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.     

Size Effects in the Catalytic Activity of Unsupported Metallic Nanoparticles

The influence of the size of nanoparticles on their catalytic activity was investigated for two systems on unsupported, i.e. gasborne nanoparticles. For the oxidation of hydrogen on Pt nanoparticle agglomerates, transport processes had to be taken into account to extract the real nanoparticle size effects. The results indicate an optimum particle size for the catalytic activity below 5nm which points clearly toward a real volume effect. In the case of the methanation reaction on gasborne Ni nanoparticles, no transport limitations were observed and the product concentration was directly proportional to the activity of the primary particles. We found an activity maximum for particles of about 19nm in diameter. This size is too large to be attributed to a real nanoparticle size effect induced by the electronic band structure. Therefore, we concluded that the particle size influences the adsorption behavior of the carbon monoxide molecules. In fact, it is known that intermediate adsorption enthalpies may favor dissociation processes, which is an essential step for the reaction, as manifested in the so called volcano-shaped curve. Then, in addition to the material dependence of the adsorption, we would also encounter a direct size dependence in the case of methanation on gasborne Ni nanoparticles.     

Modified growth theory for high supersaturation

The classical BCF (Burton, Cabrera, Frank) growth theory assumes atomic step motion driven by the diffusion of adatoms toward the step acting as sinks. Stationary solutions of the diffusion equation have been obtained by BCF neglecting the movement of the coordinate system. By using a moving frame, as already done for a single-step flow model by Mullins and Hirth, we calculate the velocity of a periodic parallel sequence of steps, the distribution of adatoms, and the condensation coefficient as a function of the step distance for various supersaturations. This modification result in significant deviations from the original theory if a dimensionless normalized supersaturation parameterb which is proportional to the supersaturation exceeds one-half. Large values of this parameterb may occur for the high supersaturation found in Si-MBE (molecular beam epitaxy) for temperatures far below the melting point.     

Antioxidant activity of rosemary extracts in solution and embedded in polymeric systems

The rosemary extract was encapsulated in polyethylene or in covalently-based network gels. The covalent gels were obtained by the reaction of isocyanate end-capped polyethylene glycol (PEG) with β-cyclodextrin or glycerol. The 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay was used to evaluate the antioxidant activity (AA) of rosemary extract entrapped in polymeric structures and in ethanol or water solutions. The AA of the rosemary extract was determined using a DPPH radical for samples prepared in ethanol, and a water-soluble derivative, the sulphonated DPPH radical (DPPH-SO₃Na), for the rosemary extract in water. Formulation of the rosemary extract in polymeric gels ensures a rapid release which determines the AA values similar to those in solution.     

Synthesis,characterization of nanosized CoAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and its electrocatalytic activity for enhanced sensing application

Nanosized cobalt aluminate (CoAl₂O₄) was prepared by thermolysis of heteronuclear coordination compound, namely [Al₂Co(C₂O₄)₄(OH₂)₆]. The synthesized precursor was characterized by chemical analysis, vibrational spectra and thermal analysis. The cobalt aluminate obtained after a heating treatment of the precursor at 700 °C was characterized by IR, XRD, TEM coupled with SAED measurements. Two types of carbon-based electrodes, glassy carbon and boron-doped diamond electrodes were decorated with the obtained cobalt aluminate in order to enhance the electroanalytical performance for the tetracycline (TC) detection in the aqueous solutions. Cyclic voltammetry technique was used to determine the effect of the nanosized CoAl₂O₄ on the electrochemical oxidation of TC and as consequence, for TC detection at both carbon-based electrodes. The obtained cobalt aluminate exhibited the electrocatalytic activity toward TC detection in direct relation with the type of the carbon substrate, which allowed enhancing the electroanalytical parameters of TC detection in the aqueous solution.