摘要：
Piezo-catalysis emerges as an efficient, safe, and affordable strategy for removing hazardous substances from aquatic environments. Here, the BiFeO(3) @In(2) Se(3) heterojunction demonstrates remarkable prowess as a piezo-catalyst, enabling the high-efficiency removal of uranium (U) from U(VI)-containing water. A total U(VI) removal efficiency of 94.6% can be achieved under ultrasonic vibration without any sacrificial agents. During the entire catalytic process, piezo-induced electrons, hydroxyl radicals, and superoxide radicals play important roles in U(VI) removal, while the generated H(2) O(2) is responsive to the transformation of soluble U(VI) into insoluble (UO(2) )O(2) •2H(2) O and UO(3) . Furthermore, auxiliary illumination can accelerate the increase of free charges, enabling the piezo-catalyst to retain more charges. This leads to an improved U(VI) removal efficiency of 98.8% and a significantly increased reaction rate constant. This study offers a comprehensive analysis of the fabrication of high-efficiency piezo-catalysts in the removal or extraction of U(VI) from U(VI)-containing water.
作者机构：
[Zeng, Min; Jiang, Zihan; Li, Peiqiang; Quan, Yuanting] Department of Biochemistry and Molecular Biology, School of Basic Medicine, Hengyang Medical School, University of South China, Hengyang, Hunan 421001, China;[Wu, Baibei] The Key Laboratory of Ecological Environment and Critical Human Diseases Prevention of Hunan Province Department of Education, Hengyang Medical School, University of South China, Hengyang, Hunan 421001, China;[Wei, Wenjie] Institute of Biochemistry of Hengyang Medical School, University of South China, Hengyang, Hunan 421001, China.;[Hu, Xiaobo] Department of Biochemistry and Molecular Biology, School of Basic Medicine, Hengyang Medical School, University of South China, Hengyang, Hunan 421001, China<&wdkj&>The Key Laboratory of Ecological Environment and Critical Human Diseases Prevention of Hunan Province Department of Education, Hengyang Medical School, University of South China, Hengyang, Hunan 421001, China
摘要：
Cancer is a major global health issue. Effective therapeutic strategies can prolong patients' survival and reduce the costs of treatment. Drug repurposing, which identifies new therapeutic uses for approved drugs, is a promising approach with the advantages of reducing research costs, shortening development time, and increasing efficiency and safety. Disulfiram (DSF), an Food and Drug Administration (FDA)-approved drug used to treat chronic alcoholism, has a great potential as an anticancer drug by targeting diverse human malignancies. Several studies show the antitumor effects of DSF, particularly the combination of DSF and copper (DSF/Cu), on a wide range of cancers such as glioblastoma (GBM), breast cancer, liver cancer, pancreatic cancer, and melanoma. In this review, we summarize the antitumor mechanisms of DSF/Cu, including induction of intracellular reactive oxygen species (ROS) and various cell death signaling pathways, and inhibition of proteasome activity, as well as inhibition of nuclear factor-kappa B (NF-κB) signaling. Furthermore, we highlight the ability of DSF/Cu to target cancer stem cells (CSCs), which provides a new approach to prevent tumor recurrence and metastasis. Strikingly, DSF/Cu inhibits several molecular targets associated with drug resistance, and therefore it is becoming a novel option to increase the sensitivity of chemo-resistant and radio-resistant patients. Studies of DSF/Cu may shed light on its improved application to clinical tumor treatment.
摘要：
In the photoreduction of U(VI), protective gases and additional sacrificial agents are still the major obstacles. Herein, we developed an oxygen-deficient WOx/g-C3N4 catalyst for the simultaneous reduction of U(VI) and preparation of benzaldehyde by selective oxidation of benzyl alcohol without protective gases and sacrificial agents. The removal of U(VI) by WOx/g-C3N4 could reach 98.5% and the conversion of benzyl alcohol was nearly 32% with a selectivity close to 100%. Compared with single g-C3N4 and defect-free WO3, the photoreduction activity of WOx/g-C3N4 was 10.4 and 7 times higher, respectively. Besides, the role of oxygen and oxygen defects was explored. Owing to oxygen defects in the catalyst, oxygen was adsorbed on the oxidation end (WOx) of the catalyst and activated without entering the reduction end to interfere with the photoreduction of U(VI), while favoring the generation of center dot O2- to improve the selectivity of benzaldehyde. Finally, a new mechanism was proposed.
