The influence of the shape of Au nanoparticles on the catalytic current of fructose dehydrogenase

Graphite electrodes were modified with triangular (AuNTrs) or spherical (AuNPs) nanoparticles and further modified with fructose dehydrogenase (FDH). The present study reports the effect of the shape of these nanoparticles (NPs) on the catalytic current of immobilized FDH pointing out the different contributions on the mass transfer–limited and kinetically limited currents. The influence of the shape of the NPs on the mass transfer–limited and the kinetically limited current has been proved by using two different methods: a rotating disk electrode (RDE) and an electrode mounted in a wall jet flow-through electrochemical cell attached to a flow system. The advantages of using the wall jet flow system compared with the RDE system for kinetic investigations are as follows: no need to account for substrate consumption, especially in the case of desorption of enzyme, and studies of product-inhibited enzymes. The comparison reveals that virtually identical results can be obtained using either of the two techniques. The heterogeneous electron transfer (ET) rate constants (k_S) were found to be 3.8 ± 0.3 s⁻¹ and 0.9 ± 0.1 s⁻¹, for triangular and spherical NPs, respectively. The improvement observed for the electrode modified with AuNTrs suggests a more effective enzyme-NP interaction, which can allocate a higher number of enzyme molecules on the electrode surface.

The shape of gold nanoparticles has a crucial effect on the catalytic current related to the oxidation of D-(-)-fructose to 5-keto-D-(-)-fructose occurring at the FDH-modified electrode surface. In particular, AuNTrs have a higher effect compared with the spherical one.

     

Synthesis and luminescence behaviour of novel heterodecanuclear silver(I)-rhenium(I) alkynyl complexes. X-ray crystal structures of [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Me2bpy)(CO)3]4](PF6)2 and [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Br2phen)(CO)3]4](PF6)2

A novel series of luminescent heterodecanuclear mixed-metal alkynyl complexes, [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(N--N)(CO)3]4](PF6)2, (N--N = tBu2bpy, Me2bpy, phen, Br2phen), have been successfully synthesized; the X-ray crystal structures of [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Me2bpy)(CO)3]4](PF6)2 and [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Br2phen)(CO)3]4](PF6)2 have also been determined.     

Chemical Studies of Formosan Cobra (Naja Naja Atra) Venom: Part III. N-Terminal Amino Acid Analysis of Some Purified Protein Components by DNP and DNS Methods

N-Terminal amino acid residues of Fractions IX, X, and XII were reinvestigated by DNP and DNS methods with two-dimensional polyamide thin-layer chromatography. It was found that our previous work¹ had been erroneously concluded. By the present work, it was obvious that all three fractions had Leu as their N-terminal amino acid residues.     

Intercalating lithium into the lattice of silver nanoparticles boosts catalytic hydrogenation of carbon–oxygen bonds

Coinage metal nanoparticles with high dispersion can serve as highly efficient heterogeneous catalysts. However, owing to their low melting point, poor thermal stability remains a major obstacle towards their application under reaction conditions. It is a common practice to use porous inorganic templates such as mesoporous silica SBA-15 to disperse Ag nanoparticles (NPs) against aggregation but their stability is far from satisfactory. Here, we show that the catalytic activity for hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG) over Ag NPs dispersed on SBA-15 silica can be further promoted by incorporation of alkali metal ions at small loading, which follows the inverse order of their cationic size: Li⁺ > Na⁺ > K⁺ > Rb⁺. Among these, 5Ag₁–Li_0.05/SBA-15 can double the MG yield compared to pristine 5Ag/SBA-15 under identical conditions with superior thermal stability. Akin to the effect of an ionic surfactant on stabilization of a micro-emulsion, the cationic charge of an alkali metal ion can maintain dispersion and modulate the surface valence of Ag NPs. Interstitial Li in the octahedral holes of the face center packed Ag lattice is for the first time confirmed by X-ray pair distribution function and electron ptychography. It is believed that this interstitial-stabilization of coinage metal nanoparticles could be broadly applicable to multi-metallic nanomaterials for a broad range of C–O bond activating catalytic reactions of esters.

Coinage metal nanoparticles with high dispersion can serve as highly efficient heterogeneous catalysts.     

Electron spin-spin contact interaction in many-electron atoms

A general formulation has been developed for the evaluation of the total electron spin-spin contact interaction in many-electron atoms, including both the intra- and inter-shell contributions. Calculations have been carried out, using existing analytical Hartree-Fock functions, for the positive ions, neutral systems, and negative ions for all the atoms from He to Kr.

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Zusammenfassung Es wird ein allgemeiner Formalismus zur Berechnung der gesamten Elektronen-Spin-Spin-Kontakt-Wechselwirkung in Vielelektronen-Atomen angegeben, der sowohl die Anteile der Wechselwirkung innerhalb einer Schale als auch zwischen einzelnen Schalen berücksichtigt. Berechnungen wurden unter Benutzung vorhandener analytischer Hartree-Fock-Funktionen für die positiven Ionen, die neutralen Systeme und die negativen Ionen aller Atome von He bis Kr durchgeführt.

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This work has been supported in part by the National Research Council of Canada.     

Closed‐form rectangular atomic wave functions of an N‐dimensional atom

A closed‐form expression has been derived to obtain the N‐dimensional rectangular atomic wave functions. The wave functions can be obtained straightforwardly with the knowledge of the angular momentum quantum numbers and the dimension and there is no need to employ recursive methods as in previous works. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem 88: 263–274, 2002     

Simultaneous determination of berberine in rat blood,liver and bile using microdialysis coupled to high-performance liquid chromatography

High-performance liquid chromatography coupled to microdialysis was used for the simultaneous determination of unbound berberine in rat blood, liver and bile for a pharmacokinetic study. Microdialysis probes were simultaneously inserted into the jugular vein toward the right atrium, the median lobe of the liver, and the bile duct of male Sprague-Dawley rats for biological fluid sampling after administration of berberine (10 mg/kg) through the femoral vein. Berberine and dialysates were separated using a Zorbax SB-phenyl column and a mobile phase comprised of acetonitrile-methanol-20 mM monosodium phosphate (pH 3.0) (35:20:45, v/v) together with 0.1 mM 1-octanesulfonic acid. The detection limit for berberine was 10 ng/ml. The concentration-response relationship was linear (r2 > 0.995) over the concentration range 0.05-50 microg/ml; intra-assay and inter-assay precision and accuracy for berberine fell within predefined limits. The disposition of berberine in the blood, liver and bile fluid suggests that berberine might be metabolized in the liver and undergo hepatobiliary excretion.     

Effects of fatty acids on growth and poly-3-hydroxybutyrate production in bacteria

The effects of saturated and unsaturated fatty acids (lauric acid, palmitic acid, steric acid, oleic acid, linoleic acid, soybean oil) on Sphaerotilus natans, 0B17 (Pseudomonas sp.), and recombinant Escherichia coli DH5(/pUC19/CAB were studied. Oleic acid enhances Poly-3-hydroxybutyrate (PHB) production in these three bacterial strains, suggesting that the single double bond of the acid activates the polyhydroxylkanoate accumulation enzymatic reaction. Under the effect of lauric acid and linoleic acid, the growth of S. natans and 0B17 were totally inhibited. However, the enhanced PHB accumulation in recombinant E. coli was observed.