Determination of 25‐hydroxyvitamin D3 in human plasma using HPLC with UV detection based on SPE sample preparation

Interest in the metabolism and physiological action of vitamin D is increased exponentially. The most important metabolites of vitamin D are 25‐hydroxyvitamin and 1,25‐dihydroxyvitamin D₃. The aim of the study was to develop a rapid and simple HPLC method for the measurement of 25‐hydroxyvitamin D₃ in human plasma. A method for the measurement of 25‐hydroxyvitamin D₃ using HPLC with UV detection and investigation into the extraction techniques with regard to stability and recovery are described. For the separation, RP column LiChroCart 125‐4, Purospher RP‐18e, 5 μm, was used. The mixture of methanol and deionized water (95:5 v/v) was used as mobile phase. The analytical performance of this method is satisfactory: the intra‐ and inter‐assay coefficients of variation were below 10%. Quantitative recoveries from spiked plasma samples were between 92.0–103.2%. The LOD was 10 nmol/L. The preliminary reference range of 25‐hydroxyvitamin D₃ in a group of blood donors is 62 ± 26 nmol/L.     

2-D Simulation of Non-isothermal Fate and Transport of a Drip-applied Fumigant in Plastic-mulched Soil Beds. I. Model Development and Performance Investigation

Pre-plant application of toxic fumigants to soil beds covered by plastic film is commonly used in agriculture to control soil-borne pathogens. Plastic mulch covers tend to physically suppress the emissive loss of gaseous fumigant to the atmosphere. When liquid fumigant metham sodium (MS) is applied in irrigation water to field soil, it is rapidly transformed to the gaseous methyl isothiocyanate (MITC). The gaseous MITC is a potential atmospheric contaminant, and any untransformed MS is a potential contaminant of underlying groundwater due to the high water solubility of MS. A finite element numerical model was developed to investigate two-dimensional MITC fate/transport under non-isothermal soil conditions. Directional solar heating on soil beds, coupled heat and water flow in the soil, and non-isothermal chemical transport were included in the model. Field soil data for MITC distribution, soil water content, meteorological data, and laboratory data were used to verify the model for soil beds covered with plastic mulch. Four possible scenarios were considered: low and high drip-irrigation rates and low and high water contents. The movement of the center of MITC mass in the soil profile was effectively simulated. The lower drip-irrigation rate of MS yielded more extensive coverage of MITC in the plastic-covered soil bed. The lower soil air contents due to higher soil water contents for the higher irrigation rate resulted in high concentrations of soil MITC. NRMSE (normalized root mean square error) calculations further verified that the model predicted fumigant fate/transport well under these non-isothermal field conditions.     

有机污染物水解速度常数与腐殖质浓度定量关系的建立及验证

水解是有机污染物转化降解的重要途径.天然水体中的腐殖质影响有机化合物的水解速度常数,使之与蒸馏水缓冲系统中的测定值有较大差别.本文推导并验证了腐殖质浓度与水解速度常数的定量关系,测定了腐殖质与有机化合物的缔合系数.     

利用飞秒泵浦探测技术研究碘甲烷B态预解离动力学

应用飞秒双光泵浦-探测技术结合飞行时间质谱研究了碘甲烷分子的B态预解离动力学，其中泵浦光波长为400 nm，探测光为800 nm，碘甲烷主要的产物通道为生成CH3I+和CH3+．改变泵浦与探测光之间的延时，得到了这两种离子的时间演化曲线，每个曲线都可以用两个指数函数来拟合，拟合常数为?1和?2，?1反映了碘甲烷分子吸收三个泵浦激光所到达的高里德堡态的动力学，?2反映了吸收两个泵浦激光所到达的B里德堡态的动力学，得到的B态的带源寿命为1.57 ps，这个值和以前的文献非常符合，试验结果被解释为多光子的电离解     

Infrared reflection absorption spectroscopic study of the adsorption structures of dimethyl ether and methyl ethyl ether on Cu(1 1 1) and Ag(1 1 1)

