反相流动注射化学发光法测定单宁

在碱性介质中 ,单宁对高碘酸钾氧化鲁米诺的化学发光反应有较强的增敏作用 ,据此建立了反相流动注射化学发光测定单宁的新方法 ,并研究了最佳反应条件。该方法快速、准确、线性范围宽 ,测定单宁的检出限为 1 .1 2× 1 0 - 9g/ m L,方法的线性范围为 2 .0× 1 0 - 8～ 6 .0× 1 0 - 6 g/ m L,对于 4.0× 1 0 - 6 g/ m L单宁 1 0次测定的相对标准偏差为 0 .79%。应用于中药五倍子、诃子中单宁的测定 ,结果满意     

Pattern of separatrices and intrinsic reaction coordinates for degenerate thermal rearrangements

A structurally stable model of the standard adiabatic gradient field of the potential energy surface for certain pericyclic reactions is derived.These reactions are not subjected to the principles of orbital isomerism or to the Woodward-Hoffmann rules.Use is made of a principle established by Ariel Fernández and Oktay Sinanolu which precludes direct meta-IRC connections between transition states.It is shown that Jahn-Teller isomers of the singlet biradicals involved in the process are not interconvertible since the biradical configuration is not a transition state but a critical point with Hessian matrix with two negative eigenvalues.The topological features of the PES obtained by combinatorial methods are in full agreement with earlier results obtained from MINDO calculations.     

Fast screening of anabolic steroids and other banned doping substances in human urine by gas chromatography/tandem mass spectrometry

A fast and sensitive method for the comprehensive screening of anabolic agents and other banned doping substances using gas chromatography/tandem mass spectrometry (GC/MS/MS) with an external ionization ion trap mass spectrometer is presented. The method takes advantage of the resolving power of MS/MS to eliminate background interferences, thus speeding up the chromatographic analysis. For each compound, different fragmentation reactions were studied and their collision energies optimized to obtain the best sensitivity in terms of their signal-to-noise ratio (S/N). A dramatic reduction in overall analysis time was achieved compared with other common approaches. More than 50 substances could finally be monitored in less than 7.4 min with detection limits (S/N >3) lower than 0.5 ng ml(-1) for most of the compounds with special sensitivity requirements according to the International Olympic Committee (IOC). A validation procedure for qualitative analysis was performed. The selectivity of the method showed that no interfering peaks were observed at the retention time of the analytes. Good intermediate precision, below 25% for most of the compounds, and robustness were observed. The optimized method was successfully applied to analyse more than 100 real human urine samples with optimum sensitivity and specificity rates.     

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。     

Mass distribution in a dynamic sample zone inside a flow injection manifold: modelling integrated conductimetric profiles

A mathematical model for fitting the experimental ICM (integrated conductimetric method) curves developed by the authors in a previous work, is presented for the first time in this study. The proposed model fits the experimental curves with great precision and allows to predict physical dispersion for single-line flow injection system. The correlation of the model’s parameters with typical reactionless FIA peak parameters is also assessed. The IDQ coefficient—a novel dispersion estimator previously reported by the authors—can also be predicted when operational FIA variables are changed. Experimental and modelled profiles are compared as a function of the system’s variables, showing an excellent agreement.     

Splitless injection of up to hundreds of microliters of liquid samples in capillary GC: Part II,experimental results

Sample evaporation in splitless injection of large volumes is rapid: depending on the experiment, results indicate that 200 μl of hexane, for instance, evaporates in 2–10 s, producing vapor at a rate of many hundreds of milliliters per minute. A 60 × 4 mm packed bed of 20–35 mesh Tenax TA enabled injection of 200 μl volumes of all solvents tested, and even 1 ml injections were possible provided they were performed over a period of 30 s. Retention of volatile sample components depends on the sample solvent, the injection volume, and the injection speed, but only little on the injector temperature. Losses of n-tridecane varied from hardly 15 % (when dissolved in pentane) to ca 60 % (ethyl acetate); losses of n-heptadecane were usually below 20 %. The column temperature during injection should be at least ca 20–30°C above the standard solvent boiling point.     

Thin layer distillation for matrix isolation in flow analysis

Analyte transfer from the matrix in a thin layer distillation (TLD) cell and its subsequent measurement were investigated in a flow injection configuration. We designed the cell such that the donor and acceptor streams flowed in parallel channels separated by a thin dividing wall. The matrix transfer process involved room-temperature distillation of the analyte into the headspace of the TLD cell and its subsequent condensation/uptake by a concurrently flowing acceptor stream. There are no membranes; hence there are no membrane-related problems. The TLD system design was optimized with respect to its dimensions and operational parameters. Throughput and sensitivity were compared with a conventional pervaporation flow injection (PFI) system for ammonia and five different amines. For the higher molecular mass amines, the TLD approach provided comparable or superior performance. The TLD technique should be an attractive approach for online analysis of volatile chemical species in ‘dirty’ samples, especially for volatile analytes of higher molecular mass.     

Proline-catalyzed asymmetric aldol reactions of tetrahydro-4H-thiopyran-4-one with aldehydes

Proline-catalyzed enantioselective direct intermolecular aldol reactions of tetrahydro-4H-thiopyran-4-one with various aldehydes give anti adducts with high diastereo- and enantioselectivities in moderate to excellent yields. With the aromatic aldehydes best results were obtained in wet DMF whereas dry DMSO generally was superior with the aliphatic aldehydes. Desulfurization of the adducts with Raney Ni provides products equivalent to aldols from 3-pentanone with potential applications in polypropionate synthesis.     

The impact of flow injection on modern chemical analysis: has it fulfilled our expectations? And where are we going?

Presenting a condensation of the opening lecture of the 12th ICFIA conference, this communication presents a view of the impact that flow injection analysis (FIA) has had on modern analytical chemistry, evaluated both within the academic community and outside it, i.e. in “industry”. The ensuing developments of FIA, encompassing sequential injection analysis (SIA) and bead injection lab-on-valve (BI-LOV), are described and their individual features discussed. Finally, some recent results of the activities from the author’s own research group are briefly mentioned.     

Amperometric detection of hydrazine by cyclic voltammetry and flow injection analysis using ruthenium modified glassy carbon electrodes

Glassy carbon electrodes modified with (5-amino-1,10-phenanthroline)bis(bipyridine)ruthium(II) chloride hydrate, [(bpy)₂Ru(5-phenNH₂)]Cl₂·H₂O, are shown to oxidize hydrazine with excellent sensitivity. The presence of an amine group on the ruthenium complex facilitates electropolymerization onto the electrode surface. Using cyclic voltammetry, a large catalytic current is observed upon oxidation of hydrazine in phosphate buffer (pH 5.0), compared to the current obtained from the ruthenium-modified electrode with no hydrazine present. The sensitivity of cyclic voltammetry is sufficient for obtaining a linear calibration curve for hydrazine over the range of 10⁻⁵ to 10⁻² M. Hydrodynamic amperometry was used to determine the working potential for flow injection analysis. The limit of detection for hydrazine was determined to be 8.5 μM using FIA. The thickness of these films was shown to increase linearly with the number of electropolymerization cycles, in the range of 1000-2500 nm for 5-20 cycles, respectively, using Rutherford backscattering spectrometry (RBS). RBS analysis also suggests that the film is multilayered with the outermost layers containing a high ruthenium concentration, followed by layers where the concentration of ruthenium decreases linearly and approaches zero at the electrode surface.