Extraction and quantitation of furanic compounds dissolved in oils

There is often a need to calculate isotopic uranium activities from total uranium mass or gamma spectrometry measurement data. This calculation is based on a model of the relationship of the²³⁴U activity to that of²³⁵U since both are enriched together in the normal gaseous diffusion enrichment process. This paper presents equations for calculating these activities that have been developed from several sources of data. These equations have been used for several characterization studies and have produced very good results when compared to results from actual isotopic uranium analyses. However, because the variability in the model causes significant uncertainty in the calculated results, alpha-spectrometry is recommended for critical applications.     

A method for the evaluation of the Cs-137 ingestion following the Chernobyl accident

This paper gives the average ingestion levels of¹³⁷Cs, released during the Chernobyl accident, for three population groups living in different regions of Italy. The ingestions were determined experimentally by measuring reconstructed total diets that were collected in the three areas.A comparison between this data and the ingestion levels, estimated by using the¹³⁷Cs concentration levels measured in single food products and the national food consumption data, shows that the last method over-estimates the ingestion.Finally, it is shown that the ingestion levels of¹³⁷Cs, as determined by measuring the reconstructed total diets, the internal body burden as measured directly by whole body counting, and urinary excretion are consistant.     

Superexcited states of CH4

The energy spectrum of a superexcited state (the different between the total photoabsorption and photoionization cross section) is calculated using ultraviolet photoelectron data for CH₄ and oscillator strength data for the iso-electronic atom, Ne. From this estimate we have concluded that the superexcited state of CH₄ is interpreted in terms of Jahn-Teller distortion of high Rydberg states referring to the ²T₂ state of CH⁺₄. The inconsistency between the data of the UV optical spectrum and results of other measurements or analyses is pointed out and discussed.     

Tritium transfer from diet to human

The direct transfer of organically-bound³H (OBT) of diet to that in the human body is reasonable, since the human body needs essential amino acids and fatty acids. Metabolic models of³H which were recently developed for the human body took this direct incorporation into account. Data for fallout³H in diet and human tissues were used to validate model parameters, although such data are relatively scarce. However, a simple equilibrium between dietary³H and human body³H was assumed for such validations. The simple equilibrium assumption means completely neglecting past³H concentration in the human body. When the model consists of compartments which have long mean residence times, estimated³H concentrations in the human body from the simple equilibrium assumption can differ significantly from results of adequate calculation considering contribution of past human³H concentrations. The examples of such calculations are described in this paper. Results of the calculations show that suitable environmental³H transfer models are necessary to use fallout³H data for the validation of³H metabolism models.     

Comparative Studies of Selected Criteria Enabling Optimization of the Extraction of Polar Biologically Active Compounds from Alfalfa with Supercritical Carbon Dioxide

The aim of this research was to provide crucial and useful data about the selection of the optimization criteria of supercritical carbon dioxide extraction of alfalfa at a quarter-technical plant. The correlation between more general output, including total phenolics and flavonoids content, and a more specified composition of polar constituents was extensively studied. In all alfalfa extracts, polar bioactive constituents were analyzed by both spectrometric (general output) and chromatographic (detailed output) analyses. Eight specific phenolic acids and nine flavonoids were determined. The most dominant were salicylic acid (221.41 µg g⁻¹), ferulic acid (119.73 µg g⁻¹), quercetin (2.23 µg g⁻¹), and apigenin (2.60 µg g⁻¹). For all seventeen analyzed compounds, response surface methodology and analysis of variance were used to provide the optimal conditions of supercritical fluid extraction for each individual constituent. The obtained data have shown that eight of those compounds have a similar range of optimal process parameters, being significantly analogous for optimization based on total flavonoid content.     

Towards J/mol Accuracy for the Cohesive Energy of Solid Argon

The cohesive energies of argon in its cubic and hexagonal closed packed structures are computed with an unprecedented accuracy of about 5 J mol^?1 (corresponding to 0.05 % of the total cohesive energy). The same relative accuracy with respect to experimental data is also found for the face‐centered cubic lattice constant deviating by ca. 0.003 Å. This level of accuracy was enabled by using high‐level theoretical, wave‐function‐based methods within a many‐body decomposition of the interaction energy. Static contributions of two‐, three‐, and four‐body fragments of the crystal are all individually converged to sub‐J mol^?1 accuracy and complemented by harmonic and anharmonic vibrational corrections. Computational chemistry is thus achieving or even surpassing experimental accuracy for the solid‐state rare gases.     