Infrared reflection absorption (IRA) spectra measured for dimethyl ether (DME) adsorbed at 80 K on Cu(1 1 1) and Ag(1 1 1) give IR bands belonging only to the A₁ and B₂ species, indicating that the adsorbate takes on an orientation in which the C₂ axis bisecting the COC bond angle tilts away from the surface normal within the plane perpendicular to the substrates. The DFT method was applied to simulate the IRA spectra, indicating that the tilt angles of DME on Cu(1 1 1) and Ag(1 1 1) are about 50° and 55°, respectively, at submonolayer coverages. The results are in contrast to the case of DME on Cu(1 1 0) and Ag(1 1 0), where the C₂ axis is perpendicular to the substrates [T. Kiyohara et al., J. Phys. Chem. A 106 (2002) 3469]. Methyl ethyl ether (MEE) adsorbed at 80 K on Cu(1 1 1) gives IRA bands mainly ascribable to the gauche (G) form, whereas the IRA spectra measured for MEE on Ag(1 1 1) are characterized by the trans (T) form. The rotational isomers are identical with those on Cu(1 1 0) and Ag(1 1 0); i.e., MEE on Cu(1 1 0) takes the G form and the adsorbate on Ag(1 1 0) the T form [T. Kiyohara et al., J. Phys. Chem. B 107 (2003) 5008]. The simulation of the IRA spectra indicated that (i) the G form adsorbate on Cu(1 1 1) takes an orientation, in which the axis bisecting the COC bond angle tilts away from the surface normal by ca. 30° within the plane perpendicular to the surface to make the CH₃-CH₂ bond almost parallel to the surface, and (ii) the T form adsorbate on Ag(1 1 1) takes an orientation, in which the bisecting axis tilts away by ca. 60° from the surface normal within the perpendicular plane. Comparison of these adsorption structures of MEE on the (1 1 1) substrates with those of MEE on Cu(1 1 0) and Ag(1 1 0) indicates that the structures are mainly determined by a coordination interaction of the oxygen atom to the surface metals and an attractive van der Waals interaction between the ethyl group of MEE and the substrate surfaces. The coordination interaction plays an important role on Cu(1 1 1) and Cu(1 1 0), which makes the adsorbate on the Cu substrates to take the orientations with the bisecting axis near parallel to the surface normal and to assume the G form in order to make the ethyl group parallel to the surface, which is favorable for the van der Waals interaction. In the case of MEE on the Ag substrates the attractive van der Waals interaction plays a dominant role, resulting in the T form which is more favorable for the interaction than the G form.     

Polymerization of methyl methacrylate with ethylene bridged heterodinuclear metallocene of samarium and titanium

A novel heterodinuclear catalyst, ethylene bridged samarocene and titanocene chloride (Sm-Ti), was used both as a single component catalyst (cat.) and also by activation with triisobutyl aluminum (TIBA) to polymerize methyl methacrylate (MMA). The binary catalyst demonstrated higher activity than the single component, but the molecular weight of the resultant PMMA is lower. Ultrahigh molecular weight PMMA (1.5×10⁶) was obtained at an attractive conversion (87%) without any cocatalyst. The effects of polymerization parameters, such as temperature, time, molar ratios of Al(i-Bu)₃/cat. and MMA/cat., were studied in detail. The results showed that the catalytic activity had a rather different dependence on the polymerization temperature with/without TIBA. High molecular weight PMMA was much more easily prepared in a bulk system than in toluene solution. The polymer yielded with about 65% syndiotacticity by 1H NMR and 75% by IR spectroscopy, but its stereoregularity did not change too much with polymerization temperature and the concentration of TIBA.     

High-temperature UV absorption of methyl radicals behind shock waves

The absorption of ultraviolet narrow-line laser radiation by methyl radicals (CH₃) in the electronic system has been studied at high temperatures behind shock waves. Methyl radicals at high temperatures were generated by the shock heating of methyl precursors: azomethane, methyl iodide, and ethane. The spectral shape and intensity of the broadband absorption feature from 211.5 to 220 nm at high temperature (1565 K) has been measured. The absorption coefficient of CH₃ at 216.62 nm, the wavelength of peak absorption at high temperatures in the P+Q band, has been determined from 1200 to 2500 K. Additionally, the absorption coefficients of several interfering UV-absorbing combustion species (, and C₃H₆) have been determined at 216.62 nm.     

Lipase specificity for the hydrolysis of poly (vinyl acetate)

The effect of lipases on the side chain hydrolysis of poly (vinyl acetate) (PVAc) was investigated in toluene by various lipases, Hog-pancreas (HP), Candida Rugosa (CR), Lipolase-100T (LL), and Novozyme 435 (NV) at 60 °C. Gas chromatographs and GC–MS spectra showed the presence of different ester side chains. The different size side chain esters in PVAc get hydrolyzed at different specific rates by the various lipases. Longer side chains are hydrolyzed in the order HP>NV>LL>CR whereas the short chains are hydrolyzed in the reverse order. A continuous distribution kinetics model was proposed that accounts for lipase deactivation and determines the rate coefficients of hydrolysis of various chain lengths. Lipase deactivation and hydrolysis rate coefficients were determined for each case. The proposed model predicts the experimental data satisfactorily.     

A rapid gas chromatographic method for the analysis of acidic fermentation products

Summary A rapid and simple method for the identification of acidic fermentation products is described. Methyl esters of volatile and non-volatile acids are separated on a single chromatographic column. Retention time data for a number of acids are tabulated.