Comparison of the retention behaviour of phenol derivatives on porous graphitized and octadecylsilica columns

Summary The retention of 22 ring-substituted phenol derivatives on porous graphitized carbon (PGC) (eluents: acetonitrile — water and methanol — water mixtures) and on octadecylsilica (ODS) (eluents: methanol — 0.025 M KH₂PO₄ mixtures) was determined, and the relationship between retention and physicochemical parameters were evaluated by principal component analysis followed by two-dimensional nonlinear mapping and by cluster analysis as well as by canonical correlation analysis. Calculations proved that marked differences can be detected between the retention characteristics of PGC and ODS columns, and the electronic parameters of phenol derivatives have the highest impact on their retention. The comparison of various multivariate mathematical-statistical methods indicated that principal component analysis followed by two dimensional non-linear mapping is the most appropriate method for the evaluation of large data matrices in RP-HPLC.     

Fuzzy theory in analytical chemistry

The concept of fuzzy theory is described in order to provide the analyst with the means for dealing with vague statements, uncertain observations or the fuzziness of human perception and interpretation, in general. In a theoretical part, basic notions of fuzzy theory are given, such as types of membership functions, operations with fuzzy sets, definitions of fuzzy numbers, points, functions, and relations, and the use of linguistic variables. The difference between fuzziness and probability is outlined. The applications section demonstrates advantages of fuzzy theory methods compared to common mathematical methods with respect to data handling for calibration of analytical methods, to classification of Chromatographie and spectroscopic patterns, to component identification and multicomponent analysis, and to designing fuzzy expert systems for selection of analytical procedures.     

Improvement of the electrophoretic protein profiles of Leguminosae gums extracts using gamanase and application to the evaluation of carob-guar mixtures

A quantitative assay for guar gum in carob gum, based on the extraction of proteins in acetonitrile-water (7:3), separation by capillary electrophoresis and multiple linear regression (MLR) using the areas of nine selected peaks as predictors, was improved by performing the extraction in the presence of gamanase. In the absence of the enzyme, peak migration times and areas depended on the guar content, which complicated peak identification and evaluation. Manual correction of the migration times by comparison with standard electropherograms obtained with pure carob and carob-guar mixtures was required; however, when the proteins were extracted under sonication at 60 °C for 30 min in the presence of gamanase, the migration times and peak areas did not vary with the composition of the carob-guar mixtures, and its reproducibility improved largely. These effects were attributed to the reduction of the viscosity of the extracts and the removal of the galactomannose interactions with the proteins and the capillary walls. Peak identification and evaluation were easily and directly performed on these electropherograms without further processing. An MLR model constructed with 36 carob-guar mixtures containing up to 20% guar, and by measuring the areas of 12 selected peaks and using eight of them as predictors, yielded a detection limit of 2.8% guar (α=β=0.05 criterion). A model of similar quality was obtained by partial least-squares (PLS) regression.     

Synthese und thermische Eigenschaften von molekularen Clusterverbindungen zusammengesetzt aus Elementen der Gruppen 11‐13‐16

Syntheses and Thermal Properties of Cluster Molecules, formed from Groups 11‐13‐16 Elements In the presence of PPh₃, CuX (X = Cl, CH₃COO) or AgOC(O)C₆H₅ and GaCl₃ react in THF with S(SiMe₃)₂ or Se(SiMe₃)₂ to yield [Cu₆Ga₈Cl₄S₁₃(PPh₃)₆] ( 1 ), [Cu₆Ga₈Cl₄Se₁₃(PPh₃)₆] ( 2 ), [Ag₆Ga₈Cl₄S₁₃(PPh₃)₆] ( 4 ) and [Ag₆Ga₈Cl₄Se₁₃(PPh₃)₆] ( 5 ). The use of PⁿPr₂Ph instead of PPh₃ and subsequent layering with n‐hexane leads to the formation of the cluster [Cu₆Ga₈Cl₄Se₁₃(PⁿPr₂Ph)₁₂] ( 3a , 3b ). Reaction of CuCl, GaCl₃ and PⁿPr₃ with Se(SiMe₃)₂ in THF results in the crystallisation of the ionic cluster (HPⁿPr₃)₂[Cu₂Ga₄Cl₄Se₆(PⁿPr₃)₄] ( 6 ). The structures of 1 — 6 were determined by X‐ray single crystal structure analysis. Thermogravimetric measurements of the cluster molecules and powder diffraction patterns of the remaining powders reveal the potential use of them as single source precursor compounds for the synthesis of the related ternary solid state materials.     