摘要：
Ferroptosis is a newly recognized type of regulated cell death that is characterized by the accumulation of iron and lipid peroxides in cells. Studies have shown that ferroptosis plays a significant role in the pathogenesis of various diseases, including cardiovascular diseases. In cardiovascular disease, ferroptosis is associated with ischemia-reperfusion injury, myocardial infarction, heart failure, and atherosclerosis. The molecular mechanisms underlying ferroptosis include the iron-dependent accumulation of lipid peroxidation products, glutathione depletion, and dysregulation of lipid metabolism, among others. This review aims to summarize the current knowledge of the molecular mechanisms of ferroptosis in cardiovascular disease and discuss the potential therapeutic strategies targeting ferroptosis as a treatment for cardiovascular disease.
期刊：
Sensors and Actuators B-Chemical,2024年408:135562 ISSN：0925-4005
通讯作者：
Rong Hu
作者机构：
Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China;[Song Cheng; Li Xie; Haihai Fu; Yong Liu] AIE Institute, South China University of Technology, Guangzhou 510640, China;School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China;Department of Laboratory Medicine, General Hospital of Southern Theater Command, Guangzhou, Guangdong, China;Shenzhen Institute of Aggregate Science and Technology, School of Science and Engineering, The Chinese University of Hong Kong, Shenzhen, Guangdong 518172, China
通讯机构：
[Rong Hu] A;AIE Institute, South China University of Technology, Guangzhou 510640, China<&wdkj&>School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China
摘要：
Fluorescence immunoassay (FIA) is one of the most immunoassay diagnosis methods in clinic for biomarker quantification in recent years. The development of reliable FIA strategy with high-sensitivity, large-rang and outstanding efficiency for biomarkers rapid diagnosis, especially in complicated samples, is still a great challenge. Herein, an ultra-sensitive FIA combined with magnetic separation was established to achieve efficient point-of-care diagnosis in quantitative behavior based on bright aggregation-induced emission nanoparticles (AIE NPs). By utilizing swelling method, AIE NPs with controllable size, relatively high luminescence efficiency and large Stokes shift were prepared, moreover, the obtained NPs also exhibit narrow size distribution and well-defined spherical morphology. Stability studies prove that AIE NPs not only possess quite high photostability, but also present good resistance towards harsh acid-alkaline steadily. By using AIE NPs as the reporter, a reliable and efficient FIA sensor was successfully constructed. The precise detection of C-reaction protein (CRP) antigen was acquired with the linear range of 0.5 ng·mL−1 ∼ 1000 ng·mL−1 and the limit of detection (LOD) of 0.35 ng·mL−1, which is comparative with the conventional chemiluminescence immunoassays. Moreover, the whole detection operation could be accomplished within 10 min, which is relatively rapid and desirable for point-of-care diagnosis. In addition, this strategy also presented excellent specificity towards CRP antigens among various inflammatory antigens. These results confirm that AIE NPs-based FIA strategy provides an ideal and reliable approach for precise and quantitive biosensing of in vitro diagnostics.
作者机构：
[Rong-Nan Yi] Key Laboratory of Food & Environment & Drug Monitoring and Testing of Universities in Hunan Province, Hunan Police Academy, Changsha 41013, China;[Wei-Min He] School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China
通讯机构：
[Wei-Min He] S;School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China
通讯机构：
[Ren, XH; Ni, HW ] W;Wuhan Univ Sci & Technol, Fac Mat, State Key Lab Refractories & Met, Wuhan 430081, Peoples R China.
关键词：
Au nanoparticles;C1 chemistry;Electrocatalytic CO 2 reduction;TiO 2 nanowires
摘要：
Electrocatalytic CO2 reduction (CO2ER) to produce formic acid (HCOOH) would be an attractive means for carbon neutralization. In order to realize efficient CO2ER and economical conversion of CO2, the applying of metal active sites on surface of semiconductor has emerged as a promising strategy. Herein, we report the preparation of alkaline modified TiO2 nanowires (NWs) as the substrate for Au photodeposition. The asfabricated Au/TiO2 NWs exhibits high activity and selectivity towards HCOOH production compared with traditional catalysts. The key factors including deposition time, solution, and etc. And their effects on CO2ER performance have been systematically investigated. At -0.8 V vs RHE, the Faraday efficiency of the HCOOH can reach to 86.49 %, while the current density is 15.94 mA cm-2. In addition, Au/TiO2 NWs also exhibited good stability after 18 h electrocatalytic CO2RR under the voltage of -0.8 V vs RHE. Electrochemical tests indicated that Au/TiO2 NWs process favorable intrinsic electrochemical properties, high ESCA and accelerating charge transfer process make Au/TiO2 NWs obtain abundant active sites and kinetically favorable. This work provides a convenient fabrication strategy of Au/TiO2 based catalyst, which can guide the design and modification of gold for CO2ER into formic acid.
