Feasibility of electron impact and electron capture negative ionisation mass spectrometry for the trace determination of tri- to deca-brominated diphenyl ethers in human samples

The applicability of two different MS ionisation modes (EI and ECNI) for the determination of PBDEs at low-trace levels in small-size (up to 1 mL) human samples was compared. The instrumental precision, expressed as R.S.D., obtained for both ionisation modes was similar and lower than 6% (repeatability) and 12% (intermediate precision) for all congeners investigated, except PBDE 209. The LODs obtained when using the ECNI-MS operation mode (6-507 fg) were lower than those found in EI-MS experiments (9 and 10,909 fg), mainly for those congeners with a high bromination degree, i.e., hepta- to deca-BDEs. The selectivity of the ECNI-MS method proposed in the present work was improved by using two ions of the [M−H_xBr_y]⁻ cluster as both qualifier and quantifier ions. For the final validation of the methods, serum and breast milk samples from two different inter-laboratory exercises were analysed. A good agreement was found between the results obtained using the proposed methods and the results provided by the different inter-laboratory organisations, but only ECNI-MS provided the low-LODs necessary for the quantification of high brominated congeners (mainly, PBDEs 196, 197 and 209) at low concentration levels in small-size human samples. Finally, the ECNI-MS method was applied to real-life samples obtained from the Spanish population and the preliminary results obtained were in the same range as those found in other European and Asian regions and lower than the concentrations reported in USA populations.     

A new multiresponse optimization approach in combination with a D-Optimal experimental design for the determination of biogenic amines in fish by HPLC-FLD

A new strategy to approach multiresponse optimization in conjunction to a D-optimal design for simultaneously optimizing a large number of experimental factors is proposed. The procedure is applied to the determination of biogenic amines (histamine, putrescine, cadaverine, tyramine, tryptamine, 2-phenylethylamine, spermine and spermidine) in swordfish by HPLC-FLD after extraction with an acid and subsequent derivatization with dansyl chloride. Firstly, the extraction from a solid matrix and the derivatization of the extract are optimized. Ten experimental factors involved in both stages are studied, seven of them at two levels and the remaining at three levels; the use of a D-optimal design leads to optimize the ten experimental variables, significantly reducing by a factor of 67 the experimental effort needed but guaranteeing the quality of the estimates. A model with 19 coefficients, which includes those corresponding to the main effects and two possible interactions, is fitted to the peak area of each amine. Then, the validated models are used to predict the response (peak area) of the 3456 experiments of the complete factorial design. The variability among peak areas ranges from 13.5 for 2-phenylethylamine to 122.5 for spermine, which shows, to a certain extent, the high and different effect of the pretreatment on the responses. Then the percentiles are calculated from the peak areas of each amine. As the experimental conditions are in conflict, the optimal solution for the multiresponse optimization is chosen from among those which have all the responses greater than a certain percentile for all the amines. The developed procedure reaches decision limits down to 2.5 μg L⁻¹ for cadaverine or 497 μg L⁻¹ for histamine in solvent and 0.07 mg kg⁻¹ and 14.81 mg kg⁻¹ in fish (probability of false positive equal to 0.05), respectively.     

Potential of zero total charge of platinum single crystals: A local approach to stepped surfaces vicinal to Pt(111)

The electrochemical behavior of platinum single-crystal electrodes is revisited, with special emphasis on the determination of the potential of zero charge. We show that the measure of the charge displaced during CO adsorption allows the determination of the potential of zero total charge (PZTC). The estimation of the potential of zero free charge (PZFC) is discussed, with different degrees of approximation. The application of this methodology to the study of the PZTC of platinum stepped surfaces vicinal to Pt(111) reveals a marked decrease of the PZTC due to the introduction of surface steps. This effect is interpreted as the result of the existence of markedly smaller surface potentials localized on step sites. The importance of considering local aspects of the interface is emphasized with the use of N₂O reduction as a sensitive probe to the local structure of the surface. It is proposed that the different local maxima observed in the absolute value of the reduction current correspond to the local values of PZTC. It is shown that there is, in general, good agreement between the overall PZTC, obtained from the CO displacement, and that calculated from the local values inferred from the N₂O reduction. Further insight is obtained with the application of the laser-induced temperature jump method. This technique is useful to calculate the potential of maximum entropy of the double-layer formation. The resulting value of this potential for Pt(111) is discussed in the light of the PZFC value obtained from different approaches. For stepped surfaces vicinal to Pt(111), two local maxima in the entropy of the double layer are observed that are close to the local PZTC values estimated from the N₂O reduction. This result suggests the existence of cooperative effects in the organization of the water dipoles close to the electrode surface. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 11, pp. 1275–1292. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

Equatorially connected diruthenium(II,III) units toward paramagnetic supramolecular structures with singular magnetic properties

