Precision measurement of theg J factors of metastable atomic states of88Sr and138Ba using the atomic beam magnetic resonance method

Theg _J factors of the metastable states³ P ₂ of⁸⁸Sr and³ D ₁,³ D ₂,³ D ₃, and¹ D ₂ of¹³⁸Ba have been measured using the atomic-beam magnetic resonance method. The metastable states were populated by an electric discharge within the atomic-beam source. From the measurements of rf transitions between the Zeeman levels (m _J =+1)?(m _J =?1) we obtained:⁸⁸Sr:g _J (³ P ₂) =1.501124(10)¹³⁸Ba:g _J (³ D ₃)=1.3340823 (10)g _J (³ D′₂)=1.1637406(11)g _J (³ D ₁)=0.4985751(13)g _J (¹ D′₂)=1.003 1449(10). The relativistic and diamagnetic corrections for theg _J factor of the³ P ₂ state of Sr have been calculated. With these and the Schwinger correction included we getg _J (³ P ₂)=1.501119(12).     

Carbon-13, 1H spin-spin coupling. V—π-benzenechromium tricarbonyl and the π-tropyliumchromium tricarbonyl cation

The ¹³C, ¹H spin-spin coupling constants have been determined for π-benzenechromium tricarbonyl (3) and the π-tropyliumchromium tricarbonyl cation using the ¹³C{²H}double resonance technique described in a previous paper. In addition, conventional analysis of the ¹H-coupled ¹³C NMR spectrum of 3 was carried out and the ¹H NMR spectrum of 3 partially oriented in the nematic phase was analysed. Both treatments also allowed the determination of the ¹H, ¹H coupling constants for this compound. The ⁿJ(CH) results are discussed on the basis of structural data and the theoretical results available. The complexation effects for ¹J(CH) are found to correlate with the C? H overlap population and hybridization changes, and those for ³J(CH) with the CC bond lengths and π-bond orders. The dependence of ²J(CH) on CC bond length as well as on the CCH bond angle is indicated. The liquid crystal results are compared with those of related studies.     

Mössbauer spectroscopy of an ordered phase (superstructure) of FeNi in an iron meteorite

Mössbauer and X-ray spectra for taenite lamellae from the iron meteorite Cape York show that the lamellae contain an ordered phase with the composition FeNi, and with the structure L10. This phase has not previously been detected in meteorites.     

Ultrasonic-assisted supramolecular solvent-based liquid phase microextraction of mercury as 1-(2-pyridylazo)-2-naphthol complexes from water samples

A separation-preconcentration method based on supramolecular solvent ultrasonic-assisted liquid-phase microextraction (Ss-USA-LPME) for spectrophotometric determination of mercury as 1-(2-pyridylazo)-2-naphthol (PAN) chelates has been established. Red coloured Hg(II)-PAN hydrophobic complex was extracted into the supramolecular phase (1-decanol/THF) at pH 9.5. The extract was separated from aqueous phase by centrifugation, diluted with ethanol and determined by UV–Vis spectrophotometer at λ_max = 560 nm. The influences of important analytical parameters such as pH, amount of PAN, 1-decanol and THF, sample volume and matrix effects for the quantitative recoveries were examined and optimised. Under the optimised experimental conditions, the amount of ligand, 1-decanol and THF were 1.0 × 10^–4 M, 200 µL and 300 µL, respectively. The optimum time of ultrasonic bath and centrifugation were found as 2 min and 5 min. A linear calibration graph was obtained linearly in the concentration ranges of 8.3–1000 µg L^?1. The preconcentration factor was obtained as 20. The limit of detection (LOD) was 2.6 µg L^?1 with the relative standard deviation (RSD) of 2.4% for mercury (C = 100 µg L^?1, n = 7). The validity of the developed Ss-USA-LPME technique was checked with a certified reference material of NIST 1641d. The presented method has been successfully applied to the determination of mercury in water samples.     

Synthesis and catalytic application of chiral 1,1'-Bi-2-naphthol- and biphenanthrol-based pincer complexes: selective allylation of sulfonimines with allyl stannane and allyl trifluoroborate

New easily accessible 1,1'-bi-2-naphthol- (BINOL-) and biphenanthrol-based chiral pincer complex catalysts were prepared for selective (up to 85% enantiomeric excess) allylation of sulfonimines. The chiral pincer complexes were prepared by a flexible modular approach allowing an efficient tuning of the selectivity of the catalysts. By employment of the different enantiomeric forms of the catalysts, both enantiomers of the homoallylic amines could be selectively obtained. Both allyl stannanes and allyl trifluoroborates can be employed as allyl sources in the reactions. The biphenanthrol-based complexes gave higher selectivity than the substituted BINOL-based analogues, probably because of the well-shaped chiral pocket generated by employment of the biphenanthrol complexes. The enantioselective allylation of sulfonimines presented in this study has important implications for the mechanism given for the pincer complex-catalyzed allylation reactions, confirming that this process takes place without involvement of palladium(0) species.     