期刊：
Journal of Molecular Liquids,2024年397:124124 ISSN：0167-7322
通讯作者：
Chang-Ming Nie<&wdkj&>Guo-Wen Peng
作者机构：
School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China;Key Laboratory of Hunan Province for Design and Application of Natural Actinide Complexes, Hengyang 421001, China;[Wen-Jun Ouyang; Meng-Zhen Guo; Yun Wang; Xiang-He Kong; Xi-Lin Xiao] School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China<&wdkj&>Key Laboratory of Hunan Province for Design and Application of Natural Actinide Complexes, Hengyang 421001, China
摘要：
There are the similar physical and chemical properties between the trivalent actinides (An(III)) and the lanthanides (Ln(III)), which makes the separation process very difficult for nuclear waste reprocessing. Designing efficient ligands with the strong ability to separate An(III)/Ln(III) is one of the ways to solve the problem, and various ligands with 1,10-Phenanthroline as the skeleton have become a hotspot in recent years. Herein we designed a series of novel ligands using (1,10-phenanthroline-2,9-diyl)bis(indolin-1-ylmethanones)(IDL-DAPhen) as a new skeleton. Using scalar relativistic density functional theory (DFT), we systematically unraveled the properties of four IDL-DAPhens modified with electron-donating groups (–CH3, –OCH3) at different substitution sites, and explored the structures of the ligands L1, L2, L3 and L4, bonding properties and thermodynamic behaviors of their complexes coordinated with Am(III)/Eu(III). Molecular orbitals (MOs), IGMH, ETS-NOCV and other analyses showed that the selectivity of the four ligands to Am(III) was higher than that to Eu(III). The bond length, dihedral angle, WBI, QTAIM and thermodynamic results and other ones indicated that L3 and L4 with para-substituents have stronger coordination ability, while L1 and L3 with methyl-substituted exhibit better Am(III)/Eu(III) separation selectivity. The ΔΔG values of L1 for Am(III)/Eu(III) reached −7.71, −7.77 and −11.57 kcal/mol in water, 1-octanol and aniline, respectively. This study provides theoretical guidance for the design of novel ligands for efficient separation of Am (III)/Eu (III), and could expand a new pathway for the design of ligands with better potential selectivity for An (III)/Ln (III) separation.
关键词：
conductivity;electron mobility;electron-transport layers;nonfullerene organic solar cells;small molecular electrolytes
摘要：
The electron-transport layer (ETL) is essential for achieving high performance and stability of organic solar cells (OSCs). However, most organic ETLs suffer from low conductivity, low electron mobility, and difficult modification, resulting in mitigation of charge collection and transport. Metal-organic complex, such as ferrocene, is a promising candidate to improve organic ETL due to their excellent film-forming property, easy preparation, and high electrical properties. Herein, a small molecule, PDIN-Fc, based on PDIN modified by ferrocene is designed, which can be synthesized by environmentally friendly esterification and quaternization reactions. PDIN-Fc displays outstanding alcohol solubility and tunable work function. Interestingly, introducing the ferrocene group can lead to increased self-doping of PDIN-Fc. As a result, PDIN-Fc shows significantly improved charge transport performance and conductivity compared to PDIN. When using PM6:L8-BO as the photoactive layer, the OSCs with PDIN-Fc as ETL achieve a remarkable power conversion efficiency of 18.45% and exhibit notable high light stability. This study demonstrates an effective strategy to design efficient ETLs by incorporating metal complexes, which enable thickness insensitivity, good stability, and high-performance photovoltaic devices. A perylene diimide-based small-molecular electrolyte, PDIN-Fc, terminated by ferrocene groups through ammonium linker is reported, which can display good alcohol solubility and tunable work function. Benefited by the increased self-doping of PDIN-Fc, corresponding PM6:L8-BO-based organic solar cells can display high efficiency of 18.45%; meanwhile, improved stability can be realized.image (c) 2023 WILEY-VCH GmbH
作者机构：
[Yao, Chen; Zhang, Ye; Yang, Yan; Liu, Cai-Ling; Huang, Wen-Yao] School of Chemistry and Chemical Engineering, University of South China, No. 28, Changsheng West Road, Hengyang, Hunan 421001, P. R. China
摘要：
The usage of a conductive hydrogel in wearable sensors has been thoroughly researched recently. Nonetheless, hydrogel-based sensors cannot simultaneously have excellent mechanical property, high sensitivity, comfortable wearability, and rapid self-healing performance, which result in poor durability and reusability. Herein, a robust conductive hydrogel derived from one-pot polymerization and subsequent solvent replacement is developed as a wearable sensor. Owing to the reversible hydrogen bonds cross-linked between polymer chains and clay nanosheets, the resulting conductive hydrogel-based sensor exhibits outstanding flexibility, self-repairing, and fatigue resistance performances. The embedding of graphene oxide nanosheets offers an enhanced hydrogel network and easy release of wearable sensor from the target position through remote irradiation, while Li(+) ions incorporated by solvent replacement endow the wearable sensor with low detection limit (sensing strain: 1%), high conductivity (4.3 S m(-1)) and sensitivity (gauge factor: 3.04), good freezing resistance, and water retention. Therefore, the fabricated wearable sensor is suitable to monitor small and large human motions on the site and remotely under subzero (-54 °C) or room temperature, indicating lots of promising applications in human-motion monitoring, information encryption and identification, and electronic skins.
