Determination of pyrethroid metabolites in human urine by capillary gas chromatography-mass spectrometry

Summary An analytical method for the simultaneous determination of the pyrethroid metabolites cis and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylic acid, cis 3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylic acid, 3-phenoxybenzoic acid and 4-fluoro-3-phenoxybenzoic acid in human urine samples is described. The urine is subjected to acid-induced hydrolysis followed by exhaustive solvent extraction, covering both conjugated and free acids, followed by a common derivatisation step yielding the corresponding methyl esters. Quantitation was by diastereomeric, capillary gas chromatography-mass spectrometry. It appears that 4-fluoro-3-phenoxybenzoic acid is a characteristic urinary marker for cyfluthrin exposure. The limits of determination are 0.5–1.0 g L^–1 urine depending on the metabolites concerned. The applicability of the method was tested on urine samples from pest control operators exposed occupationally to cypermethrin and cyfluthrin.     

Determination of trace levels of pyrethroid metabolites in human urine by capillary gas chromatography-high resolution mass spectrometry with negative chemical ionization

Summary Applications of high-resolution gas chromatography and high-resolution mass spectrometry (GC-MS) for identification and quantitation of trace amounts of pyrethroid metabolites in human urine samples are demonstrated. The method covers the pyrethroid metabolitescis- andtrans-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane carboxylic acid (cis- andtrans-DCCA),cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylic acid (cis-DBCA), 4-fluoro-3-phenoxybenzoic acid (FPBA), and 3-phenoxybenzoic acid (3-PBA). After acid-induced hydrolysis of urine samples and exhaustive solvent extraction, a carbodiimide-coupled esterification of the free carboxylic acids with hexafluoroisopropanol (HFIP) is applied. Identification of the derivatives formed is achieved by low-resolution electron-impact mass spectrometry (EIMS) using an ion-trap detector. Quantitation was by capillary gas chromatography—high-resolution mass spectrometry using negative chemical ionization (GC-NCIMS). 2-Phenoxybenzoic acid (2-PBA) served as internal standard. The limits of detection forcis- andtrans-DCCA,cis-DBCA, FPBA and 3-PBA were 0.03 μg L⁻¹ or below. The applicability of the presented method was tested on urine samples of persons exposed to low levels of pyrethroids.     

Varieties of operator semigroups representing partitions

We consider a variety of commutative operator semigroups, that is, of algebras with a unary operation and a binary commutative and associative operation. Asubpartition of a set is a partition of a subset of the set. For each integern>0, we represent the subpartitions on ann-element set asn-ary terms in the variety. We determine necessary and sufficient conditions on the variety ensuring that there be no constant terms and, for eachn>0, that these representing terms be all the essentiallyn-ary terms and moreover that distinct subpartitions yield distinct terms. We show that there is precisely one such variety of commutative operator semigroups.     

Identification of surgical practice patterns using evolutionary cluster analysis

Modern data analysis and machine learning are strongly dependent on efficient search techniques. However, in general, further exploration into high-dimensional and multi-modal spaces is needed, and moreover, many real-world problems exhibit inaccurate, noisy, discrete and complex data. Thus, robust methods of optimization are often required to generate results suitable for these data. Some algorithms that imitate certain natural principles, namely the so-called evolutionary algorithms, have been used in different fields with great success. In this paper, we apply a variant of Particle Swarm Optimization (PSO), recently introduced by the authors, to partitional clustering of a real-world data set to distinguish between perioperative practices and associate them with some unknown relevant facts. Our data were obtained from a survey conducted in Spain based on a pool of colorectal surgeons. The PSO derivative we consider here: (i) is adapted to consider mixed discrete-continuous optimization, with statistical clustering criteria arranged to take these types of mixed measures; (ii) is able to find optimum or near-optimum solutions much more efficiently and with considerably less computational effort because of the richer population diversity it introduces; and (iii) is able to select the right parameter values through self-adaptive dynamic parameter control, thus overcoming the cumbersome aspect common to all metaheuristics.     

Vibrational characterization of simple peptides using cryogenic infrared photodissociation of H2-tagged, mass-selected ions

We present infrared photodissociation spectra of two protonated peptides that are cooled in a ~10 K quadrupole ion trap and "tagged" with weakly bound H(2) molecules. Spectra are recorded over the range of 600-4300 cm(-1) using a table-top laser source, and are shown to result from one-photon absorption events. This arrangement is demonstrated to recover sharp (Δν ~6 cm(-1)) transitions throughout the fingerprint region, despite the very high density of vibrational states in this energy range. The fundamentals associated with all of the signature N-H and C=O stretching bands are completely resolved. To address the site-specificity of the C=O stretches near 1800 cm(-1), we incorporated one (13)C into the tripeptide. The labeling affects only one line in the complex spectrum, indicating that each C=O oscillator contributes a single distinct band, effectively "reporting" its local chemical environment. For both peptides, analysis of the resulting band patterns indicates that only one isomeric form is generated upon cooling the ions initially at room temperature into the H(2) tagging regime.     

Orthogonal latin square graphs

An orthogonal latin square graph (OLSG) is one in which the vertices are latin squares of the same order and on the same symbols, and two vertices are adjacent if and only if the latin squares are orthogonal. If G is an arbitrary finite graph, we say that G is realizable as an OLSG if there is an OLSG isomorphic to G. The spectrum of G [Spec(G)] is defined as the set of all integers n that there is a realization of G by latin squares of order n. The two basic theorems proved here are (1) every graph is realizable and (2) for any graph G, Spec G contains all but a finite set of integers. A number of examples are given that point to a number of wide open questions. An example of such a question is how to classify the graphs for which a given n lies in the spectrum.