Generalized Maxwell model for the viscoelastic behavior of a soda-lime-silica glass under low frequency shear loading

The linear viscoelastic behavior of a soda-lime-silica glass under low frequency shear loading is investigated in the glass transition range. Using the time-temperature superposition technique, the master curves of the shear dynamic relaxation moduli are obtained at a reference temperature of 566°C. A method to determine the viscoelastic constants from dynamic relaxation moduli is proposed. However, some viscoelastic constants cannot be directly measured from the experimental curves and others cannot be precisely obtained due to non-linearity effects at very low frequencies. The generalized Maxwell model is investigated from the experimental dynamic moduli without fixing the viscoelastic constants. A set of parameters is shown to be in good agreement with the experimental dynamic relaxation moduli, but does not give the correct values of the viscoelastic constants of the investigated glass. The soda-lime-silica glass exhibits a non-linear viscoelastic behavior at very low stress level which is usually observed for organic glasses. This non-linear behavior is questioned.     

Saint-Venant's principle in nonlinear plane elasticity with sufficiently small strains

A homogeneous, isotropic cylinder in an equilibrium state of plane strain, whose cross-section is a rectangle R : [0 < y ₁ < 2L; 0 < y ₂ < h] with h/L 1, is considered. There are no body forces and the long sides are stress free. At y ₁ = 0 and y ₁ = 2L, there are arbitrary loadings, each statically equivalent to a uniformly distributed tensile or compressive stress c. Within the theory of nonlinear elasticity and with the strains and strain gradients assumed to be sufficiently small (but with no such assumptions on the displacement gradients), it is proved that if (,=1,2) represents the Cauchy stress tensor and the Kronecker delta, then |–c₁₁| decays exponentially to zero in R with distance from the nearer end, and the decay constant depends only upon the material but is independent of L.     

Using conformationally locked nucleosides to calibrate the anomeric effect: Implications for glycosyl bond stability

Steric and electronic parameters, such as the anomeric effect (AE) and gauche effect play significant roles in steering the North&lrarr;South equilibrium of nucleosides in solution.Two isomeric oxa-bicyclo[3.1.0]hexane nucleosides that are conformationally locked in either the North or the South conformation of the pseudorotational cycle were designed to study the consequences of having the AE operational or not, independent of other parameters. The rigidity of the system allowed the orientation of the orbitals involved to be set in ‘fixed’ relationships, either antiperiplanar where the AE is permanently ‘on’, or gauche where the AE is impaired. The consequences of these two alternatives were subjected to high-level calculations and measured experimentally by X-ray crystallography, hydrolytic stability of the glycosyl bond, and pK_a values.     

Preparation of a polyacrylonitrile/multi-walled carbon nanotubes composite by surface-initiated atom transfer radical polymerization on a stainless steel wire for solid-phase microextraction

We report on the fabrication and performances of a solid-phase microextraction (SPME) fiber based on a stainless steel wire coated with a covalently attached polyacrylonitrile (PAN)/multi-walled carbon nanotubes (MWCNTs) composite. This new coating is obtained by atom transfer radical polymerization (ATRP) of acrylonitrile mixed with MWCNTs. ATRP is initiated from 11-(2-bromo-2-methylpropionyloxy)-undecyl-phosphonic acid molecules grafted on the wire surface via the phosphonic acid group. The extraction performances of the fibers are assessed on different classes of compounds (polar, non-polar, aromatic, etc.) from water solutions by headspace extraction. The optimization of the parameters affecting the extraction efficiency of the target compounds was studied as well as the reproducibility and the repeatability of the fiber. The fibers sustain more than 200 extractions during which they remain chemically stable and maintain good performances (detection limits lower than 2 μg/l, repeatability, etc.). Considering their robustness together with their easy and inexpensive fabrication, these fibers could constitute promising alternatives to existing products.     