The effect of intramolecular‐hydrogen bonds in the synthesis of novel imidates from a 13‐membered dioxadithia crown ether diester

The synthesis and structural properties of three novel imidates, 11,13‐bis‐(2‐amino‐ethylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane ( 2 ), 11,13‐bis‐(3‐aminopropylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane, ( 3 ) and 2,11‐dioxa‐5,8‐dithia‐13,16,19,22‐tetraazabicyclo[10.10.1]tricosa‐1(22),12‐diene, ( 4 ) have been described. These compounds were synthesized by treating 1,10‐dioxa‐4,7‐dithiacyclotridecane‐11,13‐diester ( 1 ) with the appropriate diamine under N₂ and their structures have been characterised by elemental analyses, ¹H‐ and ¹³C‐nmr, ir, and mass spectral studies. Elemental analyses and spectroscopic data support the proposed imidate structures. In addition, total energy and heat of formation (Figure 2) calculated for imidates 2a‐4a and 2b‐4b by the semiempirical AM1 calculations have shown that imidates 2b‐4b having intramolecular hydrogen bonds are more stable (5‐10 kcal/mol) than compounds 2a‐4a .     

Doubly labeled water analysis using cavity ring-down spectroscopy

The doubly labeled water method provides an objective and accurate measure of total energy expenditure in free‐living subjects and is considered the gold‐standard method for this measurement. Its use, however, is limited by the need to employ isotope ratio mass spectrometry (IRMS) to obtain the high‐precision isotopic abundance analyses needed to optimize the dose of expensive ¹⁸O‐labeled water. Recently, cavity‐ring down spectroscopy (CRDS) instruments have become commercially available and may serve as a less expensive alternative to IRMS. We compared the precision and accuracy of CRDS with those of IRMS for the measurement of total energy expenditure from urine specimens in 14 human subjects. The relative accuracy and precision (SD) for total body water was 0.5 ± 1% and for total energy expenditure was 0.5 ± 6%. The CRDS instrument displayed a memory between successive specimens of 5% for ¹⁸O and 9% for ²H. The memory necessitated carefully ordering of specimens to reduce isotopic disparity, performance of several injections of each specimen to condition the analyzer, and use of a mathematical memory correction on subsequent injections. These limited the specimen throughput to about one urine specimen per hour. CRDS provided accuracy and precision for isotope abundance measurements of urine that were comparable with those of IRMS. The memory problems were easily recognized by our experienced laboratory staff, but future efforts should be aimed at reducing the memory of the CRDS so that it would be less likely to result in poor reproducibility in laboratories using doubly labeled water for the first time. Copyright © 2010 John Wiley & Sons, Ltd.     

Multi-geometry241AmBe neutron irradiator: Design and calibration for total-body neutron activation analysis

Neutron activation analysis provides an accurate elemental assessment of body compositional compartments; the analytical technique identifies skeletal, muscle, protein, and fat masses. Our irradiator system uses 56²⁴¹AmBe sources (4.4·10⁷ n/s each) which can be arranged in four basic geometries to examine body sizes from a preterm infant (500 g, 30 cm) to a very large adult (120 kg, 2m). Both in vivo and human cadaver studies have been performed. Precisions of 1 to 2% for total body Ca, P, Na, and Cl have been obtained.     

Application of attenuated total reflectance Fourier transform infrared spectrometry to the determination of sodium percarbonate in washing powder detergent

In this paper, a novel and precise analytical procedure has been developed for quantitative determination of sodium percarbonate (SPC) in washing powder. The method is based on the partial least squares (PLS) treatment of data obtained by attenuated total reflectance Fourier transform infrared (ATR FT-IR) spectrometry in wavenumber region of 1435-1342 cm⁻¹. The statistical parameters such as R², RSD, SEC and SECV have been evaluated, and number of factors, number of scan and the resolution have been optimized. In this method R² and RSD for five independent analyses of a 0.552 g per 100 g solution of SPC, SEC for 10 standard samples and SECV for five validation samples were 0.998, 1.011, 0.002 and 0.039 respectively.Results obtained for six different commercial washing powders compared well with those obtained with a standard method.     

Carbon-13 NMR Studies: 82. Carbon-13 spectra of several 10-methyl-cis-decalins. Conformational preferences of some cis-decalin derivatives

The ¹³C spectra of a series of 21 cis-decalins, 17 of which bear 10-methyl substituents, have been recorded to examine geometrical and conformational effects on the ¹³C shieldings. Although the data for a few of the simpler examples have been reported, these compounds were examined to obtain results for a common medium and temperature. All of the derivatives are conformationally mobile and their spectra were examined as a function of temperature to obtain shieldings representative of the slow exchange limit. The examples include compounds which populate both available chair-chair conformations equally, some which exhibit a preference for one of these conformations and some which exist essentially in a single conformation. The data for the latter group combined with the observed temperature dependencies and results for other decalin systems led to specific assignments for each carbon. The internal consistency of the entire body of data offers strong support for these assignments. The conformational preferences observed for a number of decalones and Δ³-10-methyldecalin derivatives are discussed.     

