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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Comparative study of the anti-corrosive properties of thiols induced superhydrophobic surfaces

Xiaomeng Chang,Haoxu Yu,Ziai Liu,Zhen Yang,Faze Chen,Yanling Tian

Fluoroalkyl thiols and alkyl thiols are widely used as low surface energy reagents for the preparation of superhydrophobic surfaces and corrosion resistant surfaces. Although the corrosion resistance of thiol-induced superhydrophobic surfaces has been well addressed previously, few studies have devoted to revealing the difference of fluoroalkyl thiol and alkyl thiol modified surfaces towards anti-corrosion. In this work, two types of superhydrophobic surfaces were prepared by respectively coating self-assembled monolayers (SAMs) of 1 H,1 H,2 H,2 H-perfluorodecanethiol (PFDT) and 1-dodecanethiol (DDT) on femtosecond laser engineered copper substrates. The formation mechanism of the SAMs was explained by analyzing the surface chemical composition . The water contact angle of the PFDT and DDT modified surfaces were measured to be 157.7° and 154.6°, respectively. Electrochemical tests showed that both SAMs significantly reduced the corrosion current density ( I corr ) and corrosion rate of the copper surfaces, while simultaneously increased the charge transfer resistance ( R ct ) value by an order of magnitude compared to the pristine copper surface. The surface with PFDT SAM had the smallest I corr and its R ct value was about 1.5 times larger than that with the DDT SAM. These results confirmed that both the SAMs enhanced the anti-corrosion properties of the copper surfaces, and the PFDT SAM was proved to be more effective. Furthermore, the anti-corrosion durability of the PFDT and DDT modified surfaces were compared after exposing them to salt, acid, and alkali solutions for 12 h, and the results showed that the surfaces maintained to be hydrophobic and anti-corrosive, and the PFDT induced superhydrophobic surface indicated better durability. Our results demonstrated that thiols SAMs could significantly improve the anti-corrosion property of structured metal surfaces , and that fluoroalkyl thiol was more desired for long-term anti-corrosive applications in comparison with alkyl thiol.

研究领域: 材料科学 · 腐蚀与防护 · 表面工程
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JOURNAL OF POLYMER RESEARCH · 2016 ·Vol. 23 ·期 6 ·1-12 · IF 1.969

Self-healing polymers based on eugenol via combination of thiol-ene and thiol oxidation reactions

Cheng Chuanjie,Zhang Xu,Chen Xinghe,Li Jin,Huang Qinghua,Hu Zhongyu,Tu Yuanming

Eugenol, a relatively cheap and abundant renewable resource, is used to design terminal diene compounds. Thiol-ene click reactions between the terminal diene intermediates and 1,6-hexanedithiol afford the corresponding oligomers with molecular mass of about 1.3 kDa. Finally, the oligomers and tricapto compound trimethylolpropane tris(3-mercaptopropionate) undergo thiol-oxidation reactions to form disulfide-crosslinked polymers. The brown polymers indicate self-healable behavior under UV light irradiation, presumably due to reversible reshuffling of weak disulfide bonds and/or reversible addition-dissociation reaction between benzoxazine and thiol groups.

研究领域: 材料科学 · 有机化学
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SYNTHETIC COMMUNICATIONS · 2024 · IF 1.8

Photochemical oxidative coupling of thiols to disulfides using Bi quantum dots: Mild and efficient catalysis

Haiyan Xu,Yuanyuan Huang,Yinchun Liang,Nan Wang,Dejun Dong,Mengke Wang,Weichun Huang,You Zi,Zhanping Yang

Herein, we present an efficient synthesis method utilizing Bi quantum dots (QDs) as catalysts for the photochemical oxidative coupling of thiols to disulfides under mild conditions. The protocol offers low catalyst loading, simplicity in reaction setup as well as high efficiency. Aromatic thiols and aliphatic thiols are successfully transformed into disulfides with good to quantitative yields, demonstrating tolerance to various substituents and heterocycles. Additionally, the protocol extends to the synthesis of asymmetric disulfides and allows for gram-scale synthesis.