The application of multiplexed,multi‐dimensional ultra‐high‐performance liquid chromatography/tandem mass spectrometry to the high‐throughput screening of lysosomal storage disorders in newborn dried bloodspots

Lysozomal storage disorders are just beginning to be routinely screened using enzyme activity assays involving dried blood spots and tandem mass spectrometry (MS/MS). This paper discusses some of the analytical challenges associated with published assays including complex sample preparation and potential interference from excess residual substrate. Solutions to these challenges are presented in the form of on‐line two‐dimensional chromatography to eliminate off‐line liquid‐liquid extraction (LLE) and solid‐phase extraction (SPE), the use of ultra‐high‐performance liquid chromatography (UHPLC) to separate excess substrate from all other analytes and multiplexed sample introduction for higher throughput required of a population screening assay. High sensitivity, specificity and throughput were demonstrated using this novel method. Copyright © 2010 John Wiley & Sons, Ltd.     

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Fresnel incoherent correlation hologram—— a review （Invited Paper）

Holographic imaging offers a reliable and fast method to capture the complete three-dimensional （3D） information of the scene from a single perspective. We review our recently proposed single-channel optical system for generating digital Fresnel holograms of 3D real-existing objects illuminated by incoherent light. In this motionless holographic technique, light is reflected, or emitted from a 3D object, propagates through a spatial light modulator （SLM）, and is recorded by a digital camera. The SLM is used as a beamsplitter of the single-channel incoherent interferometer, such that each spherical beam originated from each object point is split into two spherical beams with two different curve radii. Incoherent sum of the entire interferences between all the couples of spherical beams creates the Fresnel hologram of the observed 3D object. When this hologram is reconstructed in the computer, the 3D properties of the object are revealed.     

The enantioselective synthesis of (R)- and (S)-3-amino-3,4-dihydro-1H-[1,8]naphthyridin-2-one

A number of approaches to the enantioselective synthesis of (R)- and (S)-3-amino-3,4-dihydro-1H-[1,8]naphthyridin-2-one were studied. A novel one-pot asymmetric reduction/lactamization provided the desired products in high yield and enantiomeric excess.     

Tripodal Thiols as Ligands for Molecular Magnets: Very Strong Antiferromagnetic Exchange Interactions in Vanadium(III) Clusters

The synthesis, structural and magnetic characterisation of [V^III₃O(tmme)₂(diimine)₂Cl] [diimine=2,2′‐bipyridine ( 1 ) or 1,10‐phenanthroline ( 2 )] and (HNEt₃)₂[V^III₄O(tmme)₄] ( 3 ) is reported, in which H₃tmme is tris(mercaptomethyl)ethane, MeC(CH₂SH)₃, the thiol analogue of the famous tripodal alcohol ligands typified by H₃thme [tris(hydroxymethyl)ethane, MeC(CH₂OH)₃]. Complexes 1 and 3 have “T‐shaped” and square topologies, respectively, and the latter is centred on a rare example of a square‐planar oxide. The tri‐thiolate ligands bind the periphery of the clusters and provide such strong antiferromagnetic exchange pathways that in both cases only a single total spin state is occupied up to room temperature, in the absence of metal–metal bonding. Magnetic data, electronic structure calculations and electrochemical data are reported.     

Predictive modeling of positive mode IMS gas-phase ionization: is 2nd-order Møller-Plesset perturbation theory adequate?

Low level ab initio Quantum Chemistry (QC) is shown to be a promising technique for predicting the relative ordering of a wide variety of potential analyte, dopant, and interferent molecules, by their proton affinities (PA). Computed PAs, using a single level of chemical theory, are summarized for 53 compounds and when compared to literature reference data have a mean unsigned error of ∼9.5 kJ/mol. Where applicable, multiple conformations of the protonated species were explored. In these cases, the Boltzmann weighted PA is reported. Finally, examples are shown in which QC modeling is used to predict potential fragmentation products initiated by the positive mode ionization.