Electrooxidation Mechanism of Methanol at Pt-Ru Catalyst Modified GC Electrode in Electrolytes with Different pH Using Electrochemical and SERS Techniques

The electrochemical and in-situ surface-enhanced Raman spectroscopy （SERS） techniques were used to investigate the electrooxidation behavior of methanol in acidic, neutral and alkaline media at a Pt-Ru nanoparticle modified glassy carbon （Pt-Ru/GC） electrode. The results showed that methanol could be dissociated spontaneously at the Pt-Ru/GC electrode to produce a strongly adsorbed intermediate, CO. It was found that CO could be oxidized more easily in the alkaline medium than in the acidic and neutral media. The peak potential of methanol oxidation was shifted from 0.663 and 0.708 V in the acidic and neutral media to -0.030 V in the alkaline medium, which is due to that the adsorption strength of CO on the Pt surface in the alkaline medium is weaker than that in the acidic and neutral media. The final product of the methanol oxidation is CO2. However, in the alkaline medium, CO2 produced would form CO3^2- and HCO3^- resulting in the decrease in the alkaline concentration and then in the decrease in the performance of DMFC. Therefore, the performance of the alkaline DMFC is not Stable.     

Distribution of Helium Isotopes in Western Pacific Upper Layer

3He/4He ratios in samples of sea water obtained at depths from surface to 300 m in the upper layer of the Western Pacific Ocean were measured by a mass spectrometer VG5400. The lateral and vertical distribution of He isotopes in the studied area was discussed in detail on the basis of 3He/4He ratios. Excess and depleted 3He. in relation to δ3He value of surface water in equilibrium with air has been discussed in the area, which may be mainly attributed to the incorporation of the North Pacific Intermediate Water with the Equatorial Upwelling and the exchange of water masses between the South China Sea and the Western Pacific, respectively. The present work in Western Pacific has also indicated that He isotopes may be used as a tracer for mixing processes of water masses and oceanic circulation.     

单核锌双卟啉配合物构象平衡的理论研究及光谱分析

合成了一系列以不同长度柔韧链相连的p/p型单核锌双卟啉配合物。选用Tripos力场,利用分子动力学模拟退火和分子力学构象搜索相结合的方法对该系列双卟啉进行了能量优化和构象分析。理论计算结果表明:该类双卟啉稳定存在的最低能量构象为叠合式,最高能量构象为伸展式,并存在一系列的中间能量构象;双卟啉分子内π-π作用和能量转移与双卟啉存在的两种主要构象密切相关;分析了分子内π-π作用的本质。运用不同光谱测试手段验证了理论计算结果: 利用可见和相应二阶导数吸收光谱研究了双卟啉主要存在的叠合式和伸展式构象,通过红外光谱观察了对双卟啉构象和卟啉环间π-π作用较为敏感的吸收谱带;利用荧光光谱计算了双卟啉的分子内能量转移效率。     

非晶聚对苯二甲酸乙二醇酯薄片在低温退火过程中的声发射现象

Acoustic emission during sub-Tg annealing fort amorphous polyethylene terephthalate (PET) sheet quenched from melt has been observed. The mechanical properties, texture and glass transition of annealed specimens have been studied. It is shown that some of PET chains change from non-equilibrium state to equilibrium state during sub-Tg annealing, which leads to stress concentration in specimen. When the level of internal stress approaches to the limit, the acoustic waves are emitted due to sudden releasing of stress and the micro-defects are for-med. This is one of the important reasons,the causes the loss of mechanical properties to an-nealed specimens.     

螺旋共轭分子2,2′-螺二茚-1,1′, 3,3′-四酮及其衍生物的二阶非线性光学性质与分子结构关系的研究

采用AM1和ZINDO系列方法研究了螺旋共轭分子2,2′-螺二茚-1,1′, 3,3′-四酮及其含氮衍生物的几何构型和各分子的稳定构型, 并以稳定构型为基础, 计算了这些分子的电子光谱、二阶非线性光学系数βμ, β0及电荷转移, 考察了取代基变化对βμ的影响. 计算结果表明, 所设计分子兼具较大的二阶非线性光学系数和较高的透过率, 有希望成为一类新型的二阶非线性光学材料.     

A Novel Method for Quantification of Circulating DNA in Serum by Capillary Zone Electrophoresis

In this paper, we first presented a novel method for quantification of circulating DNA in human serum based on capillary zone electrophoresis with laser-induced fluorescence detection (CZE-LIF). The serum was digested by proteinase to release free DNA, and then CZE-LIF system was used for the quantification of total circulating DNA. This method was successfully used to quantify the circulating DNA levels in sera from healthy individuals and certain cancer patients.We found the significantly elevated circulating DNA levels in certain prostate cancer patients. Our results demonstrated that CZE-LIF system has good linearity, excellent sensitivity (0.5 ng/mL DNA),satisfactory reproducibility (RSDs in one day and between days were both less than 5%) and reliability, and is well suitable to the quantification of the circulating DNA in human serum or plasma.     

甲醇氨化反应中交联皂石的催化行为

层柱材料是具有规则孔结构且其表面酸性及孔结构可调变的固体酸催化剂.本文合成了皂石,并用十三聚铝羟基络离子(Al_(13))与其交联,在醇氨化反应中研究了此层柱材料孔结构及表面酸性与催化性能间的关系.     

铂电极上异黄樟油和胡椒醛电氧化的SERS研究

采用循环伏安(CV)法和原位表面增强拉曼光谱(SERS)技术, 研究了非水体系中反应物异黄樟油和目标产物胡椒醛在粗糙铂电极上的电氧化行为, 发现胡椒醛在电位≥1.50 V时将进一步氧化, 而且从分子水平证实, 在胡椒醛的氧化电位(≥1.50 V) 下, 波长为632.8 nm的激光对胡椒醛的氧化有助催化作用. 由异黄樟油直接电氧化合成胡椒醛的电位(E)应控制在1.20 V相似文献   

Influence of vanadium doping on the behavior of YBa_2Cu_3O_7-y

YBa2Cu3-xVxO7-y(x=0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) superconductors have been prepared. X-ray diffraction shows that the system remains orthorhombic for all compositions studied, but for x > 0.4 V2O5 was detected as an impurity phase. Substitution of V5+ for Cu2+ occurs in the Cu(2) sites on the Cu(2)-O planes. The introduction of the high valence element, vanadium, produces the extra free-electrons. These electrons recombine with the positive carrier of the system. It makes depression of the mobility and the Hall number of YBa2Cu3-xVxO7-v and also results in a depression of TC.     

2003～2011年中国科普法规政策与化学普及书籍关系研究

2002年中国颁布科普法后,2003至2011年出版的化学普及书籍种数总体呈上升趋势。出版地和出版社总体上较为分散,局部集中度高。主题上基础知识类化学普及书籍最多,科学文化类次之,实用知识类较少,化学前沿类最少。涉及科普的一般法律、法规和政策对化学普及书籍的创作影响甚微。只有与国家约束性社会发展指标相关,发生涉及公民生命安全的重大社会事件,针对特定人群的具体实施政策出台,科普法规和政策才对化学普及书籍的出版起到推动作用。