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Chlorination of UV Filters with Antioxidant Shield in Swimming Pool Waters - Products Identification and Toxicity Assessment. 游泳池水体中带有抗氧化保护层的紫外线过滤器的氯化--产品识别和毒性评估。
IF 1.2 4区 化学
Acta Chimica Slovenica Pub Date : 2023-11-24 DOI: 10.17344/acsi.2023.8411
Mojca Bavcon Kralj, Albert T Lebedev, Polonca Trebše
{"title":"Chlorination of UV Filters with Antioxidant Shield in Swimming Pool Waters - Products Identification and Toxicity Assessment.","authors":"Mojca Bavcon Kralj, Albert T Lebedev, Polonca Trebše","doi":"10.17344/acsi.2023.8411","DOIUrl":"https://doi.org/10.17344/acsi.2023.8411","url":null,"abstract":"<p><p>This work summarizes our research on synthesis, characterization and toxicity of selected UV-A filters and their antioxidant shield in commercial formulation - resveratrol. Benzophenone type of UV filters react under disinfection conditions with chlorine and form different mono- and dichlorinated products, while dibenzoylmethane derivatives, such as avobenzone, react with chlorine and form two main bridge chlorinated products followed by numerous chlorinated species at the advanced stages of the process. Resveratrol showed three main susceptible centers to chlorination, starting from the electrophilic addition to the double bond and continuing with the chlorination of the phenolic moieties. Several experiments conducted under different disinfection conditions (pool/sea water, addition of salts, irradiation) showed basically similar chlorination patters with some variations in terms of product formation. The results of toxicity assessment using different test organisms (Vibrio fischeri, microalgae, daphnids) have shown different sensitivity of testing organisms to the parent UV filters in comparison with chlorinated products as well as different toxicity for specific UV filter in comparison to the others. As the closing loop of all experiments in the laboratory, an up-scaling to the real human skin is presented.</p>","PeriodicalId":7122,"journal":{"name":"Acta Chimica Slovenica","volume":"70 4","pages":"601-610"},"PeriodicalIF":1.2,"publicationDate":"2023-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138827646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis, Crystal Structure and In Vitro Cytotoxicity of Novel Cu(II) Complexes Derived from Isatine Hydrazide-Hydrazone Ligands. 异汀肼-腙配体衍生的新型 Cu(II) 配合物的合成、晶体结构和体外细胞毒性。
IF 1.2 4区 化学
Acta Chimica Slovenica Pub Date : 2023-11-23 DOI: 10.17344/acsi.2023.8398
Cansu Topkaya
{"title":"Synthesis, Crystal Structure and In Vitro Cytotoxicity of Novel Cu(II) Complexes Derived from Isatine Hydrazide-Hydrazone Ligands.","authors":"Cansu Topkaya","doi":"10.17344/acsi.2023.8398","DOIUrl":"https://doi.org/10.17344/acsi.2023.8398","url":null,"abstract":"<p><p>The research focuses on investigating the cytotoxic effects of Cu(II) complexes bearing isatine groups on cancer cells. These complexes were tested against lung carcinoma (A549) and breast carcinoma (MCF-7) cell lines using the MTT assay, with cisplatin as a positive control. Additionally, their effects on human normal cell line 3T3 were assessed. The Cu(L1)2 complex exhibited significant inhibitory effects on tumor cells in a dose-dependent manner, although not as potent as cisplatin. The cytotoxic selectivity indices (SI) indicated acceptable selectivity levels for both cancer cell lines, indicating potential for selective lethality. The crystal structure of one compound was confirmed, revealing van der Waals interactions and hydrogen bonding in the packing.</p>","PeriodicalId":7122,"journal":{"name":"Acta Chimica Slovenica","volume":"70 4","pages":"620-627"},"PeriodicalIF":1.2,"publicationDate":"2023-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138827571","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Development of QSAR model based on Monte Carlo optimization for predicting GABAA receptor binding of newly emerging benzodiazepines. 开发基于蒙特卡罗优化的 QSAR 模型，用于预测新出现的苯并二氮杂卓的 GABAA 受体结合。
