; Qing-Qing Yang] C;College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002, China<&wdkj&>Hubei Three Gorges Labratory, Yichang 443007, China
关键词：
Visible light;Tetrabromomethane;Molecular oxygen;Photocatalyst- and additive-free;Azaspiro[4,5]trienones
摘要：
A visible-light-induced brominated spirocyclization of N-arylpropiolamides and CBr4 for the synthesis of 3-bromo-azaspiro[4,5]trienones is reported here. This process allows the formation of C–Br, C–C, and C=O bonds in a single reaction via a cascade radical addition/ipso-cyclization/oxidative dearomatization sequence. This protocol also features high functional group tolerance, operational simplicity and the use of molecular oxygen as an oxidant as well as sustainable photocatalyst- and additive-free reaction conditions at room temperature. Meanwhile, the presented straightforward and sustainable strategy has also been applied to the synthesis of several biologically active compounds.
摘要：
As one of the most widely used disinfectants, active chlorine is synthesized predominantly through electrolysis of saturated sodium chloride solutions, an industrial process known as the chlor-alkali process, with high energy consumption. Seawater is an abundant source of chloride and thus an ideal alternative electrolyte. However, substantial challenges are to be addressed, notably the competing oxygen evolution reaction and progressive anode passivation due to the presence of rich cations in seawater. Here, we show durable and efficient active chlorine electrosynthesis directly from natural seawater with intrinsic turnover frequency and mass activity two orders of magnitude higher than the state of the art. The essential chemistry is an Fe-doped Ti4O7 anode that strengthens the electrophilicity of lattice oxygen to allow for site-selective chloride activation at remarkably lowered kinetic overpotentials relative to the oxygen evolution reaction, while also impeding the precipitation of alkaline earth metal cations on the Ti4O7 surface. A seawater splitting device with an integrated commercial silicon photovoltaic cell delivers an impressive active chlorine production rate of 3.15 mg min-1 for effective simulated ballast water disinfection. This work suggests the possibility to substantially improve the sustainability of the chlor-alkali process without compromising the synthetic performance for the mass production of disinfectants. This work shows a delicate titanium suboxide-based anode design for electrolysis of seawater, delivering selective production of active chlorine for on-site disinfection.
摘要：
Ammonia (NH3) is an essential chemical and a promising fuel, but its industrially produced process is carbon-intensive and highly energy-consuming. Developing a green and sustainable NH3 synthesis route is extremely urgent. Electrochemical ammonia synthesis (EAS) powered by renewable electricity energy under ambient conditions is fascinating, while exploring the efficient electrocatalysts and suitable nitrogen source is critical. Due to the unique characteristics of adjustable porosity and component, large specific surface area and diverse structure, metal-organic frameworks (MOFs) and their various derivatives have captured immense interest in EAS. Herein, the advance in EAS via electrocatalytic reduction reactions (ERRs) from various nitrogen source under ambient conditions over MOF-based electrocatalysts is timely summarized, aiming to offer a deep insight to the structure-activity relationship of MOF-based electrocatalysts for EAS. Current challenges and future prospects for EAS are proposed at the end of this review as well.
作者机构：
[Zhu, Chengzhou; Fang, Qie; Wei, Xiaoqian; Zhu, CZ; Ling, Ling] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Asahi, Toru; Zhao, Yingji; Wei, Xiaoqian] Waseda Univ, Fac Sci & Engn, Tokyo 1698555, Japan.;[Yamauchi, Yusuke; Zhao, Yingji; Wei, Xiaoqian] Nagoya Univ, Grad Sch Engn, Dept Mat Proc Engn, Nagoya, Aichi 4648603, Japan.;[Song, Weiyu; Song, Shaojia] China Univ Petr, State Key Lab Heavy Oil Proc, Beijing 102249, Peoples R China.;[Cai, Weiwei] China Univ Geosci, Fac Mat Sci & Chem, Energy Lab, Wuhan 430074, Peoples R China.
通讯机构：
[Yamauchi, Y ] N;[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.;Nagoya Univ, Grad Sch Engn, Dept Mat Proc Engn, Nagoya, Aichi 4648603, Japan.;Univ Queensland, Australian Inst Bioengn & Nanotechnol AIBN, Brisbane, Qld 4072, Australia.
