Vibronic intensities in centrosymmetric lanthanide complex ions. I

Summary A theoretical model to calculate the vibronic intensities induced by the odd vibrational modes in centrosymmetric lanthanide complexes is developed and applied to octahedral complex ions, LnX ₆ ^3– , such as occur in the hexachloroelpasolites Cs₂NaLnCl₆. Both the crystal field and the ligand polarisation contributions are evaluated using a standard set of symmetry coordinates. For the crystal field term a truncated expansion of the intermediates states is employed rather than the more conventional closure approximation. Special care is necessary to ensure that the phases of the contributions are correctly determined since the cross-term between the ligand polarisation and crystal field contributions is signed. General equations applicable to anyf ⁿ complex ion are derived and an example of their application to the PrCl ₆ ^3– ion is given The agreement with experiment is satisfactory.     

A new imidazolylquinoline for organic thin film transistor

A new active electronic material, 2-(naphtho[3,4]imidazol-2-yl)quinoline (NIQ), 1, has been synthesized and fully characterized. This compound exhibits field-effect carrier mobility and behaves as a p-type semiconductor (μ_FET = 0.148 cm²/V s at V_DS = 10 V). NIQ and its related imidazolylquinoline compounds may have possible applications as active materials in organic thin film transistors.     

Semi-micro solvent extraction as a rapid and efficient preconcentration technique for the determination of n-alkanes in oil-contaiminated water and soil samples by capillary gas chromatography

Summary In this study, a rapid and efficient semi-micro extraction procedure is presented for the extraction of some higher n-alkanes from water and soil samples. In the case of water samples n-hexane was used as the organic phase in a phase volume ratio (volume of aqueous phase/volume of organic phase) higher than 285, while in the case of soil samples, extraction with n-hexane was carried out in the presence of an excess of 2 M NaCl solution. The extraction rate from soil samples is very high and is better than Soxhlet extraction, comparable with supercritical fluid extraction. High preconcentration factor in water samples allows the limits of detection to be in the ng.mL⁻¹ level with the use of gas chromatographic analysis. Flame ionization detector was used for monitoring the analytes. The obtained recoveries of all studied compounds from both water and soil samples are higher than 90%. This method was successfully used to determine some n-alkanes in municipal wastewater and contaminated soil.     

Shape analysis based critical Eotvos numbers for buoyancy induced partial detachment of oil drops from hydrophilic surfaces

Removal of oil drops from solid surfaces immersed in an aqueous medium is of interest in many applications. It has been shown that drop shape analysis can be used to predict conditions at which the stability limit of a lighter than water oil drop on a solid surface immersed in an aqueous bath is reached (Adv. Colloid Interface Sci. 98 (2002) 265). However the above analysis is restricted to cases where the contact angle made by the drop is below 90degrees and when the surface conditions result in a 'pinned' contact line. In this paper, it is shown that drop shape analysis can be used to predict the critical conditions at which drop stability limit is reached for drop contact angles of 90degrees and above, which is encountered with 'hydrophilic' surfaces. This critical condition can predict the occurrence of partial oil drop detachment, before complete removal due to 'roll-up', which occurs when the hydrophilic surface is adequately smooth which prevents 'pinning' of the contact line. The critical conditions at which partial drop detachment occurs can also be approximately predicted from simple force balances. It has been shown (Adv. Colloid Interface Sci. 98 (2002) 265) that for contact angles less than 90degrees, the critical limit based on shape analysis appears to resolve the differences that arise due to alternate expressions for capillary retention force. This paper shows that even for contact angles above 90degrees, the critical conditions predicted from the shape analysis resolves the differences in the predictions from the alternate force balances. Drop shape analysis used in this paper is based on the 'Arc-length' form of Young-Laplace or 'drop shape' equation, which is different from the 'Y vs X' form of the above equation that is used in Adv. Colloid Interface Sci. 98 (2002) 265. The above drop shape equation is solved by a fourth order Runge-Kutta technique and it is shown that for angles less than 90degrees, the two forms of the drop shape equation, predict almost identical values of the critical Eotvos number. This paper highlights the competing effects of interfacial tension lowering induced drop instability and 'roll-up', a term that is used to describe the retraction of the contact line of an oil drop on a surface, in being the primary c ause for drop detachment.     

河南的红菇科真菌资源的研究（Ⅱ）

红菇属（Ｒｕｓｓｕｌａ）是红菇科（Ｒｕｓｓｕｌａｃｅａｅ）的一个重要的属。本文依据在河南山区采集的标本,鉴定、整理出红菇属的种类有３１种,其中食用菌２４种、药用菌４种、毒菌５种。此外,它们多是菌根菌,与林业有着密切的关系,还有不少种类的子实体中含有抗癌物质,具有抑制肿瘤的作用。     

Selective spectrophotometric determination of TNT in soil and water with dicyclohexylamine extraction

