Sample restriction using radiofrequency field selective pulses in high-resolution solid-state NMR

In this article a method is suggested for restricting a sample (spatial localization) by preparing the magnetization with a phase-modulated radiofrequency pulse which inverts magnetization only over a very narrow range of radiofrequency field strengths. This is the most efficient method, in terms of sensitivity, of restricting the sample to improve rf homogeneity. The method is demonstrated by using it to improve the resolution obtained in a homonuclear dipolar decoupling experiment.     

Two-dimensional high-resolution NMR spectra in matched B(0) and B(1) field gradients

In a recent publication we presented a method to obtain highly resolved NMR spectra in the presence of an inhomogeneous B(0) field with the help of a matched RF gradient. If RF gradient pulses are combined with "ideal" 90 degrees pulses to form inhomogeneous z rotation pulses, the line broadening caused by the B(0) gradient can be refocused, while the full chemical shift information is maintained. This approach is of potential use for NMR spectroscopy in an inhomogeneous magnetic field produced by an "ex-situ" surface spectrometer. In this contribution, we extend this method toward two-dimensional spectroscopy with high resolution in one or both dimensions. Line narrowing in the indirect dimension can be achieved by two types of nutation echoes, thus leading to depth-sensitive NMR spectra with full chemical shift information. If the nutation echo in the indirect dimension is combined with a stroboscopic acquisition using inhomogeneous z-rotation pulses, highly resolved two-dimensional correlation spectra can be obtained in matched field gradients. Finally, we demonstrate that an INEPT coherence transfer from proton to carbon spins is possible in inhomogeneous B(0) fields. Thus, it is possible to obtain one-dimensional (13)C NMR spectra with increased sensitivity and two-dimensional HETCOR spectra in the presence of B(0) gradients of 0.4 mT/cm. These schemes may be of some value for ex-situ NMR analysis of materials and biological systems.     

Entropy and enthalpy of formation and migration of lattice defects in Na(I)

The self-diffusion coefficients of Na⁺ and I^?, as well as the ionic conductivity, are measured in Na(I) single crystals, pure and doped with Ca²⁺ ions. The computer analysis of the whole set of data shows that the atom transport in Na(I) is ensured essentially by the free vacancies with a very small contribution (～4%) of the vacancy pairs. The thermodynamic parameters of vacancy formation and migration are derived by taking the long range interactions into account (activity coefficients on the concentrations and relaxation factors on the mobilities). The respective entropies of Schottky defect formation, cation migration and anion migration are equal to 7.64, 3.23 and 2.91 k while the corresponding enthalpies are equal to 2.00, 0.58 and 0.77 eV.     

The threshold for random -SAT is

Let be a random -CNF formula formed by selecting uniformly and independently out of all possible -clauses on variables. It is well known that if , then is unsatisfiable with probability that tends to 1 as . We prove that if , where , then is satisfiable with probability that tends to 1 as .

Our technique, in fact, yields an explicit lower bound for the random -SAT threshold for every . For our bounds improve all previously known such bounds.

     

Generalized layerwise mechanics for the static and modal response of delaminated composite beams with active piezoelectric sensors

A coupled linear layerwise laminate theory and a beam FE are formulated for analyzing delaminated composite beams with piezoactuators and sensors. The model assumes zig-zag fields for the axial displacements and the electric potential and it treats the discontinuities in the displacement fields due to the delaminations as additional degrees of freedom. The formulation naturally includes the excitation of piezoelectric actuators, their interactions with the composite laminate, and the effect of delamination on the predicted sensory voltage. The quasistatic and modal response of laminated composite Gr/Epoxy beams with active or sensory layers having various delamination sizes is predicted. The numerical results illustrate the strong effect of delamination on the sensor voltage, on through the thickness displacement and on the stress fields. Finally, the effect of delamination on modal frequencies and shapes are predicted and compared with previously obtained experimental results.     

