原位合成分子筛膜毛细管色谱柱的研制

吸附型多孔层毛细管柱既耐高温又对气体及烃类异构体有选择性，同时又具有毛细管色谱快速、高效等优点，是解决难分离组分的重要柱型．常用作气一固吸附色谱固定相的有强极性的硅、中极性的氧化铝、非极性的碳质及特殊吸附作用的分子筛．其中分子筛以其独特的吸附作用，在永久性气体和烃类碳数族组成分析中有重要地位．Pruecell和Soulages[1，2]等制备了涂渍型5A和13X型分子筛的毛细管柱，对低碳烃类化合物显示了良好的分离能力，分析柱温较填充柱降低约100℃．邹乃忠等[3～5]也先后制备了分子筛层的毛细管柱用来作直馏汽油的分析．由于通…     

Measurement of lactate in whole human blood with near-infrared transmission spectroscopy

We have evaluated the potential of near-infrared spectroscopy (NIRS) as a technique for rapid analysis of lactate in whole blood. To test the NIRS technique, a comparison was made with a standard clinical method using whole blood samples taken from five exercising human subjects at three different stage of exercise. To expand lactate concentration within the physiological range, standard additions method was used to generate 45 unique data points. Spectra were collected over the 2050-2400 nm spectral range with a 1 mm optical path length quartz cell. Reference lactate concentrations in the samples were determined by enzymatic measurements. Estimates and calibration of the lactate concentration with NIRS was made using partial least squares (PLS) regression analysis and leave-N-out cross validation on second derivative spectra. Separate calibrations were determined from each of the subject samples and cumulative PRESS was used to determine the number of PLS factors in the final model. The results from the PLS model presented are generated from the five individual calibration coefficient vectors and provided a correlation coefficient of 0.978 and a standard error of cross validation of 0.65 mmol l⁻¹ between the enzymatic assay and the NIRS technique. To study the parameters that impact the spectra baseline and the correlation between the calculated model and the data, referenced measurements of lactate against baseline spectrum were made for each individual. A correlation coefficient of 0.992 and a standard error of cross validation of 0.21 mmol l⁻¹ were found. The results suggest that NIRS may provide a valuable tool to assess physiological status for both research and clinical needs.     

Ag-MoO3催化丙烯直接气相环氧化反应的原位红外研究

制备了对丙烯直接气相环氧化具有较好催化性能的Ag-MoO3催化剂, 采用原位FT-IR技术研究了丙烯、环氧丙烷及丙烯+氧气的混合气在Ag和Ag-MoO3催化剂表面上的吸附及反应行为. 研究表明, 丙烯在Ag和Ag-MoO3催化剂表面上吸附后, 均不发生化学反应, 而环氧丙烷吸附后在较高温度下则发生开环和聚合反应直至产生积炭. 与Ag催化剂相比, 在Ag-MoO3催化剂上, MoO3的加入在降低催化剂活性的同时, 在一定程度上抑制了产物环氧丙烷的开环及深度反应, 使环氧丙烷的选择性提高. 另外, 在较低的反应温度和较短的滞留时间下, 环氧丙烷发生深度反应的程度明显降低.     

Phosphate-selective electrodes containing immobilised ionophores

Phosphate selective electrodes have been produced based upon rubbery membranes containing heterocylic macrocycles as sensors covalently bound to a cross-linked polystyrene-block–polybutadiene-block–polystyrene (SBS) polymer. The membranes were robust and the best HPO₄²⁻-selective membrane fabricated was composed of 7.1% (m/m) dicumyl peroxide, 28.3% (m/m) 2-nitrophenyloctylether, 9.8% (m/m) 3-(10-undecenyl)-1,5,8-triazacyclodecane-2,4-dione, 31.0% (m/m) SBS and 23.8% (m/m) PoleStar™ 200R (clay-based filler). The characteristics of this electrode were a linear Nernstian range of 3.9×10⁻³ to 1×10⁻⁶ mol dm⁻³ HPO₄²⁻ with a limit of detection of 1.0×10⁻⁶ mol dm⁻³ HPO₄²⁻, a slope of −29.7±0.9 mV per activity decade and a pH range from 6 to 8. Selectivity coefficients for phosphate against various interfering anions (chloride, sulfate and nitrate) were determined. Response times were 2 min or under, stability of response and electrode lifetime in continuous use were also very satisfactory. The response behavior of HPO₄²⁻-ISEs based upon mobile and bound ionophores was comparable and suggests that mobility of the ionophore is not necessary to obtain a working ISE and that covalent binding of ionophores can be used to produce ISEs of increased stability and robustness.     