IF 1.2 4区 化学
Acta Chimica Slovenica Pub Date : 2023-11-23 DOI: 10.17344/acsi.2023.8465
Aleksandra Antović, Radovan Karadžić, Jelena Živković, Aleksandar Veselinovic
{"title":"Development of QSAR model based on Monte Carlo optimization for predicting GABAA receptor binding of newly emerging benzodiazepines.","authors":"Aleksandra Antović, Radovan Karadžić, Jelena Živković, Aleksandar Veselinovic","doi":"10.17344/acsi.2023.8465","DOIUrl":"https://doi.org/10.17344/acsi.2023.8465","url":null,"abstract":"<p><p>Benzodiazepines and their derivatives belong to a category of new psychoactive substances that have been introduced into the continually expanding illicit market. However, there is a notable absence of available pharmacological data for these substances. To gain a deeper understanding of their pharmacology, we employed the Monte Carlo optimization conformation-independent method as a tool for developing QSAR models. These models were built using optimal molecular descriptors derived from both SMILES notation and molecular graph representations. The resulting QSAR model demonstrated robustness and a high degree of predictability, proving to be very reliable. Moreover, we were able to identify specific molecular fragments that exerted both positive and negative effects on binding activity. This discovery paves the way for the swift prediction of binding activity for emerging benzodiazepines, offering a faster and more cost-effective alternative to traditional in vitro/in vivo analyses.</p>","PeriodicalId":7122,"journal":{"name":"Acta Chimica Slovenica","volume":"70 4","pages":"634-641"},"PeriodicalIF":1.2,"publicationDate":"2023-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138827649","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synergistic, Additive and Antagonistic Interactions of Grapes' Phenolic Compounds and Organic Acids. 葡萄酚类化合物和有机酸的协同、相加和拮抗作用
IF 1.2 4区 化学
Acta Chimica Slovenica Pub Date : 2023-11-18 DOI: 10.17344/acsi.2023.8214
Crina Vicol, Gheorghe Duca
{"title":"Synergistic, Additive and Antagonistic Interactions of Grapes' Phenolic Compounds and Organic Acids.","authors":"Crina Vicol, Gheorghe Duca","doi":"10.17344/acsi.2023.8214","DOIUrl":"https://doi.org/10.17344/acsi.2023.8214","url":null,"abstract":"<p><p>The antioxidant interactions between several natural phenolic and non-phenolic compounds (catechin, quercetin, rutin, resveratrol, gallic acid and ascorbic acid) and organic acids (tartaric, citric and dihydroxyfumaric acids) have been investigated through the DPPH method. Main additive and antagonistic interactions have been found for the combinations of catechin, quercetin, resveratrol and gallic acid with tartaric and citric acids; such behavoir can be due to the enhanced stability of the phenolic compounds in the acidic media. Rutin and ascorbic acid demonstrated good synergistic effects with tartaric and citric organic acids, which may rely on the polymerization processes for rutin, and change of the mechanism of action in case of ascorbic acid. In combination with dihydroxyfumaric acid, the mixtures showed dose - dependent synergistic, additive or antagonistic antioxidant interactions. Good synergystic effects have been registered for the binari mixtures of dihydroxyfumaric acid with ascorbic acid, catechin and rutin.</p>","PeriodicalId":7122,"journal":{"name":"Acta Chimica Slovenica","volume":"70 4","pages":"588-600"},"PeriodicalIF":1.2,"publicationDate":"2023-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138827654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis, Crystal Structure, Hirshfeld Surface Analysis, and DFT Calculations of the Novel Binuclear Copper(I) Complex Containing 2-Benzimidazolethiole and Triphenylphosphine Ligands. 含 2-苯并咪唑硫醚和三苯基膦配体的新型双核铜(I)配合物的合成、晶体结构、Hirshfeld 表面分析和 DFT 计算。