研究领域: 催化 · 有机化学 · 纳米技术
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COMPOSITES SCIENCE AND TECHNOLOGY · 2017 · IF 4.873

Facile synthesis of imidazole microcapsules via thiol-click chemistry and their application as thermally latent curing agent for epoxy resins

Chunmei Li,Jiaojun Tan,Junwei Gu,Ying Xue,Lei Qiao,Qiuyu Zhang

A novel method was developed to encapsulate 1-benzyl-2-methylimidazole (1B2MZ) to produce microcapsule-type latent curing agent using thiol-click reaction in an oil/water emulsion. The fabrication process was significantly simplified and required reaction time was greatly shortened due to the efficiency of click chemistry. In the oil phase, 1B2MZ was mixed with reactive monomers , 1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-trione (TTT) and tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate (TEMPIC) which would polymerize to result in polythioether shell of microcapsules by following a photoinitiated thiol-ene mechanism. Polyvinyl alcohol (PVA) aqueous solution acted as water phase. The whole reaction process lasted for 20 min, which was enough for almost full conversions of monomers . The generated latent curing agent had good spherical shapes with smooth outer surfaces and the mean diameter distributed in the range of 105.7 to 18.17 μm by adjusting PVA concentration or viscosity of oil phase. The curing behavior, kinetics and releasing mechanism of latent curing agent were studied by differential scanning calorimetry (DSC) and scanning electron microscope (SEM). This microcapsule-type latent curing agent had a long storage life for 30 days when mixed with epoxy resin at 20 °C, and the mixture could be cured at 100 °C within 1 h.

研究领域: 材料科学 · 化学工程
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ACS Omega · 2020 · IF 2.87

Thermal Conductivity and Stability of Hydrocarbon-Based Nanofluids with Palladium Nanoparticles Dispersed by Modified Hyperbranched Polyglycerol

Xiaomei Qin,Shihao Yang,Yapei Chen,Xiaoyun Qin,Jianbo Zhao,Wenjun Fang,Dan Luo

Palladium nanoparticles, which were prepared by modified hyperbranched polyglycerol (mHPG) as stabilizers, can be dispersed well in nonpolar organic solvents and form highly stable nanofluids. The influences of three mHPG products modified with cyclohexanethiol (CSHPG), dodecanethiol (DSHPG), and octadecanethiol (OSHPG) on the preparation and stability of the palladium nanoparticles were investigated. The stability and thermal conductivity enhancement of the hydrocarbon-based nanofluids with Pd@mHPG (Pd@CSHPG, Pd@DSHPG, and Pd@OSHPG) compared to the corresponding base fluid were investigated at different temperatures. The average diameters of nanoparticles stabilized by CSHPG, DSHPG, and OSHPG are within 2.7–3.6 nm. The palladium nanoparticles could be dispersed well in the nonpolar base fluid such as decalin. The nanofluids with Pd@DSHPG and Pd@OSHPG could remain stable for up to 330 days at room temperature. The nanofluid with Pd@DSHPG or Pd@OSHPG could be stable for more than 24 h at 110 °C. The thermal conductivity of the nanofluids improved with increasing temperature and the mass fraction of nanoparticles compared to the corresponding base fluid. The long alkyl chain-modified HPG can give better protection for nanoparticles from agglomeration and assist metal nanoparticles in enhancing the thermal conductivity of nanofluids.

研究领域: 材料科学 · 纳米技术 · 化学工程
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RESEARCH ON CHEMICAL INTERMEDIATES · 2017 ·Vol. 43 ·期 7 ·3847-3858 · IF 1.369

Three-dimensionally ordered macroporous metal oxide–silica composite for removal of mercaptan

Yang Chao,Wang Jian,Fan Hui-Ling

A series of 3DOM and non-3DOM metal oxide–silica composites were prepared and tested dynamically in a packed-bed reactor at room temperature to remove ethanethiol from a gas stream containing ethyl mercaptan in moist N 2. The obtained sorbents were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption–desorption techniques. The experimental results showed that the adsorption ability of different kinds of metal oxide–silica composites with 3DOM structure decreased in the sequence: 3D-CuO/SiO 2  > 3D-NiO/SiO 2  > 3D-Co 3 O 4 /SiO 2  > 3D-ZnO/SiO 2 . The best ratio of CuO to SiO 2 of 3DOM copper–silicon oxide sorbents for ethanethiol removal was found to be 1:2. The 3DOM structure could improve the removal activity of sorbents remarkably because of the high porosity with ordered interconnected macropores as well as the large surface area and high dispersion of CuO. It was also found that a moist atmosphere greatly benefited the adsorption of ethanethiol at ambient condition.

研究领域: 材料科学 · 环境科学
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PEST MANAGEMENT SCIENCE · 2020 ·Vol. 76 ·期 9 ·2978-2985 · IF 3.75

Antifungal effects of 3-(2-pyridyl)methyl-2-(4-chlorphenyl) iminothiazolidine against Sclerotinia sclerotiorum

