Benefits of the implementation of a metrological structure for water analyses

Traceability of measurements still often remains a non-operational notion for end-user chemists. A practical project, sponsored by the French Ministry of Research, has been conducted to evaluate and to demonstrate possible benefits of the implementation of a metrological structure for improvement of the quality of water analyses. LNE (Laboratoire National d'Essais) was in charge of the build up of the traceability chain in a concrete case of determination of some heavy metals (cadmium and lead) in a groundwater. Pure solutions for calibration and a matrix RM have been certified by LNE and then used by 46 labs (mainly French) in a inter-laboratory study. Results have shown a measurable bias in lead analysis in the groundwater for all methods in routine use by laboratories. This project has demonstrated the interest of a metrological approach for method calibration, method validation and estimation of measurement uncertainty.     

Control of Li2 wave packet dynamics by modification of the quantum mechanical amplitude of a single state

Sequences of pulses with different spectra are used to control rotational wave packet dynamics in Li(2) by exploiting quantum interference phenomena. Wave packet superpositions are excited in a two-step resonant Raman process by two different pulses. Interferences between individual states shared by both wave packets can be used to enhance or destroy specific components of a superposition by varying the time delay between the pulses and/or the relative phase within the pulses. Elimination of selected quantum beats is achieved by greater than 94% for each case. A simple, yet effective, method for generating different color phase-locked pairs of laser pulses in a liquid-crystal pulse shaper setup without the need for interferometric stabilization schemes is described. The ability to manipulate single states of a superposition is an important advancement for intuitive control schemes and provides a potential new approach for initialization schemes in the field of quantum information.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

Effects of lysophospholipids on membrane order of phosphatidylcholine

Lysophospholipids are known to play a role in a wide range of cellular processes involving membrane–protein or membrane–membrane interactions; however lysolipids–lamellar lipids interactions remain unclear. The effects of lysolipids on membrane order and dynamics were examined using optical birefringence and fluorescence techniques. We found that lysophosphatidic acid (LPA) induces a considerable disorder in chain orientation for synthetic lipid of dimyristoyl-phosphatidylcholines (DMPC), whereas a slight order for natural lipid of egg yolk phosphatidylcholine (Egg-PC), e.g. the chain order decreases by 10% at 0.1 mole ratio for DMPC in comparison with the membranes without LPA and increases by 3.4% at 0.09 mole ratio for Egg-PC. Also, membrane fluidity corresponds with the change in the chain disorder, namely, the fluidity increases for DMPC membranes, while decreases for Egg-PC membranes by addition of LPA. The difference in the effects of LPA is interpreted by a difference in the chain packing between the synthetic and the natural lipid bilayers. LPA can be incorporated into natural lipid membranes without disturbance, and readjusts itself to a more favorable hydrophobic match with the bilayers. Lysophophatidylcholine (LPC) also induces a disorder in DMPC membranes, but the decrease in chain order is only half compared with that for LPA.     

Reactivity of singlet oxygen toward strained substrates and a novel non-photochemical method for determination of quenching constants of singlet oxygen.

Rate constants for quenching of ¹O₂ by a number of strained molecules have been determined by the competitive rubrene photooxidation method; the rate constant for quenching by Q may be evaluated by adaption of a kinetic analysis already in the literature for the rubrene photooxidation method.     

Numerical Simulation of Rayleigh–Bènard Instability in Solutions Containing Ions of Three Types

The conditions for appearance of a Rayleigh–Benard instability (RBI) induced by a constant current between two horizontal electrodes in solution containing electroactive ions and indifferent electrolyte (system with three kinds of ions) are analyzed. It is taken into account that all the components take part in the formation of buoyant forces. The problem is solved for a stationary case (as an expansion to a series by a small parameter), and then equations for low perturbations are solved by the Galerkin method. The calculation is performed with a program that accounts for any number of members in a Galerkin expansion. A diagram is obtained, which determines conditions for the RBI emergence in terms of ratios of partial Raleigh numbers. The ratio of diffusion coefficients for supporting cations and anions significantly affects position of the boundary dividing ranges of convective stability and RBI in a diagram of nonequilibrium phase transitions.     