关键词：
Mn single atoms;Pt nanoparticles;atomic pairs;oxygen reduction reactions;synergistic effects
摘要：
The intrinsic roadblocks for designing promising Pt-based oxygen reduction reaction (ORR) catalysts emanate from the strong scaling relationship and activity-stability-cost trade-offs. Here, a carbon-supported Pt nanoparticle and a Mn single atom (Pt(NP)-Mn(SA)/C) as in situ constructed Pt(NP)-Mn(SA) pairs are demonstrated to be an efficient catalyst to circumvent the above seesaws with only ∼4 wt % Pt loadings. Experimental and theoretical investigations suggest that Mn(SA) functions not only as the "assist" for Pt sites to cooperatively facilitate the dissociation of O(2) due to the strong electronic polarization, affording the dissociative pathway with reduced H(2)O(2) production, but also as an electronic structure "modulator" to downshift the d-band center of Pt sites, alleviating the overbinding of oxygen-containing intermediates. More importantly, Mn(SA) also serves as a "stabilizer" to endow Pt(NP)-Mn(SA)/C with excellent structural stability and low Fenton-like reactivity, resisting the fast demetalation of metal sites. As a result, Pt(NPs)-Mn(SA)/C shows promising ORR performance with a half-wave potential of 0.93 V vs reversible hydrogen electrode and a high mass activity of 1.77 A/mg(Pt) at 0.9 V in acid media, which is 19 times higher than that of commercial Pt/C and only declines by 5% after 80,000 potential cycles. Specifically, Pt(NPs)-Mn(SA)/C reaches a power density of 1214 mW/cm(2) at 2.87 A/cm(2) in an H(2)-O(2) fuel cell.
摘要：
Engineering isolated metal sites resembling the primary coordination sphere of metallocofactors enables atomically dispersed materials as promising nanozymes. However, most existing nanozymes primarily focus on replicating specific metallocofactors while neglecting other supporting cofactors within active pockets, leading to reduced electron transfer (ET) efficiency and thus inferior catalytic performances. Herein, we report a metal–organic framework UiO-67 nanozyme with atomically dispersed iron sites, which involves multiple tailored enzyme-like nanocofactors that synergistically drive the ET process for enhanced peroxidase-like catalysis. Among them, the linker-coupled atomic iron site plays a critical role in substrate activation, while bare linkers and zirconia nodes facilitate the ET efficiency of intermediates. The synergy of three nanocofactors results in a 4.29-fold enhancement compared with the single effort of isolated metal site-based nanocofactor, holding promise in immunoassay for sensitive detection of chlorpyrifos. This finding opens a new way for designing high-performance nanozymes by harmonizing various nanocofactors at the atomic and molecular scale.
期刊：
Pesticide Biochemistry and Physiology,2024年199:105769 ISSN：0048-3575
通讯作者：
Sun, Y;Zhang, AD
作者机构：
[Zhou, Yaqing; Wang, Jili; Sun, Yong; Sun, Y; Zhou, Xin; Wu, Wenhai] Hanjiang Normal Univ, Coll Chem & Environm Engn, Shiyan 442000, Peoples R China.;[Zhang, Aidong; Han, Mengying] Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
通讯机构：
[Zhang, AD ] C;[Sun, Y ] H;Hanjiang Normal Univ, Coll Chem & Environm Engn, Shiyan 442000, Peoples R China.;Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
The discovery of safe, effective, and selective chemical algicides is the stringent need for the algicides development, and it is also one of the effective routes to control cyanobacteria harmful algal blooms and to meet the higher requirements of environmental and ecological. In this work, a series of novel bromo-N-phenyl-5-ohydroxyphenylpyrazole-3-carboxyamides were rationally designed as pseudilin analogs by bioisosteric replacement and molecular hybridization strategies, in which the pyrrole unit of pseudilin was replaced with pyrazole and further combined with the dominant structural fragments of algicide diuron. The synthesis was carried out by a facile four-step routeincluding cyclization, amidation, transanulation, and halogenation. The biological activity evaluation on AtIspD, EcIspD, Synechocystis sp. PCC6803 and Microcystis aeruginosa FACHB905 revealed that most compounds had good EcIspD and excellent cyanobacteria inhibitory activity. In particular, compound 6bb exhibited potent algicidal activity against PCC6803 and FACHB905 with EC50 = 1.28 mu M and 0.37 mu M, respectively, 1.4-fold and 4.0-fold enhancement compared to copper sulfate (EC50 = 1.79 and 1.49 mu M, respectively), and it also showed the best inhibitory activity of EcIspD. The binding of 6bb to EcIspD was explored by molecular docking, and it was confirmed that 6bb could bind to the EcIspD active site. Compound 6bb was proven to be a potential structure for the further development of novel algicides that targets IspD in the MEP pathway.