摘要：
L<bold>-</bold>Tryptophan (L-Trp), one of the essential amino acids, is crucial for human physiological homeostasis and a limiting amino acid in animal feed. In addition, L-Trp is a precursor of some important biomolecules in the body, such as pentraxin and melatonin. Disorders of L-Trp metabolism in the body may cause Alzheimer's or Parkinson's disease. Therefore, monitoring L-Trp levels in the body fluids quickly and accurately is essential. A colorimetric biosensor was developed for the rapid detection of L-Trp in solutions by coupling a novel, screened, and validated peptide aptamer with Au nanoparticles via the Au-S bond. The biosensor showed a wide linear detection range of 1 mu M - 1000 mu M, and in addition, it was simple to construct, and the reaction time was as short as 10 s. In the analysis of L-Trp in actual porcine serum samples, the relative standard deviations were 4.52 % to 3.01 % compared with those of the high-performance liquid chromatography method, and the spiked recoveries were 99.2 % to 100.2 %. This new type of recognition probe is likely to gain attention in the field of bioanalysis owing to its biocompatibility, ease of modification, and easy linkage to nanomaterials.
作者机构：
[Tang, Xian; Han, Hai] Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Peoples R China.;[Li, Le] Univ South China, Sch Publ Hlth, Hengyang 421001, Peoples R China.;[Wang, Hongqing] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Wang, Hongqing] Univ South China, Hunan key Lab Design & Applicat Actinide Complexes, Hengyang 421001, Hunan, Peoples R China.
通讯机构：
[Tang, X ; Li, L ] U;Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Peoples R China.;Univ South China, Sch Publ Hlth, Hengyang 421001, Peoples R China.
摘要：
Uranium, highly chemically toxic and radioactive with a long half-life, poses environmental risks due to activities like uranium mining, refining, and nuclear power plant operations. Detecting uranyl ion in real-time is crucial to assess human health risks and control uranium pollution. Electrochemical sensing offers advantages such as sensitivity, selectivity, simplicity, rapidity, and cost-effectiveness, making it ideal for on-site detection of uranyl ion. This paper summarizes recent research progress in electrochemical detection of uranyl. Various techniques including cyclic voltammetry, differential pulse voltammetry, stripping voltammetry, and electrochemical impedance spectroscopy are discussed along with their respective advantages. Detection methods utilizing electrode-modified functional materials like biomaterials, polymers, and nanomaterials are investigated. Probes like DNAzyme, ion-imprinted polymers, and 2D materials are highlighted for their detection mechanism and effectiveness. Electrochemical sensing with these probes achieves nanomolar-level detection limits (nM) with excellent stability and selectivity, suggesting practical applications. Lastly, predictions are made regarding sensing mechanisms, electrode material selection, and adaptability to field conditions for electrochemical detection of uranyl ion.