Development and validation of an analytical method for detection of estrogens in water

An analytical procedure enabling routine analysis of four environmental estrogens at concentrations below 1 ng L^–1 in estuarine water samples has been developed and validated. The method includes extraction of water samples using solid-phase extraction discs and detection by gas chromatography (GC) with tandem mass spectrometry (MS–MS) in electron-impact (EI) mode. The targeted estrogens included 17- and 17-estradiol (aE2, bE2), estrone (E1), and 17-ethinylestradiol (EE2), all known environmental endocrine disruptors. Method performance characteristics, for example trueness, recovery, calibration, precision, accuracy, limit of quantification (LOQ), and the stability of the compounds are presented for each of the selected estrogens. Application of the procedure to water samples from the Scheldt estuary (Belgium – The Netherlands), a polluted estuary with reported incidences of environmental endocrine disruption, revealed that E1 was detected most frequently at concentrations up to 7 ng L^–1. aE2 was detected once only and concentrations of bE2 and EE2 were below the LOQ.Presented at the 9th FECS Conference on Chemistry and the Environment, Bordeaux, France, 29 August–1 September 2004     

Vibrational analysis of 3-trifluoromethylphenol

The molecular geometry and molecular vibrations of 3-trifluoromethylphenol have been investigated by means of quantum chemical calculations and vibrational spectroscopy. The computations indicated the preference of the conformer with the OH hydrogen pointing in the direction of the trifluoromethyl group by 0.9 kJ/mol with respect to the anti conformer. FT-IR spectra of the vapour and CCl₄ solution as well as FT-IR and FT-Raman spectra of the pure liquid have been recorded in the range of 4000–150 cm⁻¹. The interpretation of the spectra was based on a scaled quantum mechanical (SQM) analysis for which the initial force field was calculated at the Becke3-Lee-Yang-Parr (B3LYP) DFT level supplemented with a 6-311++G** basis set. Using 11 scale factors refined in the present study an rms deviation of 7.6 cm⁻¹ between the experimental and SQM frequencies has been achieved. On the basis of the computations 40 of the total of 42 fundamentals of the title compound have been assigned.     

Refining adsorption parameters of n-butyl alcohol at the interface of mercury electrode with aqueous NaF and Na2SO4 solutions by correcting the adsorbate concentration

As an adjunct to the regression analysis of differential capacitance curves, which allows refining the adsorption parameters, a program, which takes into account possible errors in volume concentrations of organic substances, is developed. Using this procedure, the earlier data on the differential capacitance of a mercury electrode in aqueous solutions of normal butanol (1-BuOH) containing either 0.1 M NaF or 0.05 and 0.5 M Na₂SO₄ as the supporting electrolyte are analyzed. This allows obtaining the most accurate values of adsorption parameters for the systems mentioned above within the framework of the model of two parallel capacitors and the Frumkin isotherm. It is shown that, when a linear dependence of the intermolecular interaction parameter on the electrode potential is taken into account, the standard deviation of experimental capacitance values from those calculated using the mentioned model is 6.8–8.8%, which points to very high accuracy of this phenomenological model.     

Analysis to obtain precise density fluctuation of supercritical fluids by small-angle X-ray scattering

A procedure of analysis for small-angle X-ray scattering (SAXS) data has been established to obtain density fluctuation of supercritical fluids near the critical point. It is indispensable for the certain analysis to utilize both of high-quality SAXS data measured under stable thermodynamic condition and accurate P–ρ–T data in supercritical region. As a standard example, SAXS measurements have been performed for supercritical CO₂, which is a suitable sample satisfying the condition for both experiment and analysis. The measurements were carried out along four isothermal conditions at reduced temperature of T_r = T/T_c = 1.020, 1.022, 1.043 and 1.064. Comparing the experimental density fluctuation with calculated one from the most reliable equation of state, the differences are within 8% at most.     

流动注射在线液—液萃取原子吸收光谱法测定生物样品中的铅

本文利用所设计的一种新型流动注射液－液萃取重力分相器，建立了流动注射液溶剂萃取原子吸收光谱法测定铅的新方法，详细地研究了流动注射在线萃取的实验条件及流路系统，方法的精密度和检出限分别为２．５％（ｎ＝１１）和２．８μｇ／Ｌ（ｋ＝３）。用拟定的方法测定了峰蛹，粮食等生物样品中的铅，结果与参考值相吻合。     

活性酚醛树脂中羟甲基含量的测定

本文提出一种酚醛树脂中羟甲基含量的化学分析法，分别以＾１３ＣＮＭＲ和化学分析法测定酚醛树脂的羟甲基含量。将两种测试结果与已知的投料量进行比较，证明所建立的化学分析法可行。