The reaction of Ru2Cl(O2CMe)(DPhF)3 (DPhF = N,N'-diphenylformamidinate) with mono- and polycarboxylic acids gives a clean substitution of the acetate ligand, leading to the formation of complexes Ru2Cl(O2CC6H5)(DPhF)3 (1), Ru2Cl(O2CC6H4-p-CN)(DPhF)3 (2), [Ru2Cl(DPhF)3(H2O)]2(O2C)2 (3), [Ru2Cl(DPhF)3]2[C6H4-p-(CO2)2] (4), and [Ru2Cl(DPhF)3]3[C6H3-1,3,5-(CO2)3] (5). The preparation of [Ru2(NCS)(DPhF)3]3[C6H3-1,3,5-(CO2)3] (6) and {[Ru2(DPhF)3(H2O)]3[C6H3-1,3,5-(CO2)3]}(SO3CF3)3 (7) from 5 is also described. All complexes are characterized by elemental analysis, IR and electronic spectroscopy, mass spectrometry, cyclic voltammetry, and variable-temperature magnetic measurements. The crystal structure determinations of complexes 2.0.5THF and 3.THF.4H2O (THF = tetrahydrofuran) are reported. The reactions carried out demonstrate the high chemical stability of the fragment [Ru2(DPhF)3]2+, which is preserved in all tested experimental conditions. The stability of this fragment is also corroborated by the mass spectra. Electrochemical measurements reveal in all complexes one redox process due to the equilibrium Ru2(5+) <--> Ru2(6+). In the polynuclear complex 7, some additional oxidation processes are also observed that have been ascribed to the presence of two types of dimetallic units rather than two consecutive reversible oxidations. The magnetic behavior toward temperature for complexes 1-7 from 300 to 2 K is analyzed. Complexes 1-7 show low values of antiferromagnetic coupling in accordance with the molecular nature in 1 and 2 and the absence of important antiferromagnetic interaction through the carboxylate bridging ligands in 3-7, respectively. In addition, the magnetic properties of complex 7 do not correspond to any magnetic behavior described for diruthenium(II,III) complexes. The experimental data of compound 7 are simulated considering a physical mixture of S = 1/2 and 3/2 spin states. This magnetic study demonstrates the high sensitivity of the electronic configuration of the unit [Ru2(DPhF)3]2+ to small changes in the nature of the axial ligands. Finally, the energy gap between the pi and delta orbitals in these types of compounds allows the tentative assignment of the transition pi --> delta.     

Influence of rotation and isotope effects on the dynamics of the N((2)D)+H(2) reactive system and of its deuterated variants

Integral cross sections and thermal rate constants have been calculated for the N((2)D)+H(2) reaction and its isotopic variants N((2)D)+D(2) and the two-channel N((2)D)+HD by means of quasiclassical trajectory and statistical quantum-mechanical model methods on the latest ab initio potential-energy surface [T.-S. Ho et al., J. Chem. Phys. 119, 3063 (2003)]. The effect of rotational excitation of the diatom on the dynamics of these reactions has been investigated and interesting discrepancies between the classical and statistical model calculations have been found. Whereas a net effect of reagent rotation on reactivity is always observed in the classical calculations, only a very slight effect is observed in the case of the asymmetric N((2)D)+HD reaction for the statistical quantum-mechanical method. The thermal rate constants calculated on this Potential-Energy Surface using quasiclassical trajectory and statistical model methods are in good agreement with the experimental determinations, although the latter are somewhat larger. A reevaluation of the collinear barrier of the potential surface used in the present study seems timely. Further theoretical and experimental studies are needed for a full understanding of the dynamics of the title reaction.     

Characterization of the surface structure of gold nanoparticles and nanorods using structure sensitive reactions

The surface structure of gold nanorods has been determined by studying the behavior of electrochemical reactions sensitive to the structure and compared to that obtained by other structure characterization techniques. Lead underpotential deposition (UPD) reveals that the surface of the nanorods is composed by (111) and (110) domains, while (100) domains are practically absent from the surface. In the case of the oxygen reduction reaction, the formation of hydrogen peroxide as a final product of the reaction in the whole potential range also indicates that (100) domains are absent on the surface of the nanoparticles, corroborating the previous result. These results are compared with other surface structure information provided by other techniques.     

Determination of organic compounds from wood combustion aerosol nanoparticles by different gas chromatographic systems and by aerosol mass spectrometry

Organic compounds in atmospheric nanoparticles have an effect on human health and the climate. The determination of these particles is challenged by the difficulty of sampling, the complexity of sample composition, and the trace-level concentrations of the compounds. Meeting the challenge requires the development of sophisticated sampling systems for size-resolved particles and the optimization of sensitive, accurate and simple analytical techniques and methods. A new sampling system is proposed where particles are charged with a bipolar charger and size-segregated with a differential mobility analyzer. This system was successfully used to sample particles from wood pyrolysis with particle sizes 30–100 nm. Particles were analyzed by four techniques: comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry, gas chromatography–time-of-flight mass spectrometry, gas chromatography–quadrupole mass spectrometry, and aerosol mass spectrometry (aerosol MS). In the chromatographic techniques, particles were collected on a filter and analyzed off-line after sample preparation, whereas in the aerosol MS, particle analysis was performed directly from the particle source. Target compounds of the samples were polyaromatic hydrocarbons and n-alkanes. The analytical techniques were compared and their advantages and disadvantages were evaluated. The sampling system operated well and target compounds were identified in low concentrations.     

Diffusion of muonium and hydrogen in diamond

Jump rates of muonium and hydrogen in diamond are calculated by quantum transition-state theory, based on the path-integral centroid formalism. This technique allows us to study the influence of vibrational mode quantization on the effective free-energy barriers DeltaF for impurity diffusion, which are renormalized with respect to the zero-temperature classical calculation. For the transition from a tetrahedral (T) site to a bond-center (BC) position, DeltaF is larger for hydrogen than for muonium, and the opposite happens for the transition BC-->T. The calculated effective barriers decrease for rising temperature, except for the muonium transition from T to BC sites. The calculated jump rates are in good agreement with available muon spin rotation data.