稀土配合物的时间分辨光谱分析法研究(Ⅰ)TFA-TOPO-农乳-100体系用于测定铕和钐

本文采用自己组装的时间分辨荧光光谱测定装置,研究了铕(钐)-三氟乙酰丙酮-三正辛基膦化氧(Eu(Sm)-TFA-TOPO)在非离子表面活性剂农乳-100存在下的光谱特性、荧光衰减动力学特性和发光机理。提出了能量传递机制和第二配体TOPO在荧光发射过程中的作用,制定出TFA-TOPO-农乳-100体系测定痕量铕和钐的时间分辨荧光光谱分析方法,用于测定高纯氧化钇中的痕量铕和钐,结果令人满意。     

高效液相色谱指纹图谱应用于地黄的研究

利用高效液相色谱建立了地黄的色谱指纹图谱。采用反相C1 8柱 (5 μm ,1 5 0mm× 4.6mm) ,流动相甲醇∶水 (V V =5∶95 ) ,检测波长为 2 80nm ,流速 1 .0mL min进行实验。根据相对保留值和相对面积值对色谱指纹图谱进行分析对比研究 ,建立了控制地黄药材质量的新方法。该法为中药样品的鉴定提供了较全面的信息 ,并为HPLC在复杂组分的样品分析领域开拓了新的应用途径。     

Physicochemical properties and catalytic performance of Pr2 − x SrxCoO4 ± y mixed oxides for NO reduction by CO

Using the polyglycol gel method, a series of Pr_{2 − x} Sr_xCoO_{4 ± y} (0.2 ≤ x ≤ 1.0) mixed oxides were prepared, and their catalytic activities were studied in the test reaction of NO reduction by CO. The solid-state physicochemical properties, including crystal structure, defect structure, IR spectrum, valence state of B-site ions, nonstoichiometry oxygen (y), oxygen species, and redox properties, were characterized by means of XRD, IR, TPD, TPR, XPS, and chemical analysis. The results show that all mixed oxides display a K₂NiF₄ structure. When x = 0.2 and 1.0, the obtained samples still have little uncertain mixed oxides; however, the mixed oxides (x = 0.4, 0.6, 0.8) all represent a single A₂BO₄ phase. With the increase of x, lattice parameters, unit-cell volume, and average crystalline size decrease gradually, whereas microstrain density, the concentration of Co³⁺, the amounts of lattice oxygen released and the concentration of oxygen vacancy increase. The catalytic activities of Pr_{2 − x} Sr_xCoO_{4 ± y} catalysts for NO reduction by CO are closely correlated with oxygen vacancy and the concentration of Co³⁺. Published in Russian in Kinetika i Kataliz, 2006, Vol. 47, No. 3, pp. 431–437. The text was submitted by the authors in English.     

激光诱导荧光光谱分析法研究 Ⅳ.钐-三氟乙酰丙酮-三正辛基膦化氧-浓乳-100的荧光特性研究及应用

采用激光诱导荧光光谱测定装置研究了Sm-三氟乙酰丙酮(TFA)-三正辛基膦化氧(TOPO)体系的激光诱导发光特性和发光机理。根据配合物体系中各组份的光谱特性和光谱能级,提出Sm-TFA-TOPO体系的能量传递机制。拟定了在农乳-100存在下,TFA-TOPO体系测定痕量钐的激光诱导荧光光谱分析新方法。不经分离,用于氧化钇和合成水样中痕量钐的测定,操作简便、快速,结果令人满意     

射频磁控溅射CNx薄膜的结构与衬底温度关系的研究

使用射频磁控溅射方法在不同衬底温度下（ts=室温，350，500℃）于Si(001)衬底上沉积了CNx膜，并利用拉曼（Raman)光谱、傅里叶变换红外光谱（FTIR）及X射线衍射光电子能谱（XPS）对CNx膜的化学结合状态与温度的关系进行了研究。Raman光谱结果表明，随衬底温度（ts) 增加，D带向低频方向移动，G带向高频方向移动；它们的半高宽分别由375和150cm^-1减小至328和142cm^-1；ID／IG由3．76减小至2.88。FTIR谱中除无序D带（1400cm^-1)和石墨G带（1570cm^-1)外，还有－700cm^-1,～2210cm^-1(C=N),2330cm^-1(C-O)及3255－3351cm^-1(N-H)等峰。XPS测试结果表明：随衬底温度增加，N与C的物质的量比由0.49下降至0.38，sp^2(C-N)组分与sp^3(C-N)组分强度比呈增大趋势。低温（350℃）退火并未对CNx膜的化学结合状态产生较大影响；高温（900℃）退火样品则显示出较好的结晶化程度。     