Copper(II)–nickel(II) complexes of novel 1,9-dioxa-3,6-dithiacyclotridecane-10,12-dione and 1,4-dioxa-7,10-dithiacyclododecane-2,3-dione ligands

1,9-Dioxa-3,6-dithiacyclotridecane-10,12-dione (L¹), and 1,4-dioxa-7,10-dithiacyclododecane-2,3-dione, (L²), two novel ligands, and their mono- and di-nuclear copper(II) and/or nickel(II) complexes have been prepared and characterized by elemental analyses, ¹H- and ¹³C-n.m.r., i.r., magnetic moments and mass spectral studies. Elemental analyses, stochiometric and spectroscopic data on the complexes indicate that the metal ions are coordinated to the nitrogen, oxygen and sulphur atoms and the data support the proposed structure for the diones and their mono–dinuclear copper(II) complexes. Moreover, copper(II) complexes of the dione ligands have a 1:1 metal:ligand ratio.     

13C n.m.r. spectra of steroids —a survey and commentary

The literature on ¹³C n.m.r. examinations of steroids has been reviewed and the shielding data for over 400 examples are tubulated. The assignments for each compound have been considered and, where necessary, revised in the light of more recent evidence and for consistency throughout each series. The methods available for assignments are reviewed and, in many cases, illustrated with specific examples. The major practical features concerning ¹³C studies of steroids are discussed as a guide to the use of the technique. From the main body of shielding data, an extensive set of substituent effects has been generated to aid the examination of new systems. The utility and the limitations of these effects are described.     

Arsenic Speciation in Urine and Blood Reference Materials

Acute and chronic exposure to arsenic is a growing problem in the industrialized world. Arsenic is a potent carcinogen and toxin in humans. In the body, arsenic is metabolized to produce several species, including inorganic forms, such as trivalent (As^III) and pentavalent (As^V), and the methylated metabolites such as monomethylarsonic acid, (MMA^V), and dimethylarsinic acid (DMA^V), in addition to arsenobetaine (AsB) which is ingested and excreted from the body in the same form. Each of these species has been reported to possess a specific but different degree of toxicity. Thus, not only is the measurement of total As required, but also quantification of the individual metabolites is necessary to evaluate the toxicity and risk assessment of this element. There are a large number of reference materials that are used to validate methodology for the analysis of As in blood and urine, but they are limited to total As concentrations. In this study, the speciation of five arsenic metabolites is reported in blood and urine from commercial available control materials certified for total arsenic levels. The separation was performed with an anion exchange column using inductively coupled plasma mass spectrometry as a detector. Baseline separation was achieved for As^III, As^V, MMA^V, DMA^V, and AsB, allowing us to quantify all five species. Excellent agreement between the total arsenic levels and the sum of the speciated As levels was obtained.     

Synthesis,spectral, thermal,solid-state DC electrical conductivity and biological studies of Co(II) complexes with Schiff bases derived from 3-substituted-4-amino-5-hydrazino-1,2,4-triazole and substituted salicylaldehydes

A series of Co(II) complexes have been synthesized with Schiff bases derived from 3-substituted-4-amino-5-hydrazino-1,2,4-triazole and substituted salicylaldehydes. These complexes are insoluble in water but more soluble in DMF and DMSO. The complexes have been characterized by elemental analyses, spectral (IR, UV–Vis, ¹H-NMR, FAB-mass, fluorescence), magnetic, thermal, solid-state DC electrical conductivity and molar conductance data. The molar conductivity values indicate that they are non-electrolytes. The elemental analyses of the complexes suggest a stoichiometry of the type Co · L1–L16 · 2H₂O. The complexes have been considered as semiconductors on the basis of the solid-state DC electrical conductivity data. Fluorescence spectra of one Schiff base and its complex were investigated in various solvents and some of the Schiff bases and their complexes were evaluated for their antimicrobial activities.     