Xianfei Zhang,Jiuyong Xu,Solange Muhayimana,Hui Xiong,Xuefeng Liu,Qingchun Huang

BACKGROUND Sclerotinia stem rot (SSR) caused by Sclerotinia sclerotiorum threatens oilseed rape cultivation, and the emergence of fungicide-resistant strains has led to control failures worldwide. Identifying novel chemical alternatives with different modes of action and high antifungal activities is thus crucial. Herein we evaluated the antifungal effects of 3-(2-pyridyl)methyl-2-(4-chlorphenyl)imino- thiazolidine (PMAS) on S. sclerotiorum to determine its efficacy for SSR management. RESULTS PMAS had an inhibitory effect on mycelial growth; the EC 50 values were 17.83 and 21.15 μg mL −1 for the carbendazim-susceptible strain Ss01 and carbendazim-resistant strain Hm25, respectively. PMAS treatment changed the color of inhibited mycelia to green, and the hyphae were sustained in the undifferentiated stage. Cysteine supplementation made this green color disappear, whereas methionine enhanced the color. Moreover, PMAS treatment markedly inhibited oxalic acid biogenesis, increased free thiol content in mycelia, and weakened the activities of oxaloacetase and malate dehydrogenase, but had little effect on the activity of glyoxylate dehydrogenase. Cysteine could reverse the inhibitory effects of PMAS on mycelial morphogenesis and biochemical constituents, except thiol production. In the pot-culture experiment, PMAS showed a good protective effect, with the control efficacy being >91% on SSR. CONCLUSION PMAS appears to be an effective fungicide for SSR management. © 2020 Society of Chemical Industry

研究领域: 植物病理学 · 农学 · 分子生物学
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Royal Society Open Science · 2019 ·Vol. 6 ·期 5 · IF 2.515

UV185+254 nm photolysis of typical thiol collectors: decomposition efficiency, mineralization and formation of sulfur byproducts

Pingfeng Fu,Gen Li,Xiaoting Wu,Xiaofeng Lin,Bolan Lei

The decomposition of toxic flotation reagents upon UV185+254 nm irradiation was attractive due to operational simplicity and no dosage of oxidants. In this work, the degradation of typical thiol collectors (potassium ethyl xanthate (PEX), sodium diethyl dithiocarbamate (SDD), O-isopropyl-N-ethyl thionocarbamate (IET) and dianilino dithiophoshoric acid (DDA)) was investigated by UV185+254 nm photolysis. The degradation efficiencies and mineralization extents of collectors were assessed. The formation of CS2 and H2S byproducts was studied, and the mechanisms of collector degradation were proposed under UV185+254 nm irradiation. The PEX, SDD and IET were decomposed with nearly 100% removal upon 75 min of UV185+254 nm irradiation. The decomposition rate constants decreased in the order SDD > PEX > IET ≫ DDA, and the DDA was the refractory collector. After 120 min of UV185+254 nm irradiation, 15−45% of carbon and 25−75% of sulfur of collectors were completely mineralized, and the mineralization extent decreased in the order PEX > SDD > IET > DDA. The percentage of gaseous sulfur (CS2 and H2S) ranged from 0.48 to 4.85% for four collectors, showing the fraction of emitted sulfur byproducts was small. The aqueous CS2 concentration increased in the first 10−20 min, and was decreased to a low level of 0.05–0.1 mg l−1 at 120 min. Two mechanisms, i.e. direct UV254 nm photolysis and indirect oxidation with free radicals, were responsible for collector decomposition in the UV185+254 nm photolysis.

研究领域: 环境科学 · 化学工程
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JOURNAL OF ORGANIC CHEMISTRY · 2022 · IF 4.198

Nickel-Catalyzed Decarbonylative Thioetherification of Carboxylic Acids with Thiols

Tianhao Xu,Xingyu Zhou,Xiong Xiao,Yan Yuan,Long Liu,Tianzeng Huang,Chunya Li,Zhi Tang,Tieqiao Chen

A nickel-catalyzed decarbonylative thioetherification of carboxylic acids with thiols was developed. Under the reaction conditions, benzoic acids, cinnamic acids, and benzyl carboxylic acids coupled with various thiols including both aromatic and aliphatic ones produce the corresponding thioethers in up to 99% yields. Moreover, this reaction was applicable to the modification of bioactive molecules such as 3-methylflavone-8-carboxylic acid, probenecid, and flufenamic acid, and the synthesis of acaricide chlorbenside. These results well demonstrated the potential synthetic value of this new reaction in organic synthesis.

