Solvent/substrate effects on the micelle-catalyzed aquation reactions of some iron(II) phenanthroline complexes, I. Influence of water and acid on the aquation of Fe(Ph2Phen)32+ in acetone

The effects of a substrate additive, H⁺ and solvents (water and acetone), on the micelle-catalyzed aquation of tris-(4,7-diphenyl-1, 10-phenanthroline)iron(II), Fe(Ph₂Phen)₃ ²⁺, have been investigated using^#Triton X-100 micelles. The k₀ vs. [TX-100] profiles at fixed [H₂O] are structured, exhibiting maxima. Catalytic factors of 46.6–171.7 are observed for 5.56×10⁻²≤[H₂O] 55.60×10⁻² mol dm⁻³. On the other hand, at fixed [H⁺], the k₀ vs. [TX-100] exhibit broad maxima. The aquation reaction is inhibited by H⁺ and catalytic factors decrease rapidly and exponentially from 422.5 to 20.9 for 0.20×10⁻³≤[H⁺]≤2.00×10⁻³ mol dm⁻³. The aquation is found to be faster (ca. 160–1200 fold) in acetone than in the aqueous medium depending on the added [H₂O]. These observations are rationalized on the basis of a proposed modified lamellar structure for the Triton X-100 (TX-100) micelles in which direct substitution of water molecules into the coordination sphere of the complex occurs.     

单壁碳纳米管在不同材质基片银膜上的表面增强拉曼光谱

在玻璃、白宝石和石英基片上,利用化学沉积法和溶胶法制备了纳米结构活性银膜,系统地研究了两种不同方法制备的单壁碳纳米管(SWNT)的表面增强拉曼光谱(SERS)的G带和D带.同一样品的G带,在不同基片上的峰移量不同,在白宝石基片上移动更大,峰强更高,可以更敏感地反映SERS效应.D带的峰形随基片不同而改变.金属性管的含量较高的样品,其D带光谱的峰移较半导体性管含量较高的样品更显著,表明金属性碳纳米管与SERS活性银膜的界面相互作用更强.     

Continuous-flow protease assay based on fluorescence resonance energy transfer

A homogeneous continuous-flow assay using fluorescence resonance energy transfer (FRET) for detection was developed to measure the hydrolysis of HIV Protease Substrate 1 (to which two choromophores, EDANS and DABCYL are covalently attached) by a protease (e.g. Subtilisin Carlsberg) and the influence of inhibitors. In the continuous-flow assay, an inhibitor solution and an enzyme solution were first eluted into the system and allowed to react with each other in a reaction coil. Subsequently, the substrate solution was added to an enzyme-inhibitor mixture in a second reaction coil and incubated for 1 min. Finally, the fluorescence intensity was monitored.The system was also utilized to measure the inhibition of the protease by two weak acidity inhibitors which are 4-(2-aminoethyl)benzenesulfonyl fluoride hydrochloride (AEBSF) and ethylenediaminetetraacetic acid (EDTA). Using the obtained optimum conditions for AEBSF, a detection limit of 0.3 mmol/l was achieved and the relative standard deviation was below 3.7% in the 2.5-7.5 mmol/l range. For EDTA, which required a 20 times higher substrate concentration than AEBSF, a detection limit of 0.2 mmol/l was obtained and the relative standard deviation was below 9.6% in the 0.5-7.5 mmol/l range.The optimization of pH, substrate concentration, enzyme concentration, reaction time and temperature are described. Organic modifier effects were also investigated. Methanol, acetonitrile and DMSO could be tolerated up to 30%.     

Determination of Attogram Quantities of Silver via Quenching of the Solid Substrate Room-Temperature Phosphorescence of Rhodamine B Based on the Catalysis of its Oxidation by Potassium Persulfate

A new method of SS-RTP for the determination of trace silver has been established. This method is based on the fact that Ag⁺, when activated by ,-bipyridyl (bipy) in a media of HAc–NaAc (pH=4.9), can catalyze the reaction of Rhodamine B (RhoB) oxidized by K₂S₂O₈, thus causing the Solid Substrate Room-Temperature Phosphorescence (SS-RTP) of RhoB to be quenched. The activating efficiency of bipy is 6.7 times higher than that of o-phenanthroline (phen). The reduction of the phosphorescence intensity (I_p) of RhoB is directly proportional to the concentration of Ag⁺ ions in the range of 1.6016.0agspot^–1 (0.40µLspot^–1). The regression equation of the working curve can be expressed as I_p=18.78+5.100m_Ag+ (agspot^–1) (r=0.9994, n=6), the detection limit is 0.28agspot^–1. This rapid, accurate and sensitive method has been successfully applied to the determination of trace silver in tea and human hair samples, and the results agree well with the Atomic Absorption Spectroscopy (AAS) method. The mechanism of the catalyzing reaction is also discussed.     

