Setting up of recovery profiles: A tool to perform the compliance with recovery requirements for residue analysis

The use of the recovery term has presented some confusion in Analytical Chemistry. Recent IUPAC recommendations propose to distinguish between two terms: recovery or recovery factor, ℜ, and apparent recovery, ℜ*. Apparent recovery includes recovery factor and a new recovery term proposed in this paper, named calibration recovery, ℜ^C, which depends of the type of systematic error due to the matrix effect (constant and/or proportional) and is related to the applied calibration methodology. This paper highlights the dependence of the calibration recovery on the sample analyte concentration and, for extension, of the apparent recovery, defines the recovery profile, and makes evident the need to determine a “fit for purpose” analyte concentration interval to comply with a regulated recovery requirements. An approach to estimate the calibration recovery and its associated uncertainty in relation to the above-mentioned dependence is presented. The usefulness of the proposed methodology has been shown in the quantification of a pesticide by GC-ECD for assessing dermal exposure.     

Size exclusion chromatographic characterization of sodium hyaluronate fractions prepared by high energetic sonication

Summary A high molecular weight sodium hyaluronate isolated from rooster combs was degraded by ultrasonication. High-performance size exclusion chromatography allowed rapid and accurate determination of molecular weight parameters (M_z, M_w, M_n) and distributions. The time dependence of hyaluronan ultrasonication to the molecular characteristics of the polymer was investigated. A non-random nature of the degradation process was demonstrated and the reciprocal M_n value was found to be linearly proportional to the time of ultrasonication.     

Extraction of microamounts of calcium in the two-phase water-HCl-18-crown-6-nitrobenzene-hydrogen dicarbollylcobaltate system

Summary Extraction of microamounts of calcium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B^-) in the presence of 18-crown-6 (18C6, L) has been investigated. The equilibrium data have been explained assuming that the complexes HL⁺, CaL²⁺and CaL are extracted into the organic phase. The values of extraction and stability constants of the complex species in nitrobenzene saturated with water have been determined.     

Reactions of isomeric 6-methyl-2-methylthio-4cyanomethoxypyrimidine and 6-methyl-2methylthio-3-cyanomethylpyrimidinone-4 with n-nucleophiles

It was found that 6-methyl-2-methylthio-4-cyanomethoxypyrimidine (O-isomer) reacted via the cyano group with ammonia and hydroxylamine to give an amldine and an amidoxime respectively. The O-isomer did not react with either primary or secondary amines under similar conditions, but nucleophilic substitution at position 2 of the O-isomer was effected by converting the 2-methylthio group into a 2-methylsu fonyl. 6-Methyl-2methylthio-3-cyanomethylpyrimidinone-4 (N₃-isomer) formed imidazo[1, 2-a]pyrirnidinones-5 with ammonia and primary amines, 2-amino-6-methyl-3-cyanomethylpyrirrtidinones-4 with secondary amines and either an amidoxime or an imidazo[1, 2-a]pyrimidinone-5 with hydroxylamine, depending on the reaction temperature.Vilnius University. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 703-707, May, 1996. Original article submitted November 3, 1995.     

1H and 13C assignments of two new triterpenes from Cladocolea grahami

The structure elucidation and 1H and 13C assignments of the new triterpenes 3beta-palmitoxy-7beta-hydroxyolean-12-ene (1) and its hydrolysis product 3beta,7beta-dihydroxyolean-12-ene (2) and 3beta-sn-glyceroyl-(1'-palmitoxy)urs-12-ene (3), isolated from the aerial parts of Cladocolea grahami (Loranthaceae), are reported.     

Unipolar conductivity of donor or acceptor solutions

Donor or acceptor compounds in apolar organic solvents become charged at a high-field strength electrode and are driven to a surrounding low-field strength electrode of opposite sign. At 10 kV per cm the solutions conduct 3–7 times better when the highly charged electrode is positive in donor solutions. The opposite situation occurs in acceptor solutions.     

516—Synthetic and biological membranes

Biological cell membranes are compared to artificially produced permselective membranes. In spite of the difference in their thickness and electric resistance it is shown that they are similar in many important aspects, and the behaviour of synthetic membranes can explain very many points in the behaviour of cell membranes, especially axons. It is stressed that it is seldom necessary to assume unproven channels in biological membranes which are specific in the transport of a single ion species. Most of the phenomena of selectivity, opening and closing of such membranes can be explained by the influence of pH on membrane sites, by their poisoning with higly charged and/or large counter-ions. The borderline between two oppositely charged regions of a mosaic membrane opens up because it can be traversed by both positive and negative ions and permselectively is lost. Bipolar membranes rectify the current. Amphoteric membranes undergo very complex changes in conducting properties and permselectively with pH, especially when allowance is made for the weakly dissociated sites contained within these membranes. It is suggested that black lipid membranes made in the laboratory could be used to elucidate new points of similarity if they were used under similar conditions to our technical membranes.     

Novel terpenoids from the West Indian sea whip Pseudopterogorgia elisabethae (Bayer). Elisapterosins A and B: rearranged diterpenes possessing an unprecedented cagelike framework

Four diterpenes and a nor-diterpenoid, all of which possess unusual carbocyclic skeletons, were isolated from the hexane solubles of the West Indian gorgonian Pseudopterogorgia elisabethae. The structures and relative configurations of novel metabolites elisabethin D (2), elisabethin D acetate (3), 3-epi-elisabanolide (5), elisapterosin A (6), and elisapterosin B (7) were elucidated by interpretation of overall spectral data, which included 2D NMR correlation methods, IR, UV, and accurate mass measurements (HREI-MS and HRFAB-MS), chemical reactions, and X-ray diffraction analyses. The tetracyclic carbon skeleton of the elisapterosins is undescribed and constitutes a new class of C(20) rearranged diterpenes. Elisapterosin B displays strong in vitro anti-tuberculosis activity.     

Matched/Mismatched interaction of a cyclic hexapeptide with ion pairs containing chiral cations and chiral anions

The binding of a chiral quaternary ammonium ion to a cyclopeptide containing aromatic amino acid subunits is affected not only by the configuration of the cation but also by the configuration of the chiral counterion. Analysis of the binding equilibria shows that complex formation involves interaction of the whole ion pair with the host indicating that steric requirements of the anion influence complex geometry and stability.     

Assembly of the hexameric Escherichia coli arginine repressor investigated by nano-electrospray ionization time-of-flight mass spectrometry

The arginine repressor (ArgR) from Escherichia coli regulates genes for L-arginine metabolism and is a required recombination factor for colE1 plasmid replication. Both functions require binding of L-arginine to the protein. In this work, nano-electrospray ionization time-of-flight mass spectrometry (nano-ESI-TOFMS) is used to study conformational and oligomeric states of intact ArgR and its isolated structural domains. In agreement with X-ray diffraction studies, it is shown that ArgR oligomerizes to form hexamers in both the presence and absence of L-arginine, and the basic unit of oligomerization appears to be the trimer. Higher-order assembly into dodecamers is also detected. The isolated C-terminal domain is found to associate into trimers and hexamers whereas the N-terminal domain is detected in its monomeric form. The observed species distributions suggest a role for the N-terminal domain in hexamer stabilization.