Use of long-chain alkylamines for preconcentration and determination of traces of molybdenum, tungsten and rhenium by atomic-absorption spectroscopy-II: molybdenum in soils, sediments and natural waters

Molybdenum is extracted as the thiocyanate complex with the quaternary long-chain aliphatic amine Aliquat 336 in chloroform, followed by evaporation of the solvent, dissolution in MIBK, and atomic-absorption spectroscopy. The method is simple, rapid and sensitive, with few interference problems for the determination of the Mo content of soils and sediments in the range 0.1-1.0 ppm with a relative standard deviation better than 5% when 1-g samples are used. Quantitative extraction from large volumes of aqueous solution has also been confirmed, allowing the determination of Mo in natural waters in the ppM range.     

Spectrophotometric and fluorometric determination of traces of molybdenum in soils and plants

The reaction of the molybdenum oxypentathiocyanate ion with the dyestuff Rhodamine B (RhB) produces the ternary complex. MoO(SCN)(5)(RhB)(2) The formation of this complex is accompanied by a colour change and by extinction of the fluorescence of RhB. A spectrophotometric and fluorometric method for the determination of Mo has been developed from these observations. The method is free from interferences and has detection limits of 0.1 mug and 0.05 mug of Mo for absorption and fluorescence measurements, respectively. The spectrophotometric method is applicable to the determination of Mo in soils and the fluorometric method is suited to the determination of Mo in plants.     

Exploring privileged structures: the combinatorial synthesis of cyclic peptides

Head-to-tail cyclic peptides have been reported to bind to multiple, unrelated classes of receptor with high affinity. They may therefore be considered to be privileged structures. This review outlines the strategies by which both macrocyclic cyclic peptides and cyclic dipeptides or diketopiperazines have been synthesised in combinatorial libraries. It also briefly outlines some of the biological applications of these molecules, thereby justifying their inclusion as privileged structures.     

Particulate light scattering dependence upon solute compound in atomic flame spectrometry

The relative intensities of light by compounds of 46 elements have been measured following irradiation, by electrodeless discharge lamps, of the particles formed in H₂-air and C₂H₂-air flames. A procedure which enables signals from the detector to be normalized allows comparison of results which vary greatly in absolute magnitude. Scattering by unseeded flames is shown to be significant when the flame is not in thermal equilibrium with the environment. In an H₂-air flame, scattering resulting from the nebulization of 0.05 m solutions containing the following elements is found to decrease in the series Th > La > Al > Si > Ir > U > Pt > Rh ? Ru > Ti > Zr ? Ce ? Ca > Os ? Mn ? Tl ? Pd. Compounds of other elements investigated did not lead to significant scattered radiation. The scattering is dependent upon flame composition and temperature, the form of the element as nebulized and apparently the extent of cohesion between non-volatile particles. Light scattering by the Pt group metals is considered to occur as a result of interatomic bonding.     

Conformational searching using a population-based incremental learning algorithm

A new population-based incremental learning algorithm for conformational searching of molecules is presented. This algorithm is particularly effective at determining, by relatively small number of energy minimizations, global energy minima of large flexible molecules. The algorithm is also able to find a large set of low energy conformations of more rigid small molecules. The performance of the algorithm is relation to other algorithm is examined via the test molecules: C(18) H(38) , C(39)H(80) , cycloheptadecane and a set of five drug-like molecules.     

On the structure of random plane-oriented recursive trees and their branches

This paper is an investigation of the structural properties of random plane-oriented recursive trees and their branches. We begin by an enumeration of these trees and some general properties related to the outdegrees of nodes. Using generalized Pólya urn models we study the exact and limiting distributions of the size and the number of leaves in the branches of the tree. The exact distribution for the leaves in the branches is given by formulas involving second-order Eulerian numbers. A martingale central limit theorem for a linear combination of the number of leaves and the number of internal nodes is derived. The distribution of that linear combination is a mixture of normals with a beta distribution as its mixing density. The martingale central limit theorem allows easy determination of the limit laws governing the leaves in the branches. Furthermore, the asymptotic joint distribution of the number of nodes of outdegree 0, 1 and 2 is shown to be trivariate normal. © 1993 John Wiley & Sons, Inc.     

Comparison of high-performance liquid chromatography with electrochemical detection and gas chromatography-mass fragmentography for the assay of salsolinol, dopamine and dopamine metabolites in food and beverage samples

High-performance liquid chromatography with electrochemical detection (HPLC-ED) and combined gas chromatography--mass spectrometry in the single-ion monitoring mode (GC--MS-SIM) have been used for the determination of salsolinol, dopamine, 3,4-dihydroxyphenylacetic acid, 3,4-dihydroxyphenylethanol and norepinephrine in a selection of food and beverage samples. The unique specificity of the SIM mode allows a simple one-step extraction to be used even for complex sample matrices. We have been able to demonstrate the quantitative and qualitative advantages offered by GC--MS over HPLC--ED by direct comparison of the chromatographic data obtained. We demonstrate that the specificity of SIM and the benefits offered by the incorporation of deuterated internal standards make GC--MS-SIM the method of choice for valid identification and precise quantitation of salsolinol, dopamine and dopamine metabolites in a complex sample matrix.     

On-line dual-wavelenth instrumentation for antomatic correction of light scattering interference in dispersive atomic fluorescence spectrometry

The design basis of a dual detection channel spectrometer for general application in atomic fluorescence analysis is discussed. Low frequency modulation of the radiation from a single light source is employed with one channel set at a fluorescence wavelength while the second channel measures the magnitude of scattering at a non-fluorescent wavelength. The instrument has been applied to the analysis of trace Au and Cd in high scattering matrix solutions. The statistical treatment of data, and the method of calculating detection limits, is discussed.