作者：
Yang, Xinzhe;Hu, Rong;Qin, Anjun;Tang, Ben Zhong
期刊：
European Polymer Journal,2024年204:112704 ISSN：0014-3057
通讯作者：
Tang, BZ
作者机构：
[Qin, Anjun; Hu, Rong; Yang, Xinzhe] South China Univ Technol, Guangdong Prov Key Lab Luminescence Mol Aggregates, State Key Lab Luminescent Mat & Devices, Guangzhou 510640, Peoples R China.;[Qin, Anjun; Hu, Rong; Tang, Ben Zhong; Yang, Xinzhe] South China Univ Technol, AIE Inst, Ctr Aggregat Induced Emiss, Guangzhou 510640, Peoples R China.;[Tang, Ben Zhong] Chinese Univ Hong Kong, Sch Sci & Engn, Shenzhen CUHK Shenzhen, Hong Kong 518172, Guangdong, Peoples R China.;[Tang, Ben Zhong] Hong Kong Univ Sci & Technol, Chinese Natl Engn Res Ctr Tissue Restorat & Recons, Hong Kong Branch, Clear Water Bay, Hong Kong, Peoples R China.;[Hu, Rong] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.
通讯机构：
[Tang, BZ ] S;South China Univ Technol, AIE Inst, Ctr Aggregat Induced Emiss, Guangzhou 510640, Peoples R China.;Chinese Univ Hong Kong, Sch Sci & Engn, Shenzhen CUHK Shenzhen, Hong Kong 518172, Guangdong, Peoples R China.;Hong Kong Univ Sci & Technol, Chinese Natl Engn Res Ctr Tissue Restorat & Recons, Hong Kong Branch, Clear Water Bay, Hong Kong, Peoples R China.
摘要：
Polymers with clusteroluminescence (CL) characteristics are attractive in the biological field because of their structural diversity and high biocompatibility. Benefiting from the amplification effect of the polymer, CL polymers present promising advantages in biological applications. In this review, the frontiers and progress of CL polymers were firstly introduced. Then, the bio-related applications, including sensing, bioimaging both in vitro and in vivo, and therapeutic applications, in recent years were summarized in detail. Finally, the development trend and challenges were also briefly discussed. It is hoped that this review will accelerate the development of CL polymers and their applications in biological areas.
摘要：
Metal complexes, particularly copper(II) complexes, are often used as anticancer drugs due to their ability to generate reactive oxygen species (ROS) in cells. Four copper(II) complexes have been designed based on ligands for triplet pyridine derivatives (complexes 1-4), and their structures have been determined using X-ray single crystal analysis. The interactions of these complexes with calf thymus DNA (CT-DNA) have been investigated using various techniques, including UV-vis absorption, viscosity measurements, and circular dichroism spectroscopy. The results indicate that complexes 1-4 strongly interact with DNA through partial intercalations. Further investigation using agarose gel electrophoresis shows that all four complexes can cleave pBR322 DNA in the presence of ascorbic acid as a reducing agent, and the DNA cleavage mechanism is through the generation of singlet oxygen ((1)O(2)). In vitro anticancer activities of these complexes have been evaluated using A549, MDA-MB-231, HeLa, and HepG2 cells. The calculated IC(50) values indicate significant efficacy against cancer cells. Additionally, AO/EB staining assays reveal that these complexes induce cell apoptosis in HeLa cell line.
摘要：
Research on porphyrin-based photosensitizing drugs is becoming increasingly popular. They possess unique diagnostic capabilities and therapeutic effects that have gained wide recognition in oncology drug development. In recent years, the rapid growth of nanotechnology has brought great hope for nanopharmaceutical formula-tions. By combining porphyrins with various nanomaterials, people have improved the properties of porphyrin compounds, making drug delivery easier. Porphyrin-based nanoparticles can enhance the effect of photodynamic therapy for cancer treatment, providing opportunities for achieving complex targeting strategies and versatility with promising applications in drug carriers, tumor imaging, and treatment. This paper reviews recent porphyrin nanodrugs, including inorganic-organic hybrid nanoparticles, nanomicelles, self-assembled nanoparticles, and combination therapeutic nanodrugs, and their actions and effects on cancer cells when performing photodynamic therapy. It also discusses the drawbacks as well as the prospects for development.
作者机构：
[Tan, Huaxin; Hu, Lidan; Wei, Xiaojie; Li, Yongzhen; Ma, Jiaying] Univ South China, Hunan Prov Cooperat Innovat Ctr Mol Target New Dru, Sch Basic Med,Key Lab Ecol Environm & Crit Human D, Dept Biochem & Mol Biol,Dept Educ, Hengyang 421001, Peoples R China.;[Jiang, Suhua; Wang, Peiyuan; Ma, Jiaying] Chinese Acad Sci, Fujian Inst Res Struct Matter, Key Lab Design & Assembly Funct Nanostruct, Fuzhou 350002, Peoples R China.;[Jiang, Suhua; Zhu, Fukai] Minnan Normal Univ, Collaborat Innovat Ctr Mushroom Hlth Ind, Zhangzhou 363000, Fujian, Peoples R China.;[Ji, Xiaoxuan] Xiamen Univ, Sch Pharmaceut Sci, State Key Lab Cellular Stress Biol, Xiamen 361102, Peoples R China.;[Wang, Peiyuan] Chinese Acad Sci, Xiamen Inst Rare Earth Mat, Dept Translat Med, Xiamen 361021, Peoples R China.
