Underpotential deposition studies of copper on glassy carbon

Studies on the deposition and dissolution of copper from 0·5 M sulphuric acid solutions onto glassy carbon (GC) using potential sweep techniques indicated that an additional peak occurs at higher positive potentials than the bulk stripping peak. This peak is identified as due to the stripping of underpotential deposited (UPD) copper. Results of investigations on the effect of sweep rate, deposition potential and time of deposition on the peak characteristics of UPD and bulk deposited copper are also reported.     

New stationary phases of conjugated π-electron systems for HPLC—characterization of structure and dynamics by solid state NMR spectroscopy

Four new stationary phases for HPLC were prepared by modifying silica gel with a trifrnctional aminoalkyl silane. A conjugated π-electron system was linked to the amino group either directly or with a carboxylic anhydride as a spacer in between. Characterization and dynamic measurements of the new stationary phases were performed by solid state NMR spectroscopy. The results of the ²⁹si and ¹³C CP/MAS techniques were compared with the recently developed ¹H MAS-only technique. Despite strong homonuclear dipole-dipole interactions it was possible to obtain well resolved ¹H MAS spectra of those stationaru phases with a high degree of crosslinking. Limited mobility of the aromatic ligand fragments is common for all examined stationaryu phases. The chromatographic properties of the new phases were tested by their ability tio sepatate a mixture of eight PAHS. It could be shown that the π-π interaction mechanism is responsible for the separation of the eight PAHs, because the elution order of the PAHs did not changem despite the use of both a nonpolar mobile phase (n-heptane) and a polar mobile phase (methanol/ water mixture).     

Relationships among Preparative Technique,Phase Composition and Bending Strength of Bauxite Porcelain

1 INTRODUCTION Bauxite porcelain is a novel “K2O–Al2O3–SiO2” system ceramic by using sintered bauxite, clay and potash feldspar and albite as the main raw materials with the Al2O3’s content of 50%～60(massfraction). Compared to the traditional“K2O–Al2O3–SiO2” feldspar porcelain by using quartz, bolus alb and potash feldspar and albite as the main raw materials, the bauxite porcelain possesses such advantages as high mechanical strength, excellent electrical insula- tion prop…     

Solid-phase extraction of iron(III) with an ion-imprinted functionalized silica gel sorbent prepared by a surface imprinting technique

A new Fe(III)-imprinted amino-functionalized silica gel sorbent was prepared by a surface imprinting technique for selective solid-phase extraction (SPE) of Fe(III) prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Compared with non-imprinted polymer particles, the ion-imprinted polymers (IIPs) had higher selectivity and adsorption capacity for Fe(III). The maximum static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Fe(III) was 25.21 and 5.10 mg g⁻¹, respectively. The largest selectivity coefficient of the Fe(III)-imprinted sorbent for Fe(III) in the presence of Cr(III) was over 450. The relatively selective factor (α_r) values of Fe(III)/Cr(III) were 49.9 and 42.4, which were greater than 1. The distribution ratio (D) values of Fe(III)-imprinted polymers for Fe(III) were greatly larger than that for Cr(III). The detection limit (3σ) was 0.34 μg L⁻¹. The relative standard deviation of the method was 1.50% for eight replicate determinations. The method was validated by analyzing two certified reference materials (GBW 08301 and GBW 08303), the results obtained is in good agreement with standard values. The developed method was also successfully applied to the determination of trace iron in plants and water samples with satisfactory results.     

An analysis of avidin, biotin and their interaction at attomole levels by voltammetric and chromatographic techniques

The electroanalytical determination of avidin in solution, in a carbon paste, and in a transgenic maize extract was performed in acidic medium at a carbon paste electrode (CPE). The oxidative voltammetric signal resulting from the presence of tyrosine and tryptophan in avidin was observed using square-wave voltammetry. The process could be used to determine avidin concentrations up to 3 fM (100 amol in 3 l drop) in solution, 700 fM (174 fmol in 250 l solution) in an avidin-modified electrode, and 174 nM in a maize seed extract. In the case of the avidin-modified CPE, several parameters were studied in order to optimize the measurements, such as electrode accumulation time, composition of the avidin-modified CPE, and the elution time of avidin. In addition, the avidin-modified electrode was used to detect biotin in solution (the detection limit was 7.6 pmol in a 6 l drop) and to detect biotin in a pharmaceutical drug after various solvent extraction procedures. Comparable studies for the detection of biotin were developed using HPLC with diode array detection (HPLC-DAD) and flow injection analysis with electrochemical detection, which allowed biotin to be detected at levels as low as 614 pM and 6.6 nM, respectively. The effects of applied potential, acetonitrile content, and flow rate of the mobile phase on the FIA-ED signal were also studied.     