IF 1.2 4区 化学
Acta Chimica Slovenica Pub Date : 2023-11-18 DOI: 10.17344/acsi.2023.8416
Karwan Omer Ali
{"title":"Synthesis, Crystal Structure, Hirshfeld Surface Analysis, and DFT Calculations of the Novel Binuclear Copper(I) Complex Containing 2-Benzimidazolethiole and Triphenylphosphine Ligands.","authors":"Karwan Omer Ali","doi":"10.17344/acsi.2023.8416","DOIUrl":"https://doi.org/10.17344/acsi.2023.8416","url":null,"abstract":"<p><p>The reaction of 2-benzimidazolethiole (2-BIT) with copper dichloride in the presence of two equivalents of triphenylphosphine led to a binuclear complex of the type [Cu(µ-S-2-BIT)2(Ph3P)2Cl2]: dichloridobis(μ-1,3-dihydro-2H-benzimidazole-2-thione)bis(triphenylphosphi ne)-di-copper. The Cu(I) compound has been fully identified by elemental analysis, molar conductivity, FT-IR, UV/Vis, and single-crystal X-ray diffraction (XRD). The XRD study reveals that the complex has distorted tetrahedral geometry around the Cu(I)center, which contains two bridge sulfur atoms. The Hirshfeld surface mapped over dnorm, shape index, and curvature revealed important H...H, H... C/C...H, and H... Cl/Cl...H intermolecular interactions as the main contributors to crystal packing. The natural bond orbital (NBO) was applied to understand the strength of nucleophilic and electrophilic attack between ligands and Cu(I) ions. Furthermore, density functional theory (DFT) was employed to demonstrate the molecular reactivity and stability of the ligands and copper complex.</p>","PeriodicalId":7122,"journal":{"name":"Acta Chimica Slovenica","volume":"70 4","pages":"467-478"},"PeriodicalIF":1.2,"publicationDate":"2023-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138827572","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis and Characterization of Multicolor Luminescent and Thermally Stable Thioureas and Polythioamides. 多色发光且热稳定的硫脲类和聚硫酰胺的合成与表征。
IF 1.2 4区 化学
Acta Chimica Slovenica Pub Date : 2023-11-18 DOI: 10.17344/acsi.2022.7668
Farah Qureshi, Muhammad Yar Khuhawar, Taj Muhammad Jahangir, Abdul Hamid Channar
{"title":"Synthesis and Characterization of Multicolor Luminescent and Thermally Stable Thioureas and Polythioamides.","authors":"Farah Qureshi, Muhammad Yar Khuhawar, Taj Muhammad Jahangir, Abdul Hamid Channar","doi":"10.17344/acsi.2022.7668","DOIUrl":"https://doi.org/10.17344/acsi.2022.7668","url":null,"abstract":"<p><p>Two new polythioamides were prepared through the polycondensation reaction between thiourea monomers and terephthaloyl dichloride, while the thiourea monomers were synthesized by the interaction of aromatic (4,4'-diaminophenylsulfone) or alicyclic (1,2-cyclohexanediamine) diamine with ammonium thiocyanate. The elemental composition of polythioamides was confirmed through CHN microanalysis. The structure and properties of thiourea monomers and polythioamides were determined through proton NMR, UV-Vis, FT-IR spectroscopy, fluorescence, TGA/DTA and SEM. The polythioamides indicated high thermal stabilities which were assessed from their Tmax (temperature indicating highest rate of weight loss) values (670 °C and 346 °C) observed in their DTG graphs. The thioureas and polythioamides were fluorescent and showed multicolor (violet, green, yellow, orange and red) emissions at different excitation wavelengths. All the synthesized compounds were also tested for their antifungal and antibacterial functions and showed antibacterial activity against Salmonella typhi, Bacillus subtilis and Staphylococcus aureus, and antifungal activity against Candida albicans.