A novel micellar PEGylated hyperbranched polyester as a prospective drug delivery system for paclitaxel

A hyperbranched aliphatic polyester has been functionalized with PEG chains to afford a novel water-soluble BH40-PEG polymer which exhibits unimolecular micellar properties, and is therefore appropriate for application as a drug-delivery system. The solubility of the anticancer drug paclitaxel was enhanced by a factor of 35, 110, 230, and 355 in aqueous solutions of BH40-PEG of 10, 30, 60, and 90 mg x mL(-1), respectively. More than 50% of the drug is released at a steady rate and release is almost complete within 10 h. The toxicity of BH40-PEG was assessed in vitro with A549 human lung carcinoma cells and found to be nontoxic for 3 h incubation up to a 1.75 mg x mL(-1) concentration while LD50 was 3.5 mg x mL(-1). Finally, it was efficiently internalized in cells, primarily in the absence of foetal bovine serum, while confocal microscopy revealed the preferential localization of the compound in cell nuclei. [Figure: see text].     

Alkyd resins derived from glycolized waste poly(ethylene terephthalate)

In this investigation the production of secondary value-added products, such as alkyd resins, derived from the glycolysis of poly(ethylene terephthalate) (PET) is examined as an effective way for its recycling. PET was taken from common soft-drink bottles and diethylene glycol (DEG) was used for the depolymerization at several initial molar ratios. The oligomers obtained were analyzed according to their average molecular weights. Furthermore, the glycolyzed PET products (oligomers) were reacted with maleic anhydride, phthalic anhydride and propylene glycol to form unsaturated polyester resins. These were subsequently mixed with styrene and cured using the benzoyl peroxide/amine initiator system to carry out the reaction in ambient temperature. The curing characteristics of the resins produced were investigated with respect to the initial molar ratio of DEG/PET as well as the initial initiator concentration. Finally, the mechanical properties (tensile strength and elongation at the break point) of the resins were compared with the conventional general purpose resin and were found to be comparable.     

Determination of carbendazim,thiabendazole, and<Emphasis Type="Italic"> o-</Emphasis>phenylphenol residues in lemons by HPLC following sample clean-up by ion-pairing

An efficient analytical method is presented involving effective sample clean-up with solid-phase extraction and HPLC-UV analysis for the simultaneous determination of carbendazim, thiabendazole, and o-phenylphenol residues in lemons. Sample preparation involves extraction with acetonitrile acidified with trifluoroacetic acid and an ethyl acetate/petroleum ether mixture. Purification of the crude extract was carried out with liquid–liquid partitioning after addition of an aqueous ammonia solution. Final clean-up was performed on polymeric reversed-phase cartridges pretreated with sodium dodecyl sulfate. Chromatographic analysis was performed on a reversed-phase HPLC column isocratically eluted with an acetonitrile/water/ammonia mixture and UV detection at 254 nm. The chromatographic method is repeatable, reproducible, and sensitive. Fungicide recoveries from lemon samples fortified at levels of 5 and 1 mg kg^–1 were 81–85% for carbendazim, 96–98% for thiabendazole, and 81–106% for o-phenylphenol with coefficients of variation of 2.5–7.4%. Detection limits for carbendazim, thiabendazole, and o-phenylphenol in lemons were 0.21, 0.27, and 0.51 mg kg^–1, respectively.     

Artificial compressibility, characteristics-based schemes for variable density, incompressible, multi-species flows. Part I. Derivation of different formulations and constant density limit

The paper presents various formulations of characteristics-based schemes in the framework of the artificial-compressibility method for variable-density incompressible flows. In contrast to constant-density incompressible flows, where the characteristics-based variables reconstruction leads to a single formulation, in the case of variable density flows three different schemes can be obtained henceforth labeled as: transport, conservative and hybrid schemes. The conservative scheme results in pseudo-compressibility terms in the (multi-species) density reconstruction. It is shown that in the limit of constant density, the transport scheme becomes the (original) characteristics-based scheme for incompressible flows, but the conservative and hybrid schemes lead to a new characteristics-based variant for constant density flows. The characteristics-based schemes are combined with second and third-order interpolation for increasing the computational accuracy locally at the cell faces of the control volume. Numerical experiments for constant density flows reveal that all the characteristics-based schemes result in the same flow solution, but they exhibit different convergence behavior. The multigrid implementation and numerical studies for variable density flows are presented in Part II of this study.