通讯机构：
[Huaxin Tan] D;[Peiyuan Wang] K;Department of Biochemistry and Molecular Biology, the Key Laboratory of Ecological Environment and Critical Human Diseases Prevention of Hunan Province Department of Education, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, School of Basic Medicine, University of South China, Hengyang 421001, PR China<&wdkj&>Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, PR China<&wdkj&>Department of Translational Medicine, Xiamen Institute of Rare Earth Materials, Chinese Academy of Sciences, Xiamen 361021, PR China
摘要：
Green tea is one of people's favorite drinks. However, pesticide residues in green tea can cause harm to the human body, and therefore, detection of pesticide residues in green tea is very important. In recent years, the detection of pesticide residues in tea has become a research hotspot. In this paper, a gas chromatography-mass spectrometry/mass spectrometry (GC-MS/MS) detection method of tolfenpyrad pesticide residues in green tea was established by using acetonitrile extractant, dispersive solid-phase extraction purification, temperature programming and application retention time lock with the database. After the sample was extracted with acetonitrile, then the sample was purified by QuEChERS extraction purification tube, afterward isomer B was used as the internal standard for the determination by multiple reaction monitoring mode (MRM) of GC-MS/MS. The results indicated that the experimental data accorded with the criterion on quality control of laboratoris(chemical testing of food), and the requirements of recovery, calibration curve, precision.This method was used to detect tolfenpyrad residues in actual green tea samples in multiple batches, and the satisfactory results were obtained.
期刊：
Separation Science and Technology,2023年58(10):1833-1850 ISSN：0149-6395
通讯作者：
Nie, CM
作者机构：
[Liao, Li-Fu; Nie, Chang-Ming; Ma, Ming-Jie; Xiao, Chun-Mei; Nie, CM; Xiao, Xi-Lin] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Liao, Li-Fu; Nie, Chang-Ming; Ma, Ming-Jie; Xiao, Chun-Mei; Xiao, Xi-Lin] Key Lab Hunan Prov Design & Applicat Nat Actinide, Hengyang, Peoples R China.
通讯机构：
[Nie, CM ] U;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.
关键词：
Uranyl-MMQBQ;chiral fungicides;enantiomeric separation;R/S-metalaxyls and R/S-benalaxyls;density functional theory (DFT)
摘要：
Chiral fungicides R/S-metalaxyls(R/S-MTLs) and R/S-benalaxyls(R/S-BNLs) have different biotoxicity. It is very important to unravel molecular recognition and enantiomeric separation of R/S-MTLs or R/S-BNLs. In this paper, we designed a novel asymmetric ligand: 5-methoxy-2-(4-methoxy-6”-(quinazolin-2-yl)-[2,2”−bipyridin]-6-yl)quinazoline(MMQBQ), further constructed a new asymmetric receptor Uranyl-MMQBQ by coordination of MMQBQ with uranyl. The complexation and separation of receptor Uranyl-MMQBQ with guests R/S-MTLs or R/S-BNLs were systematically studied using density functional theory (DFT) method. The respects of ESP, MBO, RFC, LOL, EDDM, EST-NOCV, QTAIM, FMOs, IGMH, and Gibbs free energy changes were calculated and analyzed. The results indicated that the MMQBQ could form a stable receptor Uranyl-MMQBQ with uranyl, which could selectively recognize and separate chiral R/S-MTLs or R/S-BNLs by receptor’s U coordinating to carbonyl oxygens of guests. For R/S-MTLs, separation factors(SFS/R) of Uranyl-MMQBQ were more than 16 in water, chlorobenzene, toluene, carbon tetrachloride and cyclohexane, enantioselectivity coefficients(ESCs) ranged of 99.92%-94.24% in the above four solvents. While for R/S-BNLs, ESCs of Uranyl-MMQBQ were over 99% and SFS/R values were a range of 533.97–2839.36 in the above organic solvents. The findings provide valuable information for design of novel uranyl ligand and its complexes, meanwhile supply useful guidance for experiments on separation of other chiral fungicides in environmental protection.