研究领域: 有机化学 · 合成化学
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Nanoscale · 2020 ·Vol. 12 ·期 24 ·13010-13016 · IF 6.895

Carbon dots for lysosome targeting and imaging of lysosomal pH and Cys/Hcy in living cells

Qiaoling Liu,Xiuyun Niu,Yan Zhang,Ying Zhao,Kaixin Xie,Boru Yang,Qing He,Shiyou Lv,Lin Li

The abnormal concentrations of both biothiols and pH in lysosomes are seriously related to many major diseases, such as Parkinson's and Alzheimer's diseases. Up to now, there are few reports that clearly illustrate the relationship between lysosomal pH and biothiols via fluorescence assay. Herein, novel carbon dots (Scy-CDs) are prepared with good water dispersibility and excellent photostability, and a large Stokes shift of 106 nm is exhibited under an excitation wavelength of 450 nm. The remarkable pH-dependent behavior of Scy-CDs is presented with the fluorescence quenching based on the donor-excited photoinduced electron transfer (d-PET) process. The pKa value is 5.30, which is in good agreement with the range of the normal and abnormal lysosomal pH. Upon the addition of cysteine (Cys) or homocysteine (Hcy), the d-PET process is effectively inhibited with fluorescence recovery totally. The significant co-localization of Scy-CDs with Lyso-Tracker Deep Red in HEp-2 cells and the Pearson correlation coefficient 0.88 strongly suggest that the Scy-CDs can target lysosomal pH and Cys/Hcy in living cells.

研究领域: 细胞生物学 · 医学 · 分析化学
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Materials · 2018 ·Vol. 11 ·期 11 ·2232 · IF 2.467

Dual-Emission Fluorescent Microspheres for the Detection of Biothiols and Hg2+

Jiahui Wang,Hao Zhang,Ruifang Guan

Dual-emission nanosensor for Hg2+detection was prepared by coupling CA-AEAPMS on the surface of RBS-doped modified silica microspheres. The CA-AEAPMS was synthesized by usingN-(β-aminoethyl)-γ-aminopropyl methyldimethoxysilane (AEAPMS) and citric acid as the main raw material. The obtained nanosensor showed characteristic fluorescence emissions of Rhodamine B (red) and CA-AEAPMS (blue) under a single excitation wavelength (360 nm). Upon binding to Hg2+, only the fluorescence of CA-AEAPMS was quenched, resulting in the ratiometric fluorescence response of the dual-emission silica microspheres. This ratiometric nanosensor exhibited good selectivity to Hg2+over other metal ions, because of the amide groups on the surface of CA-AEAPMS serving as the Hg2+recognition sites. The ratio of F450/F580linearly decreased with the increasing of Hg2+concentration in the range of 0 to 3 × 10−6M, and a detection limit was as low as 97 nM was achieved. Then, the addition of three thiol-containing amino acids (Cys, Hcy, GSH) to the quenched fluorescence solution with Hg2+can restore the fluorescence, and the detection limits of the three biothiols (Cys, Hcy, GSH) are 0.133 μM, 0.086 μM, and 0.123 μM, respectively.Keywords:dual-emission;silica microspheres;fluorescence

研究领域: 分析化学 · 环境科学 · 生物医学工程
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Nanomaterials · 2023 ·Vol. 13 ·期 4 ·775 · IF 5.3

Comparative Study of α- and β-MnO2 on Methyl Mercaptan Decomposition: The Role of Oxygen Vacancies

Hong Su,Jiangping Liu,Yanan Hu,Tianhao Ai,Chenhao Gong,Jichang Lu,Yongming Luo

As a representative sulfur-containing volatile organic compounds (S-VOCs), CH3SH has attracted widespread attention due to its adverse environmental and health risks. The performance of Mn-based catalysts and the effect of their crystal structure on the CH3SH catalytic reaction have yet to be systematically investigated. In this paper, two different crystalline phases of tunneled MnO2(α-MnO2and β-MnO2) with the similar nanorod morphology were used to remove CH3SH, and their physicochemical properties were comprehensively studied using high-resolution transmission electron microscope (HRTEM) and electron paramagnetic resonance (EPR), H2-TPR, O2-TPD, Raman, and X-ray photoelectron spectroscopy (XPS) analysis. For the first time, we report that the specific reaction rate for α-MnO2(0.029 mol g−1h−1) was approximately 4.1 times higher than that of β-MnO2(0.007 mol g−1h−1). The as-synthesized α-MnO2exhibited higher CH3SH catalytic activity towards CH3SH than that of β-MnO2, which can be ascribed to the additional oxygen vacancies, stronger surface oxygen migration ability, and better redox properties from α-MnO2. The oxygen vacancies on the catalyst surface provided the main active sites for the chemisorption of CH3SH, and the subsequent electron transfer led to the decomposition of CH3SH. The lattice oxygen on catalysts could be released during the reaction and thus participated in the further oxidation of sulfur-containing species. CH3SSCH3, S0, SO32−, and SO42−were identified as the main products of CH3SH conversion. This work offers a new understanding of the interface interaction mechanism between Mn-based catalysts and S-VOCs.Keywords:CH3SH decomposition;MnO2;oxygen vacancies;oxygen migration

CAS / MDL: 7727-54-0 10034-96-5
研究领域: 催化化学 · 环境科学
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