玻璃基板作用下高分子共混物薄膜相形态发展过程

研究了玻璃基板作用下极性高聚物为低组分的共混物薄膜在退火条件下相形态的发展过程 .选用聚苯乙烯 (PS) 聚甲基丙烯酸甲酯 (PMMA)与聚苯乙烯 (PS) 聚ε 己内酯 (PCL)两个体系 ,在玻璃基板上Spin Coating成膜后退火 .由于共混物薄膜中极性相对较大的高聚物组分 (PMMA和PCL)相对于极性较小的PS组分对玻璃基板具有更好的润湿性 ,所以在上述的两个共混薄膜体系中其相形态分别显示PMMA和PCL在低组分比例下最终发展成为连续相 .利用扫描电镜以及元素分析很好地验证了以上的结论 ,并且对其机理进行了解释 .此外 ,改变PS的分子量与PCL共混 ,研究了组分粘度对薄膜相形态发展的影响 .结果表明 ,PS组分粘度越大 ,共混物薄膜相结构发展速度越慢     

Effect of the substrate temperature on the crystallization of TiO2 films prepared by DC reactive magnetron sputtering

Titanium oxide (TiO₂) films were deposited on silicon substrates at the temperature in the range 50–600 °C by DC reactive magnetron sputtering. It was found that the anatase and rutile phases co-existed in the TiO₂ films deposited at 450–500 °C, while only the anatase phase existed in those deposited at other temperatures. The mechanism of such a crystallization behavior of TiO₂ films is preliminarily explained.     

Structural Investigation of Langmuir-Blodgett Films on Self-Assembly Modified Au Substrates

To improve the homogeneity and stability of single-layer azobenzene LB films on gold, self-assembled monolayers (SAMs) of terminally substituted alkyl thiol, HS(CH₂)₂-X(X=NH2,OH, COOH and CH₂SO₃Na, respectively), were used to modify the substrates before LB film deposition. It was found that single-layer C₈C₃ LB films on these modified substrates were more uniform and stable. Reflecion-Absorption(RA) FTIR measurements on these films indicated that at the LB/SAMs interface, ionic bonds. have formed for the modification with -NH₂ while hydrogen bonding occurred for modifications with -OH. -COOH and -SO₃Na,respectively. It can be concluded that the ionic or hydrogen bonding at the LB/SAM interface is responsible for the improvement in homogeneity and stability. It was believed that the less defected films after the time aging were most probably due to the ionic bond and hydrogen bonding mentioned above.     

药物甲氧苄氨嘧啶分子模板聚合物 结合作用及选择性研究

采用分子自组装印迹技术合成了对甲氧苄氨嘧啶有高选择性的模板聚合物受体.通过Scatchard分析、     

The effects of substrate temperatures on the electrical properties of CaZrO3 thin films prepared by RF magnetron sputtering

The radio frequency magnetron sputtering technology (RFMS) was employed to deposit perovskite structure orthogonal phase CaZrO₃ thin films on Pt/Ti/SiO₂/Si substrates. The effects of substrate temperatures on structure and electrical properties of these films were investigated in detail. The CaZrO₃ thin films were systematically characterized by means of X-ray diffraction (XRD), Scanning electron microscope (SEM), Multi-frequency LCR meter (HP4294A) and Radiant Precision Workstation to study the phase structure, cross-section morphology, dielectric and ferroelectric properties at different substrate temperatures. The result indicates that these films can withstand 80 V DC Bias voltage and have excellent stability of frequency, voltage and temperature. The CaZrO₃ thin film prepared at 550 °C turned out to be mainly orthorhombic CaZrO₃ phase with high permittivity, low dielectric loss, extremely low leakage current (at 1 MHz, the dielectric constant is 39.42, the dielectric loss is 0.00455, the quality factor is 220 and the leakage current density is 9.11 × 10⁻⁷A/cm² at 80 V applied voltage.). This work demonstrates that higher substrate temperature can boost the formation of orthorhombic CaZrO₃ phase and the CaZrO₃ thin film prepared by RF magnetron sputtering is a very promising paraelectric material in the application of thin film capacitor.     

浅海底质高光谱反射率测量系统的设计及应用

海底光谱反射率是光学浅水中太阳辐射传输的重要组成部分,影响着海水表面离水辐亮度的光谱特性,因此底质光谱信息的准确获取对于浅海遥感工作的开展至关重要。专门设计了一套海底光谱反射率测量系统填补了国际上在这方面的空白。采用可自由伸缩并旋转角度的参考白板贴近目标物测量,以消除探头到目标物之间水体吸收衰减的影响,双光路采集系统同步测量的设计避免了水下光场迅速变化对辐射测量的影响。于2018年9月3日—8日,用该系统在三亚珊瑚礁保护区进行原位海底反射率测量试验,测量对象包括珊瑚、海草、泥沙、沙滩等多种底质。各底质类型之间具有光谱可分性,具体表现为,在波长大于580 nm的长波段,浅海沙子底质与岸上沙滩光谱反射率特征差异明显,表明相对于空气中,水体和水中微藻介质的吸收散射作用严重影响着水下光谱辐射的测量,证实了空气中测量的目标光谱不可替代水中的结果。珊瑚和水草的光谱反射率特征主要区别在于海草反射率光谱在540~600 nm波段有一个宽反射峰,而珊瑚的典型特征是在575,600和650 nm附近有三个特征反射峰。此外,珊瑚、沙子和沙滩三种碳酸盐质底质在395,430,490和520 nm存在反射峰,485和585 nm处有一个小吸收峰,而海草则相反,在395,430,490和520 nm存在吸收峰,485和585 nm处显示反射峰。以上数据为将来利用底质反射率提取底栖物质组成信息奠定了基础,同时其结果也能够证实系统的可靠性和有效性。