NMR study of model compounds of vinyl polymers

Complicated NMR spectra of vinyl polymers provide conformational and configurational knowledge of the polymers in solution. Explicit expressions for the spectral frequencies and intensities are obtained by the analysis of vinyl polymers and their model compounds as weakly coupled systems. The classified spectra expected for common vinyl polymers are presented by using the results of the analysis. The analysis is applied to model compounds of poly(vinyl alcohol) and poly(vinyl acetate) in solution. The results show that conformations of poly(vinyl alcohol) are determined by the intramolecular hydrogen bonding so that the syndiotactic isomer forms a helical structure, the isotactic one a planar zigzag structure. The poly(vinyl acetate) produces a helical structure for isotactic isomer by the repulsion of side chains and a planar zigzag for the syndiotactic isomer.     

Sliding-spark spectrometry of sediment samples

Direct analysis of non-conducting solids and dielectric surface layers for elements at trace levels has been shown to be feasible by the new so-called sliding-spark spectroscopy, in which a discharge plasma is bound by, and propagates on, the surface of a dielectric sample matrix. By using a river sediment as a model matrix, bound in PVC to improve elemental atomization and excitation efficiency, as a result of the formation of volatile chlorides, the potential of the technique for environmental applications has been investigated by studying the characteristic UV-visible radiation emitted in the wavelength range 210-510 nm for the elements Fe, Cr, Ni, Cu, Pb, Cd, Zn, Co, V, Ti, and Mn. The radiation was detected by means of a CCD spectrometer and analysed for spectral line identification, selection, and the linearity of the spectral response, to determine whether this was suitable for establishing a calibration strategy for quantitative analysis using the sliding-spark source.     

Improvement of the efficiency of electrochemical refining of cobalt

To improve the purity of cobalt produced by electrochemical refining, the optimal electrolyte composition and electrolysis mode were determined and a method for diminishing the electrochemical activity of impurity metals in anodic dissolution of the raw metal and a system for deep purification of the electrolyte solution to remove impurities were developed. Cathode deposits with a conditional cobalt content exceeding 99.999 wt %, found in an analysis for the 11 main impurities, were obtained by using the above results in refining of K1A cobalt (≥99.30 wt % Co) in an electrolyzer of distinctive design.     

Qualitative interpretation of the dynamics of collinear exchange reactions

The many-channel resonance scattering theory is adapted for the purpose of investigation of the dynamics of collinear chemical exchange reactions. A general expression for the scattering matrix is presented which appears to be useful for developing a simple algebraic procedure of calculation of the parameters needed for various resonance expansions. The case of weak nonadabatic coupling between vibrational levels is studied in detail by means of a version of perturbational treatment that is valid for a resonance situation. This approach is then applied to account for the qualitative peculiarities observed in recent experimental and numerical investigations of reactive collosions A + BC → AB + C. The Polanyi rules are formulated in terms of the accessibility of a transition zone region for adiabatic channel functions. Several mechanisms of product population inversion are discussed. That of them occurring at low kinetic energies in the transition zone is supposed to arise due to the resonance scattering caused by the wells of dynamic adjabatic potentials, which have been revealed by Wu, Johnson and Levine. The estimations for Breit-Wigner reduced width amplitudes are given in framework of weak coupling approximation. They are shown to provide a meaningful background for understanding of resonance phenomena found in quantum calculations.     

Scaling analysis of coating of a plate or a fiber

The problem of coating a plate or a fiber through their withdrawal from a large reservoir was treated in the literature in various limiting cases. In the present paper, interpolation expressions are derived by scaling for Newtonian, Bingham, and viscoelastic fluids. The scaling analysis was also employed to explain the sharp increase in film thickness produced by inertia and the occurrence of a maximum thickness for an optimum velocity. It is also shown that, for a viscoelastic fluid, the film thickness tends to a finite value at very large withdrawal rates. An explanation is also provided for the existence of a maximum film thickness for an optimum surfactant concentration.     