</p>","PeriodicalId":7122,"journal":{"name":"Acta Chimica Slovenica","volume":"70 4","pages":"560-573"},"PeriodicalIF":1.2,"publicationDate":"2023-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138827566","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Glycoprotein Levels and Oxidative Stomach Damage in Diabetes and Prostate Cancer Model: Protective Effect of Metformin. 糖尿病和前列腺癌模型中的糖蛋白水平和氧化性胃损伤：二甲双胍的保护作用
IF 1.2 4区 化学
Acta Chimica Slovenica Pub Date : 2023-11-13 DOI: 10.17344/acsi.2023.8198
Onur Ertik, Pinar Koroglu Aydin, Omur Karabulut Bulan, Refiye Yanardag
{"title":"Glycoprotein Levels and Oxidative Stomach Damage in Diabetes and Prostate Cancer Model: Protective Effect of Metformin.","authors":"Onur Ertik, Pinar Koroglu Aydin, Omur Karabulut Bulan, Refiye Yanardag","doi":"10.17344/acsi.2023.8198","DOIUrl":"https://doi.org/10.17344/acsi.2023.8198","url":null,"abstract":"<p><p>Men with diabetes have a higher risk of prostate cancer and people with prostate cancer are prone to stomach metastases. Therefore, researchers are continuing in order to find new approaches in the treatment of individuals with both diseases at the same time. The protective effect of metformin (which is used in the treatment of diabetes) on cancer continues to be supported by studies. The present study aimed that the protective effect of metformin in the stomach tissue of diabetic and/or prostate cancer rats was investigated through biochemical parameters. In the study, it was determined that the biochemical parameters studied showed a protective effect on stomach tissues with the administration of metformin to cancer and diabetic+cancer groups, and as a result of the principal component analysis, it was determined that the biochemical parameters studied in the stomach tissue showed a correlation.</p>","PeriodicalId":7122,"journal":{"name":"Acta Chimica Slovenica","volume":"70 4","pages":"574-587"},"PeriodicalIF":1.2,"publicationDate":"2023-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138827651","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis, Characterization and X-Ray Crystal Structures of Oxidovanadium(V) Complexes Derived from N'-(2-Hydroxy-5-methylbenzylidene)-4-methylbenzohydrazide with Antibacterial Activity. 具有抗菌活性的 N'-(2-羟基-5-甲基亚苄基)-4-甲基苯甲酰肼衍生氧化钒(V)配合物的合成、表征和 X 射线晶体结构。
IF 1.2 4区 化学
Acta Chimica Slovenica Pub Date : 2023-11-10 DOI: 10.17344/acsi.2023.8347
Xue-Rong Tan, Wei Li, Meng-Meng Duan, Zhonglu You
{"title":"Synthesis, Characterization and X-Ray Crystal Structures of Oxidovanadium(V) Complexes Derived from N'-(2-Hydroxy-5-methylbenzylidene)-4-methylbenzohydrazide with Antibacterial Activity.","authors":"Xue-Rong Tan, Wei Li, Meng-Meng Duan, Zhonglu You","doi":"10.17344/acsi.2023.8347","DOIUrl":"https://doi.org/10.17344/acsi.2023.8347","url":null,"abstract":"<p><p>A dinuclear oxidovanadium(V) complex [V2O2L2(OMe)2] (1) was synthesized from N'-(2-hydroxy-5-methylbenzylidene)-4-methylbenzohydrazide (H2L) and VO(acac)2 in MeOH. Reaction of complex 1 with 3-hydroxy-2-methyl-4-pyrone (HL') afforded a mononuclear oxidovanadium(V) complex [VOLL'] (2). The hydrazone and both complexes were characterized by IR, UV and 1H NMR spectroscopy, as well as X-ray single crystal determination. X-ray powder diffraction of the complexes was performed. The V atoms in the two complexes are in octahedral coordination. The molecules of complex 2 are linked through non-classical hydrogen bonds of type C-H∙∙∙O to form one-dimensional chains running along the a axis. The biological assay indicates that the complexes have good antimicrobial activities on the bacteria strains P. aeroginosa, S. aureus, B. subtilis and E. coli.</p>","PeriodicalId":7122,"journal":{"name":"Acta Chimica Slovenica","volume":"70 4","pages":"509-515"},"PeriodicalIF":1.2,"publicationDate":"2023-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138827570","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis of New of 4-Thiazolidinone and Thiazole Derivatives Containing Coumarin Moiety with Antimicrobial Activity. 具有抗菌活性的含香豆素分子的新 4-噻唑烷酮和噻唑衍生物的合成。
