硫酸铜掺杂TiO2涂层对碳纤维抗氧化性能的影响

采用溶胶-浸渍法,以CuSO₄为烧结助剂在碳纤维表面制得TiO₂涂层。利用XRD、SEM和TEM分析了涂层相组成及形貌,通过静态等温氧化实验考察了涂层碳纤维抗氧化性能。结果表明：掺杂CuSO₄制备TiO₂涂层均匀完整致密,涂层相组成均为锐钛矿型TiO₂,且涂层厚度从45 nm提高至185 nm;与普通TiO₂涂层碳纤维相比,完全氧化温度从667 ℃上升到800 ℃,氧化活化能从118.390 kJ·mol^-1提高到152.562 kJ·mol^-1,CuSO₄的掺杂大大提高了TiO₂涂层碳纤维的抗氧化性能。     

季铵盐改性氧化石墨烯的制备及其性能研究

本论文采用改进的Hummers法制备了氧化石墨烯(GO),并将氧化石墨烯用十二烷基二甲基苄基氯化铵(1227)进行修饰,得到1227非共价改性的氧化石墨烯(GO-1227)。用拉曼光谱、漫反射红外光谱分析、X-射线光电子表面能谱技术表征了其化学结构;用X-射线衍射分析、扫描电子显微镜与透射电子显微镜观察了其剥离情况和微观形貌;分析了它们在不同溶剂中的分散性。结果表明,季铵盐改性后,1227阳离子通过静电作用插入到GO片层之间,使GO片层进一步剥离,且在极性较弱的有机溶剂中的溶解性增加。热失重分析表明,GO-1227的初始分解温度提高了约70℃。将GO-1227与聚甲基丙烯酸甲酯与苯乙烯的嵌段共聚物(PMMA-b-PS)凝胶聚电解质复合,制备了纳米复合凝胶聚合物电解质(NGPE),并用交流阻抗法测试其电性能,发现占聚电解质总质量2‰的GO-1227可以将其离子电导率提高8.6倍。     

重度原油注空气低温氧化过程研究(英文)

低温氧化反应对现场燃烧(ISC)技术点火的成功有十分重要的影响.采用高压氧化管,研究了不同温度压力下,新疆克拉玛依重度原油的低温氧化过程.结果表明,温度和压力的变化对低温氧化反应的放热程度、持续时间以及气体产物有明显影响.适合油样低温氧化反应的温度和压力分别为150℃和10MPa.此外,采用纯组分替代原油族组分进行低温氧化实验,研究低温氧化反应对原油族组分(饱和烃、芳香烃、胶质、沥青质)含量的影响.结果表明,原油所含族组分中,芳香烃组分最易被氧化,其含量由氧化前的19.17%减少到12.38%(150℃)和9.51%(250℃).随着低温氧化过程的进行,结构复杂的族组分(胶质、沥青质)的含量明显增加.实验数据对油藏实施注空气技术,以及该技术现场实施条件的确定有十分重要的指导意义.     

Simultaneous Voltammetric Determination of Captopril and Hydrochlorothiazide on a Graphene/Ferrocene Composite Carbon Paste Electrode

In this work, a voltammetric method has been developed for the simultaneous determination of captopril (CPT) and hydrochlorothiazide (HCT) in pharmaceutical combinations and clinical samples using a graphene/ferrocene composite carbon paste (GR/Fc/CP) electrode. The electrochemical behaviors of CPT and HCT were individually and simultaneously investigated at the surface of the GR/Fc/CP electrode. In differential pulse voltammetric (DPV) mode and under optimized experimental conditions, CPT and HCT gave linear responses over the concentration ranges 1.0–430 µM and 0.5–390 µM (r²>0.99), respectively. The prepared electrode could be used for simultaneous determination of CPT and HCT in some real samples.     

应用多接收器电感耦合等离子体质谱法测定海洋碳酸盐中稳定铅同位素组成

研究了多接收器电感耦合等离子体质谱仪(MC-ICP MS)测定铅同位素比值时,影响测试结果准确度和精密度的主要因素及其优化过程。在优化条件下,10 h内连续30次测定4 ng/mL NIST SRM 981同位素标准溶液铅同位素比值,获得208Pb/206Pb、207Pb/206Pb和206Pb/204Pb相对标准偏差(RSDs)分别为0.005%、0.004%和0.054%。长期监测208Pb/206Pb、207Pb/206Pb和206Pb/204Pb,标准偏差(2SDs)分别为0.000 06、0.000 05和0.006 7。采用NEPTUNE MC-ICP MS法测定了低铅海洋碳酸盐样品中稳定铅的同位素比值,并对南海橙黄滨珊瑚(Porites lutea)和库氏砗磲(Tridacna gigas)进行了分析,得到全流程空白为8～10 pg,重复样误差优于0.1%。经0.50 mol/L HNO3洗脱之后,得到海南珊瑚样品中208Pb/206Pb、207Pb/206Pb的比值分别为2.086 2±0.001 5、0.849 90±0.001 47(n=16);海南砗磲样品中208Pb/206Pb、207Pb/206Pb的比值分别为2.116 9±0.004 2、0.864 81±0.001 62(n=9)。进一步考察了南海海洋碳酸盐中204Pb的同位素比值。分析结果表明,南海海洋碳酸盐中稳定铅同位素比值与中国气溶胶、珠江三角洲大气沉降、黄土及南海海底玄武岩等具有很好的相关性。方法适用于复杂基体高钙低铅的海洋碳酸盐样品中铅同位素比值的分析。     

Electrochemical Detection of NADH,Cysteine, or Glutathione Using a Caffeic Acid Modified Glassy Carbon Electrode

A modified electrode was prepared using electrodeposition methods to immobilize caffeic acid (CAF) onto the surface of a glassy carbon electrode (GCE) to create a polymer suitable for biosensor development. The polymer film coverage of the surface bound species was further optimized using electrodeposition methods, thus increasing the surface coverage to ca. 10^?9 mol cm^?2. Using cyclic voltammetry, the modified carbon electrode was used to facilitate and observe the electrocatalytic oxidation of coenzymes such as NADH, cysteine, and glutathione at different concentrations. A calibration curve was determined in each case within the concentration range; 300 nM to 10 mM, with the limits of detection (LOD) of 246 µM, 99 µM, 2.2 µM for NADH, cysteine, and glutathione respectively.     