乙酰水扬酸在CTAB胶束溶液中的水解反应

乙酰水扬酸(阿斯匹林)具有较高的药用价值,对它的性质有较多的研究,如在水中的稳定性和水解等。乙酰水扬酸有一个脂键和一个羰基。脂键易水解,水解后药用价值虽未降低,但有很大的副作用,因而研究抑制乙酰水扬酸水解是很有意义的。本文用RD—Ⅲ型热导式自动量热计研究了在十六烷基三甲基溴化胺(CTAB)胶束溶液中乙酰水扬酸的水解反应热动力学。     

几种卟啉在化学还原沉积银膜上的表面增强拉曼光谱特征

应用 Ｊｏｂｉｎ－Ｙｖｏｎ Ｕ—１０００型拉曼光谱仪和ＬＡＢＲＡＭＩ型拉曼光谱系统研究了 ３种卟啉ＴＯＨＰＰ、ＴａｍＰＰ和ＴＳＰＰ在化学还原沉积法制备的银膜上的ＲＳ和ＳＥＲＳ光谱特征。结果表明：化学还原法制备的银膜可以作为这几种卟啉的拉曼增强活性载体。这３种卟啉在获谱的过程中都形成二聚态化合物和发生银离子搀和作用，较长的放置和测谱时间有利于银离子的搀和。     

Fluorescence decay and quenching of pyrene labeled on sulfonate polyelectrolytes in salt-free aqueous solutions

Fluorescence decay and quenching of pyrene labels on copolymers of 2-acrylamido-2-methylpropanesulphonic acid (AMPS) and N,N-dimethylacrylamide were observed in dilute salt-free aqueous solutions as a function of the mole fraction F_AMPS of AMPS from 0 to 0.896. Monoexponential decay was found for the samples of F_AMPS<0.35 and biexponential decay for the samples of F_AMPS>0.35. The fast decay component is 80%, and the averaged lifetime 〈τ〉 and lifetime τ₁ of the fast decay is decreased with increasing F_AMPS. Quenching efficiency of Cu²⁺, I⁻, CH₃NO₂, and dinitrobenzene to the pyrene label was investigated in the framework of Stern-Volmer plot. With increasing F_AMPS the quenching efficiency of Cu²⁺ is increased while that of I⁻ decreased. For the neutral quenchers, the quenching rate constant k_q increases when F_AMPS<0.449 then decreases, showing a decline of accessibility to the pyrene label. These results were interpreted consistently with the counterion condensation concept, where condensed counterions caused the polyelectrolyte chains to aggregate. The existence of less-polar “temporal aggregated domain” in highly charged polyelectrolytes appears to lead to the slower decay and lower accessibility of the pyrene labels.     

Cr（Ⅲ）—5—Br—PADAP—Triton X—100析相光度法测定微量铬的研究

研究Cr(Ⅲ)-5-Br-PADAP-Triton X-100析相显色体系,建立测定微量铬的析相光度法。在pH 4.5乙酸-乙酸钠介质中,Cr(Ⅲ)、5-Br-PADAP、Triton X-100加热形成的配合物,于95℃恒温浴中析相1h,即被Triton X-100相完全富集,最大吸收峰为593nm,铬含量在0～10μg/5ml服从比耳定律,以硫脲、锰-EDTA、柠檬酸钠、氟化钾为掩蔽剂,测定水样中微量铬,获得满意结果。     

Weighted two-band target entropy minimization for the reconstruction of pure component mass spectra: Simulation studies and the application to real systems

A method is proposed, on the basis of a recently developed algorithm--Band Target Entropy Minimization (BTEM)--to reconstruct mass spectra of pure components from mixture spectra. This method is particular useful in dealing with spectral data with discrete features (like mass spectra). Compared to the original BTEM, which has been applied to differentiable spectroscopies such as Fourier-transfer infrared spectroscopy (FTIR), ultraviolet (UV), Raman, and nuclear magnetic resonance (NMR), the latest modifications were obtained through: (1) Reformulating the objective function using the peak heights instead of their derivatives; (2) weighting the abstract vector VT to reduce the effect of noise; (3) using a two-peak targeting strategy (tBTEM) to deal with strongly overlapping peaks; and (4) using exhaustive search to locate all the component spectra. A set of 50 multi-component mass spectra was generated from ten reference experimental pure component spectra. Many of the compounds chosen have common MS fragments and therefore, many of the pure component spectra have considerable intensity in same data channels. In addition, a set of MS spectra from a real system with four components was used to examine the newly developed algorithm. Successful reconstruction of the ten component spectra of the simulated system and the four component spectra of the real system was rapidly achieved using the new tBTEM algorithm. The advantages of the new algorithm and its implication for rapid system identification of unknown mixtures are readily apparent.