富锂掺杂Li1.06Co0.05Cr0.1Mn1.85O4的合成及电化学性能研究

锂离子电池具有比能量高、功率大、使用寿命长、无记忆效应、性能价格比高等优点,从而成为可充式电源的主要选择对象.锰由于资源丰富、价廉、环境友好等优点,使锰酸锂(LiMn2O4)成为最有希望取代钴酸锂的正极材料.但锰酸锂的放电容量相对较低,结构欠稳定,容量衰减严重,作为正极材料还无法与钴酸锂相比,近年来做了大量的研究工作以改善它的电化学性能[1～6].最近Youngjoon Shin等研究发现[7]用少量的Li与Ni共同替代LiMn2O4中的Mn得到的LiMn2-2yLiyNiyO4的电化学性能要优于单元素替代的LiMn2-xMxO4(M=Li,Cr,Fe,Co,Ni)的电化学性能.     

Hydrogen-Related Paramagnetic Centers in Ge-Doped Sol-Gel Silica Induced by γ-Ray Irradiation

We have studied the generation mechanisms of H(II) paramagnetic centers in Ge-doped silica by investigating up to 10⁴ mol ppm sol-gel Ge-doped silica materials. We have considered materials with the same concentrations of Ge but that are produced by two different densification routes that give rise to different concentrations of Ge-related oxygen deficient centers (GeODC(II)). These centers are characterized by an optical absorption band at ∼5.2 eV (B_2β band) and two related emissions at ∼3.2 eV and ∼4.3 eV. The GeODC(II) content was estimated by absorption and emission measurements. The H(II) centers were induced by room temperature γ-ray irradiation and their concentration was determined by electron paramagnetic resonance measurements. The comparison between the two kinds of materials, obtained by different preparations, shows that the GeODC(II) concentration increases with the Ge content and is enhanced by vacuum densification. The comparison of irradiated samples shows that beyond the already known process of conversion of preexisting GeODC(II) into H(II) centers, another generation process of H(II) centers is effective that involves irradiation induced GeODC(II).     

Metal speciation measurement by diffusive gradients in thin films technique with different binding phases

Since its invention in the mid-1990s, the diffusive gradients in thin films (DGT) technique has rapidly become one of the most promising in situ sampling techniques for trace metal measurement in natural waters. We investigated here the possibility of using DGT devices with different binding phases to determine different DGT labile fractions of Cd and Cu in laboratory solutions and in natural waters. Several binding phases were studied, including conventional Chelex 100 resin imbedded polyacrylamide hydrogel (Chelex) and several recently developed binding phases, poly(acrylamide-co-acrylic acid) (PAM-PAA) gel, poly(acrylamidoglycolic acid-co-acrylamide) (PAAG-PAM) gel, Whatman P81 cellulose phosphate ion-exchange membrane (P81), and poly(4-styrenesulfonate) (PSS) aqueous solution. Laboratory testing in metal solutions spiked with EDTA or humic acid suggested that all the DGT devices measured only free metal ions and inorganic metal complexes. Upon field testing at both freshwater and seawater sites it was found that the DGT labile metal concentrations measured by different binding phases can be significantly different, suggesting that the DGT labile metal fractions were dependent on binding strength of the binding phase. By designing binding phases that can compete with different natural water complexing ligands to varying extents, it is possible to use these different DGT devices to measure metal speciation in natural waters.     