The direct total evaporation (DTE) method for TIMS analysis

The total evaporation (TE) method is an established analytical method for safeguards measurements of uranium and plutonium isotope-amount ratios using thermal ionization mass spectrometry. As fractionation effects are minimized in this analytical method, it is a method of choice in many practical applications that require high accuracy and precision isotope abundance ratio measurements. The speed of signal regulation is a critical parameter for a steady sample evaporation process. Standard TE methods use the data system to read the ion signal and its difference from the target intensity is used to determine the increment in which the filament is heated. The new, hardware-driven proprietary direct total evaporation method uses an analog regulator in the filament power supply with direct feedback of the detector intensity. Only target values are set by the data system initially. The filament heating and sample evaporation process is then carried out by the hardware. The data system just monitors, collects, and calculates the data. Due to the nature of electronic regulation the ion signal is kept stable for the duration of the run until the whole sample is consumed. For routine uranium isotopic analyses of the major isotope-amount ratio n(²³⁵U)/n(²³⁸U) using a modified MAT261 instrument with SPECTROMAT? hardware and software upgrades, precision (relative standard deviation, expressed as a percent) and accuracy (relative difference, expressed as a percent) of 0.05 % are obtained for low enriched and high enriched uranium certified reference materials.     

Design considerations for a neutron generator-based total-body irradiator

Summary The prompt- and delayed-gamma neutron activation techniques have been used for the non-invasive measurement of human body composition. In recent years, neutron irradiators have used only transuranic isotopic sources (^{238PuBe, 241}AmBe, ²⁵²Cf). However, in today’s security-minded environment, the use of alternate neutron sources may provide some advantages. We have examined several designs for an irradiator that would use a high-output, miniature D-T neutron generator (MF Physics). The use of this type of neutron source will lessen the storage, security, and transport issues associated with continuous-output isotopic neutron sources. To determine the scientific impact of this decision, we have performed Monte Carlo simulations (MCNP-4B2; Los Alamos National Laboratory) to aid in the design of the irradiator system, evaluating shielding materials, collimation, and source-to-subject distance, for the measurement of total body nitrogen (TBN). Based on internal flux distributions within the simulated body region of a subject, several design options were identified. The final design will be selected based on the optimization of precision, dose, and exposure time.     

Energy-Minimized Structures and Calculated and Experimental Isomer distributions in the hexaamine-cobalt(III) system [Co(L)2]3+ with the chiral facially-coordinating triamine (l = butane-1,2,4-triamine)

Butane- 1,2,4-triamine (trab) is the smallest tridentate aliphatic unsubstituted chiral triamine. With optically pure trab, there are three, with racemic trab five isomers of [Co(trab)₂]³⁺, One of the five isomers is centrosymmetrical, the others are chiral. For one of the isomers, there are four possible conformations (all combinations of chair and skew boat conformations for the chelate six ring of each ligand), for the others there exist only three independent conformers. All sixteen independent structures have been calculated by strain-energy minimization. The calculated isomer distribution, based on total strain energies corrected with statistical entropy contributions (21%:16%:16%:4%:43%, and 40%:30%:30%, for racemic and optically pure trab, respectively) are in excellent agreement with the experimental data based on HPLC and ¹³C-NMR analyses of equilibrium solutions of the hexaamine-Co(III) compounds prepared by oxygenation of aqueous solutions in presence of activated charcoal. The results are also briefly discussed in relation to possible stereoselectivity upon complexation of optically pure trab and a racemic chiral ligand to a transition-metal center.     

Speciation of Mercury in two Dimictic Lakes of North-East Germany During a Period of 600 Days

Abstract

The speciation of mercury was studied with respect to (a) dissolved atomic mercury, (b) dissolved ionic mercury, and (c) total mercury in two dimictic lakes of North-East Germany. Differential pulse anodic stripping voltammetry was used for the analyses. The results show that biological processes dominate the speciation. They are responsible for high concentrations of atomic mercury and also organomercury compounds. The oxidation of atomic mercury under environmental conditions in lake water is very slow, so that the equilibrium between Hg_aq° and Hg_aq and Hg_aq ²⁺ can only be established during long periods of decreased bioactivity, as in wintertime. The sedimentation of the detritus during summer leads to a very pronounced decrease of the overall mercury in the entire water body of the lakes.     

An absolute and relative rate study of the reaction of oh radicals with dimethyl sulfide

The gas phase reaction of OH radicals with dimethyl sulfide (CH₃SCH₃, DMS) has been studied using both an absolute and a relative technique at 295 ± 2 K and a total pressure of 1 atm. The absolute rate technique of pulse radiolysis combined with kinetic spectroscopy was applied. Using this technique a rate constant of (3.5 ± 0.2) × 10^?12 cm³ molecule^?1 s^?1 was obtained. For the relative rate method, rate constants for the reaction of OH with DMS were found to increase with increasing concentrations of added NO. These results are compared with the large body of kinetic and mechanistic data previously reported in the literature.