X-Band Pulsed ENDOR Study ofFe-Substituted Sodalite— The Effect of the Zero-Field Splitting

X-band (∼9.3 GHz) pulsed ENDOR measurements were carried out on⁵⁷Fe-substituted sodalite (FeSOD) which contains only one type of Fe(III) (S=) located at a framework site. The ENDOR spectrum recorded atg= 2 shows three doublets corresponding to the sixM_Smanifolds. The assignment of these signals was confirmed by hyperfine-selective and triple ENDOR experiments. The components of each of the doublets had different intensities, reflecting the different populations of the EPR energy levels at the measurement temperature, 1.8 K. ENDOR spectra were recorded at magnetic fields within the EPR powder pattern, and the field dependence observed showed an anisotropic behavior, unexpected from the isotropic character of the⁵⁷Fe(III) hyperfine coupling. This dependence was attributed to the high-order effects of the zero-field splitting (ZFS) interaction on the ENDOR frequencies. Three different theoretical approaches were used to account for the dependence of the ENDOR spectrum on the ZFS interaction. The first involves the exact diagonalization of the total spin Hamiltonian, the second uses third-order perturbation approximations, and the third employs an effective nuclear Hamiltonian for each of theM_Smanifolds. The simulations showed that the ENDOR signals of theM_S= ±5/2 (ν_±5/2) manifold are the least sensitive to the magnitude of the ZFS parameterDand are therefore the most appropriate for the determination ofa_iso. It is shown that at X band anda_isovalues of about 30 MHz, the perturbation approach is valid up toDvalues of 500 MHz if all three doublets are concerned. However, if only the ν_±5/2doublet is considered, then this approach is valid forD< 1000 MHz. The third approach was found inappropriate fora_isovalues of ∼30 MHz. Using the method of exact diagonalization together with orientation selectivity, the trends observed in the experimental spectra could be reproduced. The ENDOR spectra of the⁵⁷Fe-substituted zeolites ZSM5, L, and mazzite showed broad and ill-defined peaks since the ZFS of Fe(III) in these zeolites is significantly larger than that of FeSOD. Because this broadening is a high-order effect, it can be significantly reduced at higher spectrometer frequencies.     

Headspace-programmed temperature vaporizer-fast gas chromatography-mass spectrometry coupling for the determination of trihalomethanes in water

A new method based on the use of a headspace autosampler in combination with a GC equipped with a programmable temperature vaporizer (PTV) and an MS detector has been developed for the screening and quantitative determination of trihalomethanes (THMs) in different aqueous matrices. The use of headspace generation to introduce the sample has the advantage that no prior sample treatment is required, thus minimizing the creation of analytical artifacts and the errors associated with this step of the analytical process. The PTV inlet used was packed with Tenax-TA. The injection mode was solvent vent, in which the analytes are retained in the hydrophobic insert packing by cold trapping, while the water vapour is eliminated through the split line. This allows rapid injection of the sample in splitless mode, very low detection limits being achieved without the critical problem of initial sample bandwidth. The capillary column used allowed rapid separations with half-height widths ranging from 1.68 s (chloroform) to 0.66 s (bromoform). The GC run time was 7.3 min. The use of mass spectrometry allows the identification and quantification of the analytes at the low ppt level. The S/N ratio was at least 10-fold higher when the SIM mode was used in data acquisition as compared to the scan mode. The proposed method is extremely sensitive, with detection limits ranging from 0.4 to 2.6 ppt.     

Determination of monomethylmercury in low- and high-polluted sediments by microwave extraction and gas chromatography with atomic fluorescence detection

Laser tomography techniques were used in order to make visible the flow patterns induced by ascending bubbles in flutes poured with champagne. The stability of flow patterns was investigated in flutes showing natural (without any specific surface treatment) as well as artificial effervescence (i.e., engraved at their bottom), all along the first 15 min after pouring. Engravement conditions were found to strongly influence the kinetics and the stability with time of the mixing flow phenomena found in champagne glasses.     

Synthesis and electrochemical reaction with lithium of mesoporous iron oxalate nanoribbons

Mesoporous FeC 2O 4 was prepared by dehydration of bulk monoclinic- and micellar orthorhombic FeC 2O 4.2H 2O precursors at 200 degrees C. The micellar material shows nanoribbon shaped particles, which are preserved after dehydration. These solids are used as high-capacity lithium storage materials with improved rate performance. The mesoporous nanoribbons exhibit higher capacities close to 700 mA h/g after 50 cycles at 2C (C = 1 Li h (-1) mol (-1)) rate between 0 and 2 V.     

Convergence and superconvergence analyses of HDG methods for time fractional diffusion problems

We study the hybridizable discontinuous Galerkin (HDG) method for the spatial discretization of time fractional diffusion models with Caputo derivative of order 0 < α < 1. For each time t ∈ [0, T], when the HDG approximations are taken to be piecewise polynomials of degree k ≥ 0 on the spatial domain Ω, the approximations to the exact solution u in the L _∞(0, T; L ₂(Ω))-norm and to ?u in the \(L_{\infty }(0, \textit {T}; \mathbf {L}_{2}({\Omega }))\)-norm are proven to converge with the rate h ^k+1 provided that u is sufficiently regular, where h is the maximum diameter of the elements of the mesh. Moreover, for k ≥ 1, we obtain a superconvergence result which allows us to compute, in an elementwise manner, a new approximation for u converging with a rate h ^k+2 (ignoring the logarithmic factor), for quasi-uniform spatial meshes. Numerical experiments validating the theoretical results are displayed.     