Distillation of used liquid scintillation cocktail and the possibility of re-utilization of the recovered solvent

Liquid(toluene and dioxane)scintillation cocktail containing [methyl-3H]thymidine as a radioactive material was distilled by a rotary evaporator after storage for 0 to 12 months. The solvent obtained by distillation was then purified by several treatments, and the 3H-concentration in the solvent after each treatment was determined accurately. The 3H-concentration in the rotary evaporator-distillate of the cocktails reached about 0.2% of that of the original scintillation cocktails when they were stored for 12 months. But these radioactive materials could be removed completely from each solvent by several refining treatments: washing with water followed by dehydration with molecular sieves in case of toluene scintillation cocktail, and desiccation by adding excess amount of KOH in case of dioxane scintillation cocktail. It was concluded that the distillation followed by several simple refining treatments was useful to regenerate the refined solvent available for the preparation of liquid scintillation cocktail and also as a preliminary step to dispose of the waste scintillation cocktail.     

Determination of concentration distribution of trace elements near the detection limit

The results of a numerical simulation, performed to check the validity of a method developed for reconstruction of concentration distributions truncated by the detection limit, are reported in the context of trace element analysis in biomedical samples by total-reflection X-ray fluorescence. This method, by correcting a distribution over the whole range of concentrations in a population of samples, restores a number of measurements reporting results below the detection limit. We show by Monte Carlo simulations, assuming lognormal distributions to describe both the concentrations measured as well as the detection limits in the biomedical samples, that the method developed is accurate to within 5% for most typical situations. Moreover, we demonstrate that the factor limiting the accuracy of the correction is the number of measurements, not the correction procedure itself. We have found in simulations that the reconstruction of a concentration distribution, for a typical population size of N=100, is possible when the concentrations are measured only in 20–30% of samples. On the other hand, we show that by ignoring the truncation of a concentration distribution by the detection limit, the results can be systematically biased by as much as 50%. The method developed is applied to the analysis of trace elements in human breast tissue samples by total-reflection X-ray fluorescence (TXRF). The results are also discussed in terms of the size of the population studied.     

Total synthesis of pinnatoxins A and G and revision of the mode of action of pinnatoxin A

Pinnatoxins belong to an emerging class of potent marine toxins of the cyclic imine group. Detailed studies of their biological effects have been impeded by unavailability of the complex natural product from natural sources. This work describes the development of a robust, scalable synthetic sequence relying on a convergent strategy that delivered a sufficient amount of the toxin for detailed biological studies and its commercialization for use by other research groups and regulatory agencies. A central transformation in the synthesis is the highly diastereoselective Ireland-Claisen rearrangement of a complex α,α-disubstituted allylic ester based on a unique mode for stereoselective enolization through a chirality match between the substrate and the lithium amide base. With synthetic pinnatoxin A, a detailed study has been performed that provides conclusive evidence for its mode of action as a potent inhibitor of nicotinic acetylcholine receptors selective for the human neuronal α7 subtype. The comprehensive electrophysiological, biochemical, and computational studies support the view that the spiroimine subunit of pinnatoxins is critical for blocking nicotinic acetylcholine receptor subtypes, as evidenced by analyzing the effect of a synthetic analogue of pinnatoxin A containing an open form of the imine ring. Our studies have paved the way for the production of certified standards to be used for mass-spectrometric determination of these toxins in marine matrices and for the development of tests to detect these toxins in contaminated shellfish.     

