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.
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.
摘要：
An electrochemcial synthesis of indoline‐fused polycycles by constructing both the five‐ and six‐membered heterocyclic rings in a single step from arylamide‐tethered ynones has been developed, which provides facile access to various indoline‐based tetracyclic 6/5/6/6 skeletons with highly regioselective control in a sustainable, metal‐ and oxidant‐free condition. Abstract Indoline‐fused polycyclic scaffolds are virtually universal in biological and pharmaceutical. Here we demonstrate a facile electrooxidative cascade cyclization for indoline‐based derivatives, employing amidyl radicals with ynones under mild conditions. The efficient method enables the formation of two new C−N and C−C bonds in a single step with high regioselectivity. Various indoline‐based tetracyclic 6/5/6/6 skeletons can be achieved through a biscyclization/dehydrogenation cascade process. Additionally, this electrochemical strategy proceeds in a sustainable metal‐ and oxidant‐free condition, with H2 being the solely byproduct.
作者机构：
[Qiu, Xiaofeng; Zheng, Juan; Zhu, Xiaoxiao; Zhang, Qian; Guo, Yanbing; Zhu, Yuhua; Chen, Wei; Zhang, Baojian; Guo, YB; Luo, Zhu; Li, Weihao; Pan, Chuanqi; Fang, Yarong; Wang, Jinlong] Cent China Normal Univ, Inst Environm & Appl Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ,Coll Chem,Key Lab Pesticide & Chem Bio, Wuhan 430079, Peoples R China.;[Guo, Yanbing; Guo, YB; Luo, Zhu; Wang, Jinlong] Wuhan Inst Photochem & Technol, Wuhan 430082, Peoples R China.;[Wu, Jinsong; Wang, Yutao] Wuhan Univ Technol, Nanostruct Res Ctr, State Key Lab Adv Technol Mat Synth & Proc, Wuhan 430070, Peoples R China.;[Hu, Jinpeng; Wang, Sibo] Fujian Longxin 3D Array Technol Co Ltd, Longyan 364000, Peoples R China.;[Cui, Shuang] SINOPEC Beijing Res Inst Chem Ind Co Ltd, Div Anal, Beijing 100013, Peoples R China.
通讯机构：
[Guo, YB ; Luo, Z] C;Cent China Normal Univ, Inst Environm & Appl Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ,Coll Chem,Key Lab Pesticide & Chem Bio, Wuhan 430079, Peoples R China.;Wuhan Inst Photochem & Technol, Wuhan 430082, Peoples R China.
关键词：
(Pt−S−O)-Ti active structure;C3H8 catalytic oxidation;C−H bond activation;Pt-based catalysts;SO2 promotion
摘要：
Typically, SO(2) unavoidably deactivates catalysts in most heterogeneous catalytic oxidations. However, for Pt-based catalysts, SO(2) exhibits an extraordinary boosting effect in propane catalytic oxidation, but the promotive mechanism remains contentious. In this study, an in situ-formed tactful (Pt-S-O)-Ti structure was concluded to be a key factor for Pt/TiO(2) catalysts with a substantial SO(2) tolerance ability. The experiments and theoretical calculations confirm that the high degree of hybridization and orbital coupling between Pt 5d and S 3p orbitals enable more charge transfer from Pt to S species, thus forming the (Pt-S-O)-Ti structure with the oxygen atom dissociated from the chemisorbed O(2) adsorbed on oxygen vacancies. The active oxygen atom in the (Pt-S-O)-Ti active structure is a robust site for C(3)H(8) adsorption, leading to a better C(3)H(8) combustion performance. This work can provide insights into the rational design of chemical bonds for high SO(2) tolerance catalysts, thereby improving economic and environmental benefits.
作者机构：
[Xu, Yuling; Luo, Lishi; Sun, Yao; Pang, Yida; Yang, Jingfang; Li, Chonglu] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Luo, Lishi] Hunan Univ, State Key Lab Chemo Biosensing & Chemometr, Changsha 410082, Peoples R China.;[Sharma, Amit] Amity Univ Punjab, Amity Sch Chem Sci, Dept Phys, Mohali 140306, India.;[Liu, Shuang] Wuhan Univ Technol, Sch Mat Sci & Engn, Wuhan 430070, Peoples R China.;[Zhan, Jianbo] Hubei Prov Ctr Dis Control & Prevent, Inst Hlth Inspect & Testing, Wuhan, Hubei, Peoples R China.
通讯机构：
[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.