A Bayesian approach to assess data from radionuclide activity analyses in environmental samples

A Bayesian statistical approach is introduced to assess experimental data from the analyses of radionuclide activity concentration in environmental samples (low activities). A theoretical model has been developed that allows the use of known prior information about the value of the measurand (activity), together with the experimental value determined through the measurement. The model has been applied to data of the Inter-laboratory Proficiency Test organised periodically among Spanish environmental radioactivity laboratories that are producing the radiochemical results for the Spanish radioactive monitoring network. A global improvement of laboratories performance is produced when this prior information is taken into account. The prior information used in this methodology is an interval within which the activity is known to be contained, but it could be extended to any other experimental quantity with a different type of prior information available.     

Simultaneous determination of gasoline oxygenates and benzene, toluene, ethylbenzene and xylene in water samples using headspace-programmed temperature vaporization-fast gas chromatography-mass spectrometry

A sensitive method is presented for the fast analysis of seven fuel oxygenates (methanol, ethanol, tert-butyl alcohol (TBA), methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME) and diisopropyl ether (DIPE)) and benzene, toluene, ethylbenzene and p-xylene (BTEX) in water samples. The applicability of a headspace (HS) autosampler in combination with a GC device equipped with a programmable temperature vaporizer (PTV) and a MS detector is explored. The proposed method achieves a clear improvement in sensitivity with respect to conventional headspace methods due to the use of the PTV. Two different packed liners with materials of different trapping strengths (glass wool and Tenax-TA) were compared. The benefits of using Tenax-TA instead of glass wool as packed material for the measurement of the 11 compounds emerged as better signal-to-noise ratios and hence better detection limits. The proposed method is extremely sensitive. The limits of detection are of the order of ng/L for six of the compounds studied and of the order of microg/L for the rest, with the exception of the most polar and volatile compound: methanol. Precision (measured as the relative standard deviation for a level with an S/N ratio close to 3) was equal to or lower than 15% in all cases. The method was applied to the determination of the analytes in natural matrixes (tap, river and sea water) and the results obtained can be considered highly satisfactory. The methodology has much lower detection limits than the concentration limits proposed in drinking water by the US Environmental Protection Agency (EPA) and the European Union for compounds under regulation.     

Synthesis and Crystal Structure of Peptide‐2,2′‐Biphenyl Hybrids

1,1′‐Biphenyl derivatives with amino acid/peptide substitution at C(2) and C(2′) (‘peptide‐biphenyl hybrids', 6 – 8 ) have been prepared by direct N‐acylation of amino acid/peptide derivatives with 1,1′‐biphenyl‐2,2′‐dicarbonyl dichloride ( 5 ). Both conformers, which arise from the rotation around the aryl aryl bond, have been detected by ¹H‐NMR spectroscopy. Single atropisomers of each 6 ((R)‐configuration at the stereogenic axis) and 7 ((S)‐configuration at the stereogenic axis) have been obtained in quantitative yield by slow evaporation of methanolic solutions. The procedures are dynamic atropselective resolutions (asymmetric transformations of the second kind). The crystal structures of the peptide‐biphenyl hybrids 6 and 7 show highly ordered molecular and supramolecular structures with extensive intramolecular and intermolecular H‐bonding.     

An RVE-based multiscale modeling method for constitutive relations

This article reports an efficient method to characterize constitutive responses based on multiscale modeling for fluid flow in heterogeneous media based on the concept of representative volume element (RVE). Between different scales, it is considered as the basic principles for down-scaling information the conservation of velocity and of the strain rate tensor. Within this context, we formulate (i) the problem to be solved at the micro-scale, (ii) the up-scaling procedure which involves homogenization rules, and (iii) the generalized principle of multiscale virtual power. The complete theory for constitutive modeling is revisited and shown that when employing multiscale analysis among the suitable variational arguments we are able to obtain, in a straightforward manner, new constitutive behavior between kinematic motions and actions. Some examples of application of fluid flow in heterogeneous media with obstacles are presented to show the consequences of the proposed approach.     

Evolutionary dynamics of imatinib-treated leukemic cells by stochastic approach

The evolutionary dynamics of a system of cancerous cells in a model of chronic myeloid leukemia (CML) is investigated by a statistical approach. Cancer progression is explored by applying a Monte Carlo method to simulate the stochastic behavior of cell reproduction and death in a population of blood cells which can experience genetic mutations. In CML front line therapy is represented by the tyrosine kinase inhibitor imatinib which strongly affects the reproduction of leukemic cells only. In this work, we analyze the effects of a targeted therapy on the evolutionary dynamics of normal, first-mutant and cancerous cell populations. Several scenarios of the evolutionary dynamics of imatinib-treated leukemic cells are described as a consequence of the efficacy of the different modelled therapies. We show how the patient response to the therapy changes when a high value of the mutation rate from healthy to cancerous cells is present. Our results are in agreement with clinical observations. Unfortunately, development of resistance to imatinib is observed in a fraction of patients, whose blood cells are characterized by an increasing number of genetic alterations. We find that the occurrence of resistance to the therapy can be related to a progressive increase of deleterious mutations.