NMR study of intramolecular processes in EDTA metal complexes

The kinetics of the intramolecular acetate scramblings occurring in thirteen ethylenediaminetetraacetate (EDTA) complexes has been studied by analyzing the modification observed in the NMR spectra of their D₂O solutions, when temperature is changed. The experimental results indicate that the Δ, Λ conversion is a fast process on the NMR time scale for each of the complexes considered, whereas the nitrogen inversion occurs at an observable rate in the case of the Cd(II), In(III), Sc(III), Y(III) and Lu(III) chelates and is too rapid in the other complexes. Computer analysis of the experimental NMR spectra has been performed in order to obtain enthalpy, entropy and free energy of activation concerning the N inversion of the cited chelates. Twist and bond breaking mechanisms are discussed with reference to both scrambling processes.     

Solution phase Cerenkov counting of80g Br and80m Br in the presence of82Br

^80g Br and^80m Br (via its^80g Br daughter) were measured with high efficiency in organic solutions by means of the Cerenkov radiation from the high energy β-rays emitted in the^80g Br decay. The efficiency for the contaminating⁸²Br activity was less than 1%.     

On the optimal design of the output transformation for discrete-time linear systems

The optimization of the output matrix for a discrete-time, single-output, linear stochastic system is approached from two different points of view. Firstly, we investigate the problem of minimizing the steady-state filter error variance with respect to a time-invariant output matrix subject to a norm constraint. Secondly, we propose a filter algorithm in which the output matrix at timek is chosen so as to maximize the difference at timek+1 between the variance of the prediction error and that of the a posteriori error. For this filter, boundedness of the covariance and asymptotic stability are investigated. Several numerical experiments are reported: they give information about the limiting behavior of the sequence of output matrices generated by the algorithm and the corresponding error covariance. They also enable us to make a comparison with the results obtained by solving the former problem.This work was supported by the Italian Ministry of Education (MPI 40%), Rome, Italy.     

Low temperature properties of Pr amorphous alloys

Starting from the Fert and Campbell Hamiltonian and assuming a suitable η-distribution, the magnetization and the specific heat for Pr amorphous alloys are evaluated in the molecular field approximation with ferromagnetic interaction.Recent low-temperature experimental data on the specific heat of Pr amorphous alloys are reasonably explained.     

Caffeine and theobromine in coffee, tea and cola-beverages

Summary A new method based on reversed-phase ion-interaction HPLC is described for the identification and quantitation of theobromine, theophylline and caffeine in beverages. The interaction reagent used is octylamine orto-phosphate which also constitutes the mobile phase. The stationary phase is a microparticulate reversed-phase C-18 packing. With spectrophotometric detection at 274 nm, detection levels of 0.15, 0.30 and 0.40 ppm were achieved for theobromine, theophylline and caffeine, respectively.Quantitative analysis was performed by the standard addition method for theobromine and caffeine contents in tea, espresso-coffee, decaffeinated coffee, decaffeinated tea and cola-beverages.     

Analysis of the inclusive reaction π−p→K10 (890) X0 at 10 GeV/c

Experimental results on the reaction $\text{π}{}^{\mathrm{?}}\text{p}\text{→}\text{K}{}^{10}\text{(890)}\text{X}{}^0\text{at}\text{10}\text{GeV}\text{/c}$ are presented. By using the K¹⁰ polarization measurements, a detailed study of the production has been carried out as a function of the missing mass squared and of the four-momentum trasnfer squared to the K¹⁰. We found that: (a) K¹⁰ production is dominated by natural parity exchange; (b) K¹⁰ helicity-zero production dominates the unnatural parity exchange contribution and (c) the main features of the reaction are in agreement with the predictions of the finite mass sum rules.     

A radioanalytical method for the determination of Pb(II) with the use of a chelating cellulose filter

A functionalized cellulose filter, with iminodiacetate chelating units, has been characterized for the uptake of ultratrace Pb(II) (1 to 10^–6 mg · ^–1) with the use of²¹⁰Pb. The different behaviour in batch and in flow-through experiments has been observed both in the rate of metal uptake, as well as in the relative yield of metal recovery. Flow-through uptake appeared to be a faster process and to occur with higher % yield in the entire range investigated. A radioanalytical method for the determination of Pb(II) in liquid samples (10 to 10^–2 mg · ^–1) has been developed, based on the measurement of the²¹⁰Pb activity exchanged between a iminodiacetic acid filter loaded with²¹⁰Pb and the solution under analysis. Results and interferences are considered and discussed.     

Capillary electrophoresis/electrospray ion trap mass spectrometry for the analysis of negatively charged derivatized and underivatized glycans.

The increasing interest in the development of glycoproteins for therapeutic purposes has created a greater demand for methods to characterize the sugar moieties bound to them. Traditionally, released carbohydrates are derivatized using such methods as permethylation or fluorescent tagging prior to analysis by high performance liquid chromatography (HPLC), capillary electrophoresis (CE), or direct infusion mass spectrometry. However, little research has been performed using CE with on-line mass spectrometry (MS) detection. The CE separation of neutral oligosaccharides requires the covalent attachment of a charged species for electrophoretic migration. Among charged labels which have shown promise in assisting CE and HPLC separation is the fluorophore 8-aminonaphthalene-1,3,6-trisulfonic acid (ANTS). This report describes the qualitative profiling of charged ANTS-derivatized and underivatized complex glycans by CE with on-line electrospray ion trap mass spectrometry. Several neutral standard glycans including a maltooligosaccharide ladder were derivatized with ANTS and subjected to CE/UV and CE/MS using low pH buffers consisting of citric and 6-aminocaproic acid salts. The ANTS-derivatized species were detected as negative ions, and multiple stage MS analysis provided valuable structural information. Fragment ions were easily identified, showing promise for the identification of unknowns. N-Linked glycans released from bovine fetuin were used to demonstrate the applicability of ANTS derivatization followed by CE/MS for the analysis of negatively charged glycans. Analyses were performed on both underivatized and ANTS-derivatized species, and sialylated glycans were separated and detected in both forms. The ability of the ion trap mass spectrometer to perform multiple stage analysis was exploited, with MS5 information obtained on selected glycans. This technique presents a complementary method to existing methodologies for the profiling of glycan mixtures.     

Determination of Pesticides in the Respirable Fraction of Airborne Particulate Matter by High-performance Liquid Chromatography–Tandem Mass Spectrometry

Potential harmful effects of pesticides include risks to human health of workers involved in the wet spray application in cultivated areas. Inhalation exposure depends on several factors including pesticide concentrations in the respirable fraction of airborne particulate matter (PM₄). To ensure a high level of protection, the use of tractors with cabins provides protection against dust, aerosols, and vapors. Since tractors not providing maximum protection are still in use, PM₄ was sampled during spreading operations in agricultural fields inside and outside tractor cabins. Sample preparation technique based on accelerated solvent extraction and solid-phase extraction cleanup was optimized before analysis of nine pesticides in PM₄. Meptyldinocap, deltamethrin, myclobutanil, fluopyram, methoxyfenozide, dimethomorph, fluopicolide, cyflufenamid, and metrafenone were simultaneously determined by high-performance liquid chromatography–electrospray ionization–tandem mass spectrometry (HPLC–ESI–MS–MS). The results demonstrated the efficacy of the tractor cabs used in the sampling sites.