Mechanism and kinetics of the reduction of In(III) ions at a polycrystalline gold electrode from highly concentrated ZnCl2 solutions

Summary The mechanism of the cathodic reduction of In(III) at gold has been studied by rotating disc and ring-disc voltammetry in highly concentrated aqueous ZnCl₂ solutions. At concentration of the base electrolyte higher than 7 mol dm^–3, the voltammetric curves recorded at the disc electrode split into two well-separated waves which correspond to the successive charge transfer reactions: In(III) + 2e^– In(I) and In(I) + e^– In. By the use of coulometric and potentiometric techniques, the formal potentials of the In(III)/In(I), In(III)/In and In(I)/In redox couples as well as the equilibrium constants of the reproportionation reaction In(III) + 2 In 3 In(I) has been determined and discussed. The kinetic parameters of the In(III)/In(I) electrode reaction have been also evaluated and discussed.

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Mechanismus und Kinetik der Reduktion von In(III)-Ionen an der Goldelektrode in hochkonzentrierten wäßrigen ZnCl₂-Lösungen

Zusammenfassung Es wird der Mechanismus der Reduktion von In(III)-Ionen in hochkonzentrierten ZnCl₂ Lösungen mittels der Scheiben- und Ring-Scheiben-Elektrode aus Gold untersucht. Wenn die Konzentration des Grundelektrolyten 7 mol dm^–3 übersteigt, verteilen sich die erhaltenen Stromspannungskurven auf zwei gut gestaltete Stufen, die den konsekutiven Durchtrittsreaktionen In(III) + 2e^– In(I) und In(I) + e^– In entsprechen. Aufgrund der coulometrischen und potentiometrischen Messungen werden die Formal-Standardpotentiale der In(III)/In(I)-, In(III)/In-und In(I)/In-Redoxpaare, die Gleichgewichtskonstanten der Reproportionierungsreaktion In(III) + 2 In 3 In ermittelt. Die kinetischen Parameter der Durchtrittsreaktion In(III)/In(I) werden bestimmt und diskutiert.

     

Stir bar sorptive extraction with in situ derivatization and thermal desorption-gas chromatography-mass spectrometry for determination of chlorophenols in water and body fluid samples

A new method, stir bar sorptive extraction (SBSE) with in situ derivatization and thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS), which is used for the determination of trace amounts of chlorophenols, such as 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TrCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP) and pentachlorophenol (PCP), in tap water, river water and human urine samples, is described. The derivatization conditions with acetic acid anhydride and the SBSE conditions such as extraction time are investigated. Then, the stir bar is subjected to TD followed by GC-MS. The detection limits of the chlorophenols in tap water, river water and human urine samples are 1-2, 1-2, and 10-20 pg ml⁻¹ (ppt), respectively. The calibration curves for the chlorophenols are linear and have correlation coefficients higher than 0.99. The average recoveries of the chlorophenols in all the samples are higher than 95% (R.S.D. < 10%) with correction using added surrogate standards, 2,4-dichlorophenol-d₅, 2,4,6-trichlorophenol-¹³C₆, 2,3,4,6-tetrachlorophenol-¹³C₆ and pentachlorophenol-¹³C₆. This simple, accurate, sensitive and selective analytical method may be applicable to the determination of trace amounts of chlorophenols in liquid samples.     

Infrared spectra of two sexithiophenes in neutral and doped states: a theoretical and spectroscopic study

The FT-infrared spectra of two sexithiophenes having their end ,′-positions substituted by n-hexyl or -thiohexyl groups, in neutral and doped states, are studied with the main aim of deriving information about the π-electrons delocalization and about the electronic structure of the charged defects created upon doping with iodine. The analysis of the experimental data is aided by Density Functional Theory calculations. The modifications in the electronic structure of the sexithiophene backbone induced by the n-thiohexyl encapsulation are discussed from the point of view of single molecule interactions in thiol-terminated π-conjugated oligomers bound to metallic or cluster electrodes.