Novel tailormade Bi4MO4(PO4)2 structural type (M = Mg, Zn)

In the Bi(2)O(3)-MO-P(2)O(5) ternary system, the commonly observed sizable 1D ribbon-like units have been extended to their 2D infinite end member, leading to the novel tailormade Bi(4)MO(4)(PO(4))(2) compounds. It contains planar [Bi(2)O(2)](2+) derivatives, separated by two slabs of PO(4), which create channels hosting the M(2+) cations (M = Mg, Zn). For both compounds, supercell orderings occur comparatively to the predicted ideal crystal structure (V(Mg) = 2V(ideal) and V(Zn) = 8V(ideal)). In the Mg case a transition into the ideal lattice occurs above 450 °C. In spite of the conceptual assembly of 2D motifs, the final architecture is three-dimensional due to strong interbonds. Thus, our work gives new insights on the possibility for versatile organization of original secondary building units (SBUs) able to self-assemble into predicted structural edifices. Single-crystal and powder XRD versus temperature, high-temperature (31)P NMR, as well as transmission electron microscopy were used for structural characterization. Preliminary electric characterization is also reported.     

Multiresidue method to quantify pesticides in fish muscle by QuEChERS-based extraction and LC-MS/MS

Pesticide residues in fish muscle are an environmental and a health safety concern which requires analytical methods presenting high sensitivity and low limits of quantification. In this study, adapted QuEChERS method, coupled to liquid chromatography tandem mass spectrometry (Scheduled MRM-5500 QTRAP), was developed to quantify 13 pesticides (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl) in muscle of fish. Quantification limits were below 1 ng g⁻¹ except for clomazone (1.8 ng g⁻¹) and quizalofop (7.4 ng g⁻¹). Best recoveries were observed for perch (>80%) and roach (>68%), except for thifensulfuron-methyl. Lower recoveries had been observed for carp (6% to 86%). Relative standard deviation was lower than 28% for intra-day and 29% for inter-day analysis, respectively. This method was successfully tested on three fish species, naturally or orally exposed: roach (Rutilus rutilus), perch (Perca fluviatilis) and carp (Cyprinus carpio). Few levels were observed in fish naturally exposed, but carp and perch orally contaminated showed measurable levels in their muscles.     

Multiresidue method for the determination of 13 pesticides in three environmental matrices: water, sediments and fish muscle

Pesticides residues in aquatic ecosystems are an environmental concern which requires efficient analytical methods. In this study, we proposed a generic method for the quantification of 13 pesticides (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl) in three environmental matrices. Pesticides from water were extracted using a solid phase extraction system and a single solid-liquid extraction method was optimized for sediment and fish muscle, followed by a unique analysis by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Limits of quantification were below 5 ng L⁻¹ for water (except for fluroxypyr and iprodion) and ranged between 0.1 ng g⁻¹ and 57.7 ng g⁻¹ for sediments and regarding fish, were below 1 ng g⁻¹ for 8 molecules and were determined between 5 and 49 ng g⁻¹ for the 5 other compounds. This method was finally used as a new routine practice for environmental research.     

Ultrasound propagation in trabecular bone: A numerical study of the influence of microcracks

The accumulation of microdamage in trabecular bone tissue is suspected of being a predictive indicator of osteoporosis diagnosis. To quantify this microdamage, the Dynamic AcoustoElastic Testing (DAET) method measures the Time Of Flight (TOF) and amplitude variations of transmitted ultrasound (US) pulses, while the bone sample is submitted to a low frequency sinusoidal hydrostatic pressure (opening/closing of microcracks). However, DAET is both sensitive to viscoelastic properties changes and microcracks density. To verify the microcracks density contribution on DAET results, a numerical approach is proposed. Multliple configurations of microdamaged trabecular bone-tissue-like mesh have been simulated. A 2D pseudo-spectral time domain numerical model was then developed to simulate linear wave propagation in heterogeneous solids. The influence of the microcracks number and orientation on the US TOF was particularly investigated. Results are discussed and compared with experimental data obtained from DAET measurements in trabecular bone samples.     

Toward predictive permeabilities: Experimental measurements and multiscale simulation of methanol transport in Nafion

A polymer membrane's permeability to solutes determines its suitability for various applications: a permeability value is essential for predicting performance in diverse contexts. Using aqueous methanol permeation through Nafion as an example, we describe a methodology for determining membrane permeability that accounts for boundary layer effects and the possibility of swelling. For the materials and apparatus used herein, analysis of a permeance measurement and computational fluid dynamics simulations show that the mass transfer boundary layer is on the order of ones to tens of microns. The data are used to develop and validate a multiscale model describing solute permeation through a hydrated membrane as a series of physical mechanistic steps: reversible adsorption from solution at the membrane interface, diffusion driven by a concentration gradient within the membrane, and reversible desorption into solution at the opposite membrane interface. The validated model is used to predict methanol transport across a solar-driven CO₂ reduction device and to assess the impact of polymer changes on the measured value. The approach of combining experimental data, computational fluid dynamics, and the mechanistic multiscale model is expected to provide more accurate analysis of membrane permeation data in cases with polymer swelling or unusual device geometries, among others.     

Hamiltonian systems with indefinite kinetic energy

Some interesting features of a class of two-dimensional Hamiltonians with indefinite kinetic energy are considered. It is shown that such Hamiltonians cannot be reduced, in general, to an equivalent dynamical Hamiltonian with positive definite kinetic energy quadratic in velocities. Complex nonlinear evolution equations like the K-dV, the MK-dV and the sine-Gordon equations possess such Hamiltonians. The case of complex K-dV equation has been considered in detail to demonstrate the generic features. The two-dimensional real systems obtained by analytic continuation to complex plane of one-dimensional dynamical systems are also discussed. The evolution equations for nonlinear, amplitude-modulated Langmuir waves as well as circularly polarized electromagnetic waves in plasmas, are considered as illustrative examples.     

Highly selective hydroformylation of the cinchona alkaloids

The four naturally occurring cinchona alkaloids were subjected to hydroformylation to create an extra functional group that allows immobilization. Cinchonidine, quinine, and quinidine, could be hydroformylated with virtually complete terminal selectivity, using a rhodium/tetraphosphite catalyst. The cinchonidine aldehyde was reduced to the alcohol and subjected to reductive amination with benzylamine.     

Exact nonlinear alfvén waves

Exact localized nonlinear Alfvén waves are investigated by retaining the complete ion nonlinearity and the finite-β effects. Solitary waves with a density hump and a density dip are found to exist.     

Effect of hot ions on ion acoustic solitons and holes

In a two-electron-component plasma, we have investigated the effect of hot ions by retaining the full nonlinearities. Even an extremely small ion temperature can drastically reduce the maximum amplitude for solitons as well as holes.