全二维液相色谱（NPLC×RPLC）接口及其应用

用内径为0．53mm的填充毛细管正相液相色谱为第一维，用4．6mm（i．d．）×50mmRP-18e整体柱反相色谱为第二维，建立了定量环一阀切换接口的全二维液相色谱系统（NPLC×RPLC）．第一维色谱分离洗脱出的组分交替存储在十通阀上的两个定量环中，同时定量环中前一个组分被转移到第二维进行反相分离．因为第一维的流动相流量仅是第二维的1／500，自然解决了流动相兼容问题．采用芳香族化合物的混合物和中药丹参正己烷提取液对该全二维液相系统的分离能力进行了评价．     

Chiral separation of bupivacaine enantiomers by capillary electrophoresis partial-filling technique with human serum albumin as chiral selector

Capillary electrophoresis (CE) is a powerful technique for enantiomer separations due to its intrinsic high separation efficiencies, speed of analysis, low reagent consumption and small sample requirements. However, some chiral selectors present strong background UV absorption providing high detection limits. The present paper deals with the application of the partial-filling technique to the separation of bupivacaine enantiomers by capillary electrophoresis using human serum albumin (HSA) as chiral selector. In this procedure the cationic surfactant cetyltrimethylammonium bromide (CTAB) was used as a dinamic capillary coating in order to reduce the electro-osmotic flow and detect both bupivacaine enantiomers out of the chiral selector plug. Several experimental conditions such as CTAB concentration, pH, HSA concentration and plug length, background electrolyte concentration, temperature and voltage were studied. Under the selected conditions it is possible to detect the separated enantiomers out of the HSA plug in less than 4 min using 50 mM Tris pH 8 as background electrolyte with 50 microM CTAB, at 30 degrees C and using a separation voltage of 25 kV. The proposed methodology was then validated for analytical purposes and applied to the analysis of pharmaceutical preparations commercially available. The results obtained with the proposed methodology were in good agreement with those declared by the manufacturers. The simplicity, sample throughput, accuracy, reproducibility and low cost of the proposed method make it suitable for the control of the enantiomeric composition of bupivacaine in pharmaceuticals.     

超支化聚硅氧烷的紫外光固化行为及固化动力学研究

采用等温差示光量热技术(DPC)研究了超支化聚硅氧烷的紫外光固化行为及固化动力学. 探索了引发剂浓度、 光强度、 聚合温度和环境气氛对固化行为的影响规律. 研究结果表明, 增加光引发剂浓度和光强度及提高环境温度均可提高其固化速率和双键最终转化率. 在空气中固化时存在氧阻聚现象, 增大光强度可以显著缩短诱导期. 运用带扩散因子的自催化固化动力学模型研究了其光固化动力学, 计算出特定条件下的光固化动力学参数, 反应总级数约为6—7, 表观活化能为9.95 kJ/mol. 通过超支化聚合物与两种结构类似的低官能度单体光固化行为的对比, 研究了超支化聚合物固化行为与其分子结构的关系, 发现由于超支化大分子的独特结构, 在固化初始阶段便产生凝胶, 因此双键的最终转化率偏低.     

Unified gas and supercritical fluid chromatography on 50 μm i.d. Columns

A unified approach to sequential gas and supercritical fluid Chromatography using 50 μm i.d. open tubular columns is described. Sample introduction is performed by means of a rotary injection valve. In order that linear velocities can be optimized independently, a second rotary valve in the chromatographic oven is used to direct the flow of column eluate to the flame ionization detector through either fused silica tubing in GC, or a frit restrictor in SFC. Applications of sequential GC-SFC on a 50 μm i.d. open tubular column are demonstrated, and comparisons made between sequential GC-SFC on 50 and 100 μm i.d. columns.     

The identification of tricyclic neuroleptics and sulphonamides by high-performance thin-layer chromatography

Circular high-performance thin-layer chromatography (HPTLC) has been used to differentiate a series of twelve tricyclic neuroleptics, using both normal phase and reverse phase procedures. The use of normal phase systems also allows the resolution of geometric isomers of chlorprothixene, clopenthixol and flupenthixol. Thirteen sulphonamides and Trirnethoprim may also be distinguished using HPTLC.