Laser–Induced Fluorescence Detection of Carbamates Traces in Water

The absorption and fluorescence spectra of carbaryl (CB), carbofuran (CF) and carbendazim (MBC) have been studied. Fluorescence lifetime and fluorescence quantum yields are also reported as well as the influence of pH, solvent and presence of humic acids on fluorescence. The limit of detection (LD) of the three compounds has been measured by direct analysis by laser-induced fluorescence (LIF) using a pulsed YAG laser with an Optical Parametric Oscillator (OPO) as excitation source and an Intensified Charged Coupled Device (ICCD) camera for the fluorescence detection. Instrumental LD found for CB, for MBC and for CF are respectively 4, 50 and 1000 ng L⁻¹. In tap water, the LD obtained is 800 ng L⁻¹ for MBC and 20,000 ng L⁻¹ for CF. For CB, the use of a time shift between excitation and emission allows to reach a LD of 20 ng L⁻¹ in tap water.     

Electronic core levels of hydroxyls at the surface of chromia related to their XPS O 1s signature: A DFT + U study

The Cr 2p and O 1s binding energy (BE) levels have been calculated by first principles methods for different models of hydroxylated (0001)-Cr₂O₃ surfaces. Several surface terminations have been considered. The calculations allow us to reproduce the O 1s shifts between O in oxide and OH groups. It is found that two main effects account for the OH binding energy shifts. On the one hand, the increased covalency of the O–H bond with respect to the Cr–O bond, lowers the electronic O (1s and 2p) energy, and in consequence the BE of the core levels (O 1s) are higher. On the other hand, the lower the OH coordination number, the higher the valence and core levels energy, and the lower the BE. Consequently, mono-coordinated hydroxyls have a binding energy near that of O^2? in the oxide (ΔBE_OH–O = ? 0.2–0.0 eV). Two-fold coordinated hydroxyls have a slightly higher BE (ΔBE_OH–O = + 0.3 eV). Three-fold coordinated OH groups have a higher binding energy (ΔBE_OH–O = + 0.6?0.7 eV), corresponding to that experimentally measured for OH groups. Finally, water adsorbed above OH groups exhibits a still higher BE (ΔBE_HOH–O = + 0.9–1.0 eV). The ΔBE are slightly under-estimated under the initial state approximation, and overestimated under the final state (Z + 1) approximation.     

Accurate standard‐based quantification of X‐ray fluorescence data using metal‐contaminated plant tissue

Quantitative X‐ray fluorescence (XRF) measurements have been conducted on naturally lead‐contaminated samples. The calibration procedure using the ratio of fluorescence to Compton scattered radiation was investigated using Monte Carlo simulation. Experimental results with low‐energy photons (14 keV) and simulations show a very good linearity of the fluorescence to Compton ratio as a function of metal concentration. Lead (Pb), iron (Fe) and zinc (Zn) are measured in samples of Phaseolus vulgaris (bean seeds) that have been grown using a nutritive solution with different Pb dopings. Naturally contaminated samples are thus obtained. The calibration must be done for fixed conditions of X‐ray energy and scattering angle, while X‐ray beam intensity and detector to sample distance can change from one sample to another. Simulation allows to evaluate the matrix effect on the calibration curve, and shows that linearity is preserved even in the presence of other heavy elements in the fluorescence spectrum. However, calibration must be done using samples with similar matrix as it affects the slope of the curve. Copyright © 2010 John Wiley & Sons, Ltd.     

The complexity of generating an exponentially distributed variate

We analyze in detail an almost optimal algorithm for generating an exponentially distributed variate. The algorithm is due to Knuth and Yao and relies on a method which goes back to J. von Neumann. It is shown here that it can generate k bits of an exponentially distributed variate using an average of about k + 5.67974692 coin flippings. This solves a problem left open by Knuth and Yao.     

Temperature Dependence of 1H Paramagnetic Chemical Shifts in Actinide Complexes,Beyond Bleaney's Theory: The AnVIO22+–Dipicolinic Acid Complexes (An=Np,Pu) as an Example

Actinide +VI complexes ( = , and ) with dipicolinic acid derivatives were synthesized and characterized by powder XRD, SQUID magnetometry and NMR spectroscopy. In addition, and complexes were described by first principles CAS based and two-component spin-restricted DFT methods. The analysis of the ¹H paramagnetic NMR chemical shifts for all protons of the ligands according to the X-rays structures shows that the Fermi contact contribution is negligible in agreement with spin density determined by unrestricted DFT. The magnetic susceptibility tensor is determined by combining SQUID, pNMR shifts and Evans’ method. The SO-RASPT2 results fit well the experimental magnetic susceptibility and pNMR chemical shifts. The role of the counterions in the solid phase is pointed out; their presence impacts the magnetic properties of the complex. The temperature dependence of the pNMR chemical shifts has a strong contribution, contrarily to Bleaney's theory for lanthanide complexes. The fitting of the temperature dependence of the pNMR chemical shifts and SQUID magnetic susceptibility by a two-Kramers-doublet model for the complex and a non-Kramers-doublet model for the complex allows for the experimental evaluation of energy gaps and magnetic moments of the paramagnetic center.     