IF 1.2 4区 化学
Acta Chimica Slovenica Pub Date : 2023-11-09 DOI: 10.17344/acsi.2023.8281
Reem Al-Harbi, Marwa El-Sharief, Samir Abbas
{"title":"Synthesis of New of 4-Thiazolidinone and Thiazole Derivatives Containing Coumarin Moiety with Antimicrobial Activity.","authors":"Reem Al-Harbi, Marwa El-Sharief, Samir Abbas","doi":"10.17344/acsi.2023.8281","DOIUrl":"https://doi.org/10.17344/acsi.2023.8281","url":null,"abstract":"<p><p>Synthesizing hybrid molecules is one the best manner to achieve novel promising agents. Consequently, series of new thiazoles having coumarin nucleus were synthesized from 3-acetylcoumarin thiosemicarbazones. Cyclization of thiosemicarbazone derivatives with ethyl 2-chloroacetate, 1-chloropropan-2-one and 2-bromo-1-phenylethanone afforded the corresponding 4-thiazolidinones, 4-methylthiazoles and 4-phenylthiazoles, respectively. The expected antimicrobial propriety for the synthesized thiosemicarbazone and thiazole derivatives were investigated. The thiosemicarbazones and thiazolidin-4-ones showed moderate activities against G +ve and G -ve bacteria.</p>","PeriodicalId":7122,"journal":{"name":"Acta Chimica Slovenica","volume":"70 4","pages":"500-508"},"PeriodicalIF":1.2,"publicationDate":"2023-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138827568","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Copper(II) and Nickel(II) Complexes Derived from Isostructural Bromo- and Fluoro-Containing Bis-Schiff Bases: Syntheses, Crystal Structures and Antimicrobial Activity. 铜（II）和镍（II）配合物衍生自含溴和含氟双施氏碱的异构体：合成、晶体结构和抗菌活性。
IF 1.2 4区 化学
Acta Chimica Slovenica Pub Date : 2023-11-07 DOI: 10.17344/acsi.2023.8359
Ke-Sheng Cao, Ling-Wei Xue, Qiao-Ru Liu
{"title":"Copper(II) and Nickel(II) Complexes Derived from Isostructural Bromo- and Fluoro-Containing Bis-Schiff Bases: Syntheses, Crystal Structures and Antimicrobial Activity.","authors":"Ke-Sheng Cao, Ling-Wei Xue, Qiao-Ru Liu","doi":"10.17344/acsi.2023.8359","DOIUrl":"https://doi.org/10.17344/acsi.2023.8359","url":null,"abstract":"<p><p>A mononuclear copper(II) complex [CuLa] (1), and three mononuclear nickel(II) complexes [NiLa] (2), [NiLa]·CH3OH (2·CH3OH) and [NiLb] (3), where La and Lb are the dianionic form of N,N'-bis(4-bromosalicylidene)-1,2-cyclohexanediamine (H2La) and N,N'-bis(4-fluorosalicylidene)-1,2-cyclohexanediamine (H2Lb), respectively, were prepared and structurally characterized by spectroscopy method and elemental analyses. The detailed structures were determined by X-ray single crystal diffraction. All the copper and nickel complexes are mononuclear compounds. The metal ions in the complexes are in square planar coordination, with the two phenolate oxygens and two imine nitrogens of the Schiff base ligands. The biological effect of the four complexes were assayed on the bacteria strains Staphylococcus aureus, Escherichia coli and Candida albicans.</p>","PeriodicalId":7122,"journal":{"name":"Acta Chimica Slovenica","volume":"70 4","pages":"516-523"},"PeriodicalIF":1.2,"publicationDate":"2023-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138827648","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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