Contaminated land and groundwater remediation in military waste dumping sites often necessitates the use of simple, cost-effective, and rapid tests for detecting trinitrotoluene (TNT) residues in the field along with their dinitro-analogues. A simple, rapid, low-cost, and field-adaptable (on-site) colorimetric method was developed for quantifying TNT in the presence of RDX, PETN, picric acid, 2,4-DNT (dinitrotoluene), dinitrophenol, and dinitroaniline. Most commercialized methods for TNT assay-with the exception of Cold Regions Research and Engineering Laboratory of the U.S. Army (CRREL) method-use proprietary chemicals, and the color stability and intensity are highly dependent on the composition of the organic solution comprised of acetone or methanol. The developed colorimetric method is based on the extraction of TNT from water-acetone solution into an organic solvent mixture of dicyclohexylamine (DCHA)-isobutyl methyl ketone (IBMK) (10:1, v/v), filtration through a filter paper into a stoppered optical cell containing anhydrous sodium sulfate, and measurement of the absorbance of the organic extract at 531 nm after 5 min. The red-violet color of the extract was due to intermolecular charge-transfer (CT) between the electron attracting TNT and electron-donating DCHA, and the molar absorptivity for TNT in final organic solution was (1.16 ± 0.02) × 10⁴ L mol⁻¹ cm⁻¹.The R.S.D. of the slope of calibration line was 0.7%. The LOD of the method in the final organic phase was 0.38 μM TNT, and LOD values expressed on the basis of original soil TNT content were 0.5, 1.3, and 1.5 ppm (μg g⁻¹) for clay, loamy clay, and sandy soils, respectively. Unlike other spectrophotometric methods, the developed assay was basically tolerant to common cations and anions found in soil and water at 100-fold weight ratios, and to soil humic acids. Among a number of compounds that may be encountered in polynitro-explosive storage and waste reclaimation sites such as picric acid, dinitrophenol, 2,4-dinitrotoluene, dinitroaniline, RDX, PETN, and tetryl, only tetryl interfered with the developed TNT assay. Water tolerance and exploitability over a wide pH range were other superiorities over the CRREL method. The CT-complex was relatively stable, as the absorbance of the organic extract was not significantly influenced from the dilution of the water-acetone phase. Aside from the extractive-photometric procedure established for aqueous solutions, a simulated field colorimetric assay for TNT directly applicable to soil was also devised, based on direct color development in a 4:1 (v/v) acetone-dicyclohexylamine organic extract of soil at a liquid-to-solid ratio of 5 mL g⁻¹.     

Development and validation of a capillary electrophoresis method for the determination of phenothiazines in human urine in the low nanogram per milliliter concentration range using field-amplified sample injection

A capillary zone electrophoresis (CZE) method with ultraviolet-visible detection has been established and validated for the determination of five phenothiazines: thiazinamium methylsulfate, promazine hydrochloride, chlorpromazine hydrochloride, thioridazine hydrochloride, and promethazine hydrochloride in human urine. Optimum separation was obtained on a 64.5 cm x 75 microm bubble cell capillary using a buffer containing 150 mM tris(hydroxymethyl)aminomethane and 25% acetonitrile at pH 8.2, with temperature and voltage of 25 degrees C and 20 kV, respectively. Naphazoline hydrochloride was used as an internal standard. Field-amplified sample injection (FASI) has been applied to improve the sensitivity of the detection. Considering the influence of parameters affecting the on-line preconcentration (nature of preinjection plug, sample solvent composition, injection times, and injection voltage) and due to the significant interactions among them, in this paper we propose for the first time the application of a multivariate approach to carry out the study. The optimized conditions were as follows: preinjection plug of water for 7 s at 50 mbar, electrokinetic injection for 40 s at 6.2 kV, and 32 microm of H3PO4 in the sample solvent. Also, a solid-phase extraction (SPE) procedure is developed to obtain low detection limits and an adequate selectivity for urine samples. The combination of SPE and FASI-CZE-UV allows adequate linearities and recoveries, low detection limits (from 2 to 5 ng/mL), and satisfactory precisions (3.0-7.2% for an intermediate RSD %).     

X—射线荧光光谱法分析燃油锅炉受热面的灰渣成分

用X-射线荧光光谱(XRF)法测定了火电厂燃油锅炉受热面的灰渣成分,给出了XRF测试条件,与等离子体发射光谱法的测试结果进行了对比。     

眼镜蛇蛇油中甘油三酸酯的成分研究

用ＡｇＮＯ３－硅胶薄层板，氯仿＋丙酮（２０＋１）为展开剂，将蛇油中甘油三酸酯分离为５个组分，并用同样的色谱固定相和石油醚－氯仿－丙酮溶剂系统进行制备性分离。用质谱法对甘油三酸酯进行分子一级水平的化学研究，确定了眼镜蛇蛇油中５个主要的甘油三酸酯成分的结构形式为：１６∶０－１８∶０－１８∶０，１６∶０－１８∶０－１８∶１，１６∶０－１８∶２－１８∶１，１８∶２－１８∶２－１８∶０，１８∶２－１８∶２－１８∶１。     

Analysis of tinuvin 1577 polymer additive in edible oils using on-line coupled HPLC-GC

An application of automated on-line HPLC-HRGC is described for direct analysis of edible oils for migrated polymer additives. The sample preparation, separating the additive from the oil triglycerides, is carried out using normal phase HPLC. The fraction of the eluent containing the additive is automatically transferred to a HRGC where a second and final separation of the additive from minor oil components takes place. The method compares well with off-line separation methods. Migration data for Tinuvin 1577 from PET and PC polymers as well as an unspecified experimental polymer is given. The advantages and disadvantages of using different edible oils as food simulants are discussed.