Determination of Sulfide by Hematoxylin Multiwalled Carbon Nanotubes Modified Carbon Paste Electrode

This study investigates a new approach for the amperometric determination of sulfide using a hematoxylin multiwalled carbon nanotubes modified carbon paste electrode (HM‐MWCNTs/CPE). The experimental results show that HM‐MWCNTs/CPE significantly enhances the electrocatalytic activity towards sulfide oxidation. Cyclic voltammetric studies show that the peak potential of sulfide shifted from +400 mV at unmodified CPE to +175 mV at HM‐MWCNTs/CPE. The currents obtained from amperometric measurements at optimum conditions were linearly correlated with the concentration of sulfide. The calibration curve was obtained for sulfide concentrations in the range of 0.5–150×10^?6 mol L^?1. The detection limit was found to be 0.2×10^?6 mol L^?1 for the amperometric method. The proposed method was successfully applied to a river water sample in Pardubice, Czech Republic.     

Development and validation of a rapid and sensitive assay for the determination of anisodamine in 50 μL of beagle dog plasma by LC–MS/MS

A simple, rapid, high‐throughput, and highly sensitive LC–MS/MS was developed to determine anisodamine in a small volume (50 μL) of beagle dog plasma using atropine sulfate as the internal standard. The analyte and internal standard were isolated from 50 μL plasma samples after a one‐step protein precipitation using Sirocco 96‐well protein precipitation filtration plates. The separation was accomplished on a Hanbon Hedera CN column (100 × 4.6 mm, 5 μm) and the run time was 4 min. A Micromass Quatro Ultima mass spectrometer equipped with an ESI source was operated in the multiple reaction monitoring mode with the precursor‐to‐product ion transitions m/z 306.0→140.0 (anisodamine) and 290.0→123.9 (atropine) used for quantitation. The method was sensitive with a low LOQ of 0.05 ng/mL, and good linearity in the range 0.05–50 ng/mL for anisodamine (r² ≥ 0.995). All the validation data, such as accuracy, intra‐ and interrun precision, were within the required limits. The method was successfully applied to the pharmacokinetic study of anisodamine hydrochloride injection in beagle dogs.     

Wrinkling and Growth Mechanism of CuO Nanowires in Thermal Oxidation of Copper Foil

We report a systematic study on wrinkling and CuO nanowires （NWs） growth in the thermal oxidation of copper foil. Copper foils with thickness of 0.5 mm were thermally oxidized in air at 500℃ for 0.5-10 h. It is found that all the samples have wrinkles and the size of the wrinkles increases with the oxidation time increasing. CuO NWs can grow on both the sidehill and hilltop of wrinkle. The CuO NWs on sidehill are longer and denser than those on hilltop. The growth direction of the CuO NWs on sidehill is not vertical to the substrate but vertical to their growth surfaces. The process of wrinkling and CuO NWs growth can be divided into three stages： undulating, voiding, and cracking. The CuO NWs on both sidehill and hilltop grow at the undulating stage. However, only the CuO NWs on sidehill grow and those on hilltop stop growing at the voiding and cracking stages because of the void in hilltop. The local electric field in a wrinkle at undulating stage was calculated, and it is found that the difference of local electric field strengths between hilltop and sidehill is small, which indicates that the predominant driving force for the diffusion of Cu ion during CuO NWs growth is internal stress.     

A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [RuV(N4O)(O)]2+: Electronic Structure,Redox Properties,and Oxidation Reactions Investigated by DFT Calculations

The electronic structure and redox properties of the highly oxidizing, isolable Ru^V?O complex [Ru^V(N₄O)(O)]²⁺, its oxidation reactions with saturated alkanes (cyclohexane and methane) and inorganic substrates (hydrochloric acid and water), and its intermolecular coupling reaction have been examined by DFT calculations. The oxidation reactions with cyclohexane and methane proceed through hydrogen atom transfer in a transition state with a calculated free energy barrier of 10.8 and 23.8 kcal mol^?1, respectively. The overall free energy activation barrier (ΔG^≠=25.5 kcal mol^?1) of oxidation of hydrochloric acid can be decomposed into two parts: the formation of [Ru^III(N₄O)(HOCl)]²⁺ (ΔG=15.0 kcal mol^?1) and the substitution of HOCl by a water molecule (ΔG^≠=10.5 kcal mol^?1). For water oxidation, nucleophilic attack on Ru^V?O by water, leading to O? O bond formation, has a free energy barrier of 24.0 kcal mol^?1, the major component of which comes from the cleavage of the H? OH bond of water. Intermolecular self‐coupling of two molecules of [Ru^V(N₄O)(O)]²⁺ leads to the [(N₄O)Ru^IV? O₂? Ru^III(N₄O)]⁴⁺ complex with a calculated free energy barrier of 12.0 kcal mol^?1.