A comparison of the electrophilic reactivities of Zn2+ and acetic acid as catalysts of enolization: imperatives for enzymatic catalysis of proton transfer at carbon

The deprotonation of the alpha-CH3 and alpha-CH2OD groups of hydroxyacetone and the alpha-CH3 groups of acetone in the presence of acetate buffer and zinc chloride in D2O at 25 degrees C was followed by monitoring the incorporation of deuterium by 1H NMR spectroscopy, and the rate laws for catalysis of these reactions by acetate anion and zinc dication were evaluated. Relative to solvent water at a common standard state of 1 M, Zn2+ provides 6.3 and 4.4 kcal/mol stabilizations, respectively, of the transition states for deprotonation of the alpha-CH2OD and alpha-CH3 groups of hydroxyacetone by acetate anion, and a smaller 3.3 kcal/mol stabilization of the transition state for deprotonation of the alpha-CH3 group of acetone. There is only a 1.4 kcal/mol smaller stabilization of the transition state for the acetate-ion-promoted deprotonation of acetone by the Br?nsted acid acetic acid than by Zn2+, which shows that, in the absence of a chelate effect, there is no large advantage to the use of a metal dication rather than a Br?nsted acid to stabilize the transition state for deprotonation of alpha-carbonyl carbon.     

Spectrophotometric determination of tin in steel

A new spectrophotometric method for the determination of traces of tin in steel is presented. The tin is isolated by an acid sulfide separation and a double carbamate-chloroform extraction and then determined by a phenylfluorone method in which the selectivity is increased by the use of peroxide and oxalate as masking agents and the sensitivity is increased by extracting the colored tin compound into a small volume of MIBK for the spectrophotometric analysis.     

Evaluation of microwave-assisted extraction for the analysis of organophosphorus and pyrethroid pesticides in green onions

The aim of this study was to evaluate the efficiency of microwave-assisted extraction (MAE) for the analysis of organophosphorus (OP) and pyrethroid (PYR) pesticides in green onions by GC/MS. We optimized MAE extraction solvent, temperature, and time by using a certified reference material. As a result, the concentrations of two OP and two PYR target pesticides obtained by MAE with acetonitrile at 110 degrees C for 10 min were in good agreement with certified concentrations and comparable to the results by homogenization used as reference extraction technique. When the recovery test, performed by spiking the target pesticides into blank samples (5.0 g), was carried out with our optimized MAE conditions, mean recoveries of 16 OP and 10 PYR pesticides were 72-108% for a 1.0 pg spiking level and 70-119% for a 0.2 microg level. These results were acceptable according to the validation guideline for testing method of agricultural chemicals in food by Ministry of Health, Labour, and Welfare in Japan. The results suggested that MAE can be used for the analysis of OP and PYR pesticides in green onions.     

Development of a procedure for the multi-element determination of trace elements in wine by ICP-MS

An inductively coupled plasma mass spectrometric (ICP-MS) procedure has been developed for the determination of trace elements in wine. The procedure consists in simple 1+1 dilution of the wine and semi-quantitative analysis (without external calibration) using In as internal standard. Thirty-one elements at concentrations ranging from 0.1 mg mL(-1) to 0.5 ng mL(-1) can be determined by ICP-MS analysis with and without digestion. It was investigated whether a matrix effect observed for EtOH in the wine matrix can be overcome by application of a micro-concentric nebulizer with a membrane desolvator (MCN 6000). The results obtained for the MCN 6000 are compared with those obtained by use of a conventional Meinhard nebulizer. It is shown that the observed matrix effect can only be compensated by use of an internal standard for the Meinhard nebulizer, but not for the MCN 6000. Results for ICP-MS are compared with those obtained by total reflection X-ray fluorescence spectrometry (TXRF).     

Magnetic resonance tracking of copper ion fixation on the surface of carboxylated nanodiamonds from viewpoint of changes in carbon-inherited paramagnetism

Detonation nanodiamonds with a particle size of 5 nm and a carboxylated surface are easily modified by doubly charged copper ions to form copper chelate complexes. The concentration of copper complexes in a dry powder of such nanodiamonds is well monitored by the method of electron paramagnetic resonance, both by the signal width of intrinsic paramagnetic centers in nanodiamonds and by the signal shape for the surface Cu²⁺ ions themselves, including the set of hyperfine splitting lines for the parallel component and the line with an unresolved hyperfine structure for the perpendicular component.