Amperometric Lactate Biosensor Based on Carbon Paste Electrode Modified with Benzo[c]cinnoline and Multiwalled Carbon Nanotubes

Amperometric lactate biosensor based on a carbon paste electrode modified with benzo[c]cinnoline and multiwalled carbon nanotubes is reported. Incorporation of benzo[c]cinnoline acting as a mediator and multiwalled carbon nanotubes providing a conduction pathway to accelerate electron transfer due to their excellent conductivity into carbon paste matrix resulted in a high performance lactate biosensor. The resulting biosensor exhibited a fast response, high selectivity, good repeatability and storage stability. Under the optimal conditions, the enzyme electrode showed the detection limit of 7.0×10^?8 M with a linear range of 2.0×10^?7 M–1.1×10^?4 M. The usefulness of the biosensor was demonstrated in serum samples.     

Sparse Variational Analysis of Linear Mixed Models for Large Data Sets

It is increasingly common to be faced with longitudinal or multi-level data sets that have large numbers of predictors and/or a large sample size. Current methods of fitting and inference for mixed effects models tend to perform poorly in such settings. When there are many variables, it is appealing to allow uncertainty in subset selection and to obtain a sparse characterization of the data. Bayesian methods are available to address these goals using Markov chain Monte Carlo (MCMC), but MCMC is very computationally expensive and can be infeasible in large p and/or large n problems. As a fast approximate Bayes solution, we recommend a novel approximation to the posterior relying on variational methods. Variational methods are used to approximate the posterior of the parameters in a decomposition of the variance components, with priors chosen to obtain a sparse solution that allows selection of random effects. The method is evaluated through a simulation study, and applied to an epidemiological application.     

Functionalization of poly-SNS-anchored carboxylic acid with Lys and PAMAM: surface modifications for biomolecule immobilization/stabilization and bio-sensing applications

Poly(2-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl) (SNS) acetic acid) was electrochemically deposited on graphite electrodes and functionalized with lysine (Lys) amino acid and poly(amidoamine) derivatives (PAMAM?G2 and PAMAM?G4) to investigate their matrix properties for biosensor applications. Glucose oxidase (GOx) was immobilized onto the modified surface as the model enzyme. X-Ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were used to report the surface properties of the matrices in each step of the biosensor construction. The biosensors were characterized in terms of their operational and storage stabilities and the kinetic parameters (K and I(max)). Three new glucose biosensors revealed good stability, featuring low detection limits (19.0 μM, 3.47 μM and 2.93 μM for lysine-, PAMAM?G2- and PAMAM?G4-functionalized electrodes, respectively) and prolonged the shelf lives (4, 5, and 6 weeks for Lys-, PAMAM?G2- and PAMAM?G4-modified electrodes, respectively). The proposed biosensors were tested for glucose detection on real human blood serum samples.     

Nanocomposites Prepared by Solution Blending: Microstructure and Mechanical Properties

Composites of poly(vinyl chloride) (PVC) filled with micron‐ and nanosized calcium carbonate (CaCO₃) particles were prepared by solution blending. The influences of particle size and CaCO₃ content on the microstructure and mechanical properties of the PVC composites were investigated by means of polarized optical microscopy and mechanical testing. The polarized optical microscope images revealed that nanosized CaCO₃ particles were more agglomerated than micron‐sized CaCO₃ particles and the amount of agglomerates increased with increasing particle content. PVC/CaCO₃‐0.22 composites (PVC nanocomposite filled with 220‐nm‐particle‐sized CaCO₃) 5 phr CaCO₃ content had the maximum tensile strength. The Young's modulus of all composites increased with increasing particle content. The energy at break of all composites showed a decreasing trend as a function of CaCO₃ content and varied with particle size.     

Hydrogen activation and metal hydride formation trigger cluster formation from supported iridium complexes

The formation of iridium clusters from supported mononuclear iridium complexes in H(2) at 300 K and 1 bar was investigated by spectroscopy and atomic-resolution scanning transmission electron microscopy. The first steps of cluster formation from zeolite-supported Ir(C(2)H(4))(2) complexes are triggered by the activation of H(2) and the formation of iridium hydride, accompanied by the breaking of iridium-support bonds. This reactivity can be controlled by the choice of ligands on the iridium, which include the support.