摘要：
Albeit sonodynamic therapy (SDT) has achieved encouraging progress in microbial sterilization, the scarcity of guidelines for designing highly effective sonosensitizers and the intricate biofilm microenvironment (BME), substantially hamper the therapeutic efficacy against biofilm infections. To address the bottlenecks, we innovatively design a Ru(II) metallacycle-based sonosensitizer/sonocatalyst (named Ru-A3-TTD) to enhance the potency of sonotherapy by employing molecular engineering strategies tailored to BME. Our approach involves augmenting Ru-A3-TTD's production of ultrasonic-triggered reactive oxygen species (ROS), surpassing the performance of commercial sonosensitizers, through a straightforward but potent pi-expansion approach. Within the BME, Ru-A3-TTD synergistically amplifies sonotherapeutic efficacy via triple-modulated approaches: (i) effective alleviation of hypoxia, leading to increased ROS generation, (ii) disruption of the antioxidant defense system, which shields ROS from glutathione consumption, and (iii) enhanced biofilm penetration, enabling ROS production in deep sites. Notably, Ru-A3-TTD sono-catalytically oxidizes NADPH, a critical coenzyme involved in antioxidant defenses. Consequently, Ru-A3-TTD demonstrates superior biofilm eradication potency against multidrug-resistant Escherichia coli compared to conventional clinical antibiotics, both in vitro and in vivo. To our knowledge, this study represents the pioneering instance of a supramolecular sonosensitizer/sonocatalyst. It provides valuable insights into the structure-activity relationship of sonosensitizers and paves a promising pathway for the treatment of biofilm infections. A facile pi-expansion strategy is proposed to boost the reactive oxygen species-generation capability, resulting in the development of the first example of a supramolecular sonosensitizer (Ru-A3-TTD). Ru-A3-TTD effectively overcame challenges posed by the complex biofilm microenvironment, including hypoxia, antioxidant defense mechanisms, and hypopermeability for amplifying sonotherapeutic efficacy in eradicating multidrug-resistant biofilms.+ image
摘要：
Regioselective 1,2-dichalcogenation of alkenes has attracted significant attention in modern organic synthetic chemistry. While there are a plethora of methods to access alkene dichalcogenated architectures, sulfonylsulfination of alkenes is extremely challenging due to the inherent characteristics of the sulfur atom. Herein, a multicomponent fragment coupling of alkenes, sulfinates, and DABSO was developed to construct densely functionalized sulfonylsulfinated products, which are otherwise challenging to access, with broad substrate scope and group tolerance under mild and operationally simple conditions, using an inexpensive 100-1000 ppm organic photocatalyst. In addition, the protocol was applied to the late-stage functionalization of complex molecules, and the obtained products were converted into diverse downstream transformations to demonstrate their synthetic potential. Experimental and theoretical mechanistic investigations suggest that these reactions proceed through sequential sulfonyl and sulfinyl oxygen radical mutual transformations and radical-polar crossover coupling. This strategy provides access to previously inaccessible alkene sulfonylsulfinated products in good-to-high regio- and stereoselectivity, along with opening up previously unexplored synthetic directions.
作者机构：
[Liu, Lijuan; Zhang, Lizhi; Gong, JM; Meng, Mingxia; Gong, Jingming; Yao, Qingfeng; Cai, Zheng; Sun, Hongwei; Jiang, Fang] Cent China Normal Univ, Int Joint Res Ctr Intelligent Biosensing Technol &, Key Lab Pesticide & Chem Biol, Coll Chem,Minist Educ, Wuhan 430079, Peoples R China.
通讯机构：
[Gong, JM ] C;Cent China Normal Univ, Int Joint Res Ctr Intelligent Biosensing Technol &, Key Lab Pesticide & Chem Biol, Coll Chem,Minist Educ, Wuhan 430079, Peoples R China.
摘要：
As emerging contaminants in the environment, antibiotic resistance genes (ARGs) have aroused a global health crisis and posed a serious threat to ecological safety and human health. Thus, efficient and accurate onsite detection of ARGs is crucial for environmental surveillance. Here, we presented a colorimetric-photoelectrochemical (PEC) dual-mode bioassay for simultaneous detection of multiple ARGs by smartly incorporating rolling circle amplification (RCA) into a stimuli-responsive DNA nanoassembly, using the tetracycline resistance genes tetA and tetC as models. The tailored DNA nanoassembly containing RCA amplicons hybridized with specific signal probes: CuO nanoflowers-anchored signal DNA1 and HgO nanoparticles-anchored signal DNA2, respectively. Upon exposure to an acidic stimulus, numerous Cu(2+) and Hg(2+) were released, serving as the reporting agent of colorimetric/PEC dual-mode assay. The released Cu(2+) and Hg(2+) induced localized surface plasmon resonance shifts in Au nanorods and triangular Ag nanoplates through an etching process, respectively, enabling visual analysis of ARGs with distinguishing color changes. Meanwhile, numerous Cu(2+) and Hg(2+) triggered the amplified PEC variations via reacting with the photoactive layers of CuS/CdS and ZnS, respectively. Thus, a rapid and ultrasensitive colorimetric/PEC dual-mode detection of multiple ARGs was achieved with the detection limit down to 17.2 aM. Furthermore, such dual-mode bioassay could discriminate single-base mismatch and successfully determine ARGs in E. coli plasmids and sludge samples, holding great promise for point-of-care genetic diagnostics.
摘要：
Organic molecules bearing chiral sulfur stereocenters exert a great impact on asymmetric catalysis and synthesis, chiral drugs, and chiral materials. Compared with acyclic ones, the catalytic asymmetric synthesis of thio-heterocycles has largely lagged behind due to the lack of efficient synthetic strategies. Here we establish the first modular platform to access chiral thio-oxazolidinones via Pd-catalyzed asymmetric [3+2] annulations of vinylethylene carbonates with sulfinylanilines. This protocol is featured by readily available starting materials, and high enantio- and diastereoselectivity. In particular, an unusual effect of a non-chiral supporting ligand on the diastereoselectivity was observed. Possible reaction mechanisms and stereocontrol models were proposed. Two Pd-catalyzed asymmetric [3+2] annulations are disclosed, providing a modular platform for the enantioselective synthesis of chiral thio-oxazolidinones. Preliminary mechanistic studies are performed to rationalize the observed enantio- and diastereo-controls.+ image