Hippocampal metabolomics using ultrahigh-resolution mass spectrometry reveals neuroinflammation from Alzheimer’s disease in CRND8 mice

In the wake of genomics, metabolomics characterizes the small molecular metabolites revealing the phenotypes induced by gene mutants. To address the metabolic signatures in the hippocampus of the amyloid-beta (Aβ) peptides produced in transgenic (Tg) CRND8 mice, high-field ion cyclotron resonance–Fourier transform mass spectrometry supported by LC-LTQ-Orbitrap was introduced to profile the extracted metabolites. More than 10,000 ions were detected in the mass profile for each sample. Subsequently, peak alignment and the 80 % rule followed by feature selection based on T score computation were performed. The putative identification was also conducted using the highly accurate masses with isotopic distribution by interfacing the MassTRIX database as well as MS/MS fragmentation generated in the LTQ-Orbitrap after chromatographic separation. Consequently, 58 differentiating masses were tentatively identified while up to 44 differentiating elemental compositions could not be biologically annotated in the databases. Nonetheless, of the putatively annotated masses, eicosanoids in arachidonic acid metabolism, fatty acid beta-oxidation disorders as well as disturbed glucose metabolism were highlighted as metabolic traits of Aβ toxicity in Tg CRND8 mice. Furthermore, a web-based bioinformatic tool was used for simulation of the metabolic pathways. As a result of the obtained metabolic signatures, the arachidonic acid metabolism dominates the metabolic perturbation in hippocampal tissues of Tg CRND8 mice compared to non-Tg littermates, indicating that Aβ toxicity functions neuroinflammation in hippocampal tissue and new theranostic opportunities might be offered by characterization of altered arachidonic acid metabolism for Alzheimer’s disease.      

Laterally dibenzyloxy-branched nematogens with large nematic range and rich solid polymorphism

Mesogenic compounds containing four rings in the core usually have very high melting points. However, when two identical lateral benzyloxy groups are introduced on the same side of one of the central rings, the melting point is lowered dramatically and a large nematic range is retained. This range is affected by the bulkiness of the para-substituents in the lateral rings. Methyl groups can be introduced in the ortho- or meta-positions with a consequent decrease in the melting temperature without much affecting the nematic range. These compounds exhibit a rich solid polymorphism which is certainly related to the effect of the conformations of the lateral substituent on the molecular arrangment in the solid phase. Some preliminary NMR experiments on the nematic phase indicate that the molecular long axis coincides with the core axis, whereas the para-axis of the lateral fragment makes an angle close to the magic angle with respect to the molecular long axis.     

The Effect of Biomass Immobilization Support Material and Bed Porosity on Hydrogen Production in an Upflow Anaerobic Packed-Bed Bioreactor

The aim of this study was to investigate the effect of the support material used for biomass attachment and bed porosity on the potential generation of hydrogen gas in an anaerobic bioreactor treating low-strength wastewater. For this purpose, an upflow anaerobic packed-bed (UAPB) reactor fed with sucrose-based synthetic wastewater was used. Three reactors with various support materials (expanded clay, vegetal coal, and low-density polyethylene) were operated for hydraulic retention time (HRT) of 0.5 and 2 h. Based on the results obtained, three further reactors were operated with low-density polyethylene as a material support using various bed porosities (91, 75, and 50 %) for an HRT of 0.5 h. The UAPB reactor was found to be a feasible technology for hydrogen production, reaching a maximum substrate-based hydrogen yield of 7 mol H₂ mol^?1 sucrose for an HRT of 0.5 h. The type of support material used did not affect hydrogen production or the microbial population inside the reactor. Increasing the bed porosity to 91 % provided a continuous and cyclic production of hydrogen, whereas the lower bed porosities resulted in a reduced time of hydrogen production due to biomass accumulation, which resulted in a decreasing working volume.     

The role of nanocellulose fibers, starch and chitosan on multipolysaccharide based films

Thin nanocomposite films of thermoplastic starch, chitosan and cellulose nanofibers (bacterial cellulose or nanofibrillated cellulose) were prepared for the first time by solvent casting of water based suspensions of the three polysaccharides. The role of the different bioploymers on the final properties (thermal stability, transparency, mechanical performance and antimicrobial activity) of the films was related with their intrinsic features, contents and synergic effects resulting from the establishment of interactions between them. Thermoplastic starch displays an important role on the thermal stability of the films because it is the most stable polysaccharide; however it has a negative impact on the mechanical performance and transparency of the films. The addition of chitosan improves considerably the transparency (up to 50 % transmittance for 50 % of chitosan, in respect to the amount of starch), mechanical performance and antimicrobial properties (at least 25 % of chitosan and no more than 10 % of cellulose nanofibers are required to observe bacteriostatic or bactericidal activity) but decrease their thermal stability. The incorporation of cellulose nanofibers had the strongest positive impact on the mechanical properties of the materials (increments of up to 15 and 30 MPa on the Young′s modulus and Tensile strength, respectively, for films with 20 % of BC or NFC). Nonetheless, the impact in thermal stability and mechanical performance of the films, promoted by the addition of chitosan and cellulose nanofibres, respectively, was higher than the expected considering their percentage contents certainly because of the establishment of strong and complex interactions between the three polysaccharides.     

Principal hierarchies of infinite-dimensional Frobenius manifolds: The extended 2D Toda lattice

We define a dispersionless tau-symmetric bihamiltonian integrable hierarchy on the space of pairs of functions analytic inside/outside the unit circle with simple poles at 0/∞$0/\infty$ respectively, which extends the dispersionless 2D Toda hierarchy of Takasaki and Takebe. Then we construct the deformed flat connection of the infinite-dimensional Frobenius manifold _M0$M_0$ introduced by Carlet, Dubrovin and Mertens (2011) [3] and, by explicitly solving the deformed flatness equations, we prove that the extended 2D Toda hierarchy coincides with principal hierarchy of _M0$M_0$.