作者机构：
[Zhang, Xian; Zhang, Ruiping] The Radiology Department of First Hospital of Shanxi Medical University, Taiyuan, 030001, P. R. China;[Zhang, Xian; Dou, You; Li, Junrong; Sun, Yao] National Key Laboratory of Green Pesticides, International Joint Research Center for Intelligent Biosensor Technology and Health, College of Chemistry, Central China Normal University, Wuhan, Hubei, 430079, P. R. China;[Liu, Shuang] School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, 430070, China;[Chen, Peiyao] Key Laboratory of Fermentation Engineering (Ministry of Education), National "111" Center for Cellular Regulation and Molecular Pharmaceutics, Hubei Key Laboratory of Industrial Microbiology, School of Food and Biological Engineering, Hubei University of Technology, Wuhan, 430068, China;[Wen, Yating] Shanxi Bethune Hospital, Shanxi Academy of Medical Sciences, Tongji Shanxi Hospital, Third Hospital of Shanxi Medical University, Taiyuan, 030001, P. R. China
摘要：
Although being applied as photosensitizers for photodynamic therapy, covalent organic frameworks (COFs) fail the precise fluorescence imaging in vivo and phototherapy in deep-tissue, due to short excitation/emission wavelengths. Herein, we propose the first example of NIR-II emissive and benzobisthiadiazole-based COF-980. Comparing to its ligands, the structure of COF-980 could more efficiently reducing the energy gap (ΔE(S1-T1) ) between the excited state and the triplet state to enhance photodynamic therapy efficiency. Importantly, COF-980 demonstrates high photostability, good anti-diffusion property, superior ROS generation efficiency, promising imaging ability and ROS production in deep tissue (ཞ8mm). In vitro results reveal COF-980 combined with laser irradiation could trigger larger amount of intracellular ROS to high-efficiently induce cancer cell death. Notably, COF-980 NPs precisely enables PDT guided by NIR-II fluorescence imaging that effectively inhibit the 4T1 tumor growth with negligible adverse effects. This study provides a universal approach to developing long-wavelength emissive COFs and exploits its applications for biomedicine. This article is protected by copyright. All rights reserved.
作者机构：
[Li, Guang; Xu, Weiwei; Hameed, Muhammad Salman; Yang, Qinglin; Li, Haibing; Qu, Haonan] Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Quan, Jiaxin; Quan, JX] Hanjiang Normal Univ, Dept Chem Biol & Environm Engn, Shiyan 442000, Peoples R China.;[Zhang, J; Zhang, Jin] Yunnan Normal Univ, Coll Chem & Chem Engn, Kunming 650092, Peoples R China.;[Sun, Zhongyue] Hubei Univ Chinese Med, Sch Lab Med, Wuhan 430065, Peoples R China.
通讯机构：
[Quan, JX ; Sun, ZY ] H;[Li, HB ] C;[Zhang, J ] Y;Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;Hanjiang Normal Univ, Dept Chem Biol & Environm Engn, Shiyan 442000, Peoples R China.
关键词：
arginine;biomimetic;mimic Cyt C transport;nanochannel;pH
摘要：
Proteins are vital components in cells, biological tissues, and organs, playing a pivotal role in growth and developmental processes in living organisms. Cytochrome C (Cyt C) is a class of heme proteins found in almost all life and is involved in cellular energy metabolic processes such as respiration, mainly as electron carriers or terminal reductases. It binds cardiolipin in the inner mitochondrial membrane, leading to apoptosis. It is a challenge to design a simple and effective artificial system to mimic the complex Cyt C biological transport process. In this paper, an asymmetric biomimetic pH-driven protein gate is described by introducing arginine (Arg) at one end of an hourglass-shaped nanochannel. The nanochannel shows a sensitive protonation-driven protein gate that can be "off" at pH = 7 and "on" at pH = 2. Further studies show that differences in the binding of Arg and Cyt C at different levels of protonation lead to different switching behaviors within the nanochannels, which in turn lead to different surface charges within the nanochannels. It can be used for detecting Cyt C and as an excellent and robust gate for developing integrated circuits and nanoelectronic logic devices.
作者机构：
[Yin, Ya; Chen, Zhao; Deng, Dian-Dian] Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University, Nanchang 330013, People's Republic of China;[Guan, Qichen] State Key Laboratory of Separation Membrane and Membrane Process, School of Chemistry, Tiangong University, Tianjin 300387, People's Republic of China;[Liu, Sheng Hua; Liu, Shanting] Xi'an Key Laboratory of Functional Organic Porous Materials, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an 710129, People's Republic of China;[Sun, Yue] National Key Laboratory of Green Pesticide, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
摘要：
Achieving high-contrast tricolor emissive regulation of a single-component molecule using a single type of external stimulus is highly desirable but challenging. In the present study, we report a symmetric acceptor-donor-acceptor (A-D-A)-type aggregation-induced emission-active luminogen, which displays a sequential high-contrast fluorescence switching just by anisotropic mechanical grinding. Specifically, upon light grinding, an orange-yellow-to-blue hypsochromic mechanofluorochromic response with a distinct color contrast (change in the maximum emission wavelength, Δλ(em,max) = 122 nm) is noticed, and the slightly ground solid exhibits a blue-to-red high-contrast (Δλ(em,max) = 185 nm) bathochromic mechanofluorochromic conversion upon vigorous grinding. Thus, using a single luminogen developed here, we can realize wide-range (Δλ(em,max) > 100 nm) hypso- and bathochromic fluorescence mechanochromisms simultaneously. The tricolored mechanofluorochromic phenomenon is attributed to two different morphological transitions involving crystalline-to-crystalline and crystalline-to-amorphous states. Furthermore, three information anticounterfeiting systems are developed using the luminogen presented here.
