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.

     

Structure of CdS/SiO2 Nanocomposites: Influence of the Precursor and Cd Concentration

The influence of using TMOS or TEOS in the formation of CdS quantum dots in a silica matrix have been studied by X-ray absorption spectroscopy (XAS). The amount of Cd-S bonds have been monitored as a function of the nominal Cd concentration. The relative amount of CdS crystals depends on the precursor. The use of TEOS is not recommended because it gives a poor yield, especially for high Cd concentration. A discussion of the influence of CdS concentration in matrices from TMOS is carried out from structural models created from their pore volume distribution. The mean pore size becomes smaller and the size distribution more uniform when CdS concentration increases but the nanocrystals of low CdS nominal content present a more efficient quantum confinement.     

Particle and surface characterization of a natural illite and study of its copper retention

Illite clays are known to have a strong affinity for metallic pollutants in the environment and can be applied as low-cost adsorbents for industrial waste treatment. A crucial factor in the development of such applications, however, is the understanding of the chemical, mineralogical, and colloidal properties of these clays. It is also important to understand the mechanisms involved in the surface adsorption of metals by these adsorbants. In order to study the retention of transition metals on illite clays, we have applied surface characterization techniques such as FPIA, SEM-EDX, XRD, N2 (77 K) adsorption, and FTIR. In addition to these experimental techniques, we have also employed a theoretical model that accounts for the chemistry of transition metal ions, and considers the global retention process to be the sum of several single retention processes. This model adequately fits the experimental data and allows for the speciation of metal retention on illite surfaces. Between pH values of 2.53 and 3.01 the only adsorption processes are the electrostatic sorption of [Cu(H2O)6]2+, and the surface complexation of [Cu(H2O)6]2+ and [Cu(OH)(H2O)5]+ ions. Surface complexation of [Cu(OH)(H2O)5]+ ions increases with pH, overcoming [Cu(H2O)6]2+ retention, and thus contributing to the surface precipitation of Cu(OH)2.     

Preferred Binding of Carboxylates by Chiral Urea Derivatives Containing α‐Phenylethyl Group

An efficient, simple protocol for the synthesis of a new family of chiral ureas 1 – 4 is described. The binding properties of 1 – 4 toward different anion (acetate, benzoate, fluoride, and chloride) have been studied by ¹H‐NMR titration and have been observed in the case of 4 is a selective receptor for acetate. The theoretical calculation M06/6‐311+G(d,p) helped us explain the binding properties observed. The most interesting observation is that this calculated structure is consistent with expected, based on the concept of allylic 1,3‐strain (A^1,3 strain). When chiral caboxylates were studied, urea 1 was the best in discriminating between enantiomers.     

Selection of Planar Chiral Conformations between Pillar[5,6]arenes Induced by Amino Acid Derivatives in Aqueous Media

Chiral α-amino acids play critical roles in the metabolic process in nearly all life forms. So far, chiral recognition of α-amino acids has mainly focused on the determination of l /d enantiomers. Herein, selection of planar chiral conformations between water-soluble pillar[5]arene WP5 and pillar[6]arene WP6 was observed due to α-side chain or ethyl ester moieties of l -α-amino acid ethyl ester hydrochlorides binding with WP5 and WP6 , respectively. Therefore, α-side chain and ethyl ester moieties of l -α-amino acid ethyl ester hydrochlorides were recognized by observing the induced CD signal and its inversion. This is a rare example of being able to detect the chiral region around α-carbon of a chiral α-amino acid molecule.     

Reductive Cross-Coupling of a Vinyl Thianthrenium Salt and Secondary Alkyl Iodides

We report the first reductive vinylation of alkyl iodides. The reaction uses a vinyl thianthrenium salt, a palladium catalyst, and an alkyl zinc intermediate formed in situ to trap the L_nPd^II(vinyl) complex formed after oxidative addition before it undergoes undesired homocoupling to form butadiene.     

Estimating critical values for testing the i.i.d. in standardized residuals from GARCH models in finite samples

Taking into account that the BDS test—which is used as a misspecification test applied to standardized residuals from the GARCH(1,1) model—is characterized by size distortion and departure from normality in finite samples, this paper obtains the critical values for the finite sample distribution of the BDS test. We focus on bootstrap simulation to avoid the sampling uncertainty of parameter estimation and make use of estimated response surface regressions (RSR) derived from the experimental results. We consider an extensive grid of models to obtain critical values with the results of the bootstrap experiments. The RSR used to estimate them is an artificial neural network (ANN) model, instead of the traditional linear regression models. Specifically, we estimate critical values by using a bootstrap aggregated neural network (BANN) and by employing functions of the sample size and parameters used in the experiment as the embedding dimension and proximity parameters in the BDS statistic, GARCH parameters and even the q-quantiles of the BDS distributions. The main results confirm that the sample size and BDS parameters play a role in size distortion. Finally, an empirical application to three price indexes is performed, to highlight the differences between decisions made using the asymptotic or our predicted critical values for the BDS test in finite samples.     

Brownian Paths Homogeneously Distributed in Space: Percolation Phase Transition and Uniqueness of the Unbounded Cluster

We consider a continuum percolation model on \(\mathbb {R}^d\), \(d\ge 1\). For \(t,\lambda \in (0,\infty )\) and \(d\in \{1,2,3\}\), the occupied set is given by the union of independent Brownian paths running up to time t whose initial points form a Poisson point process with intensity \(\lambda >0\). When \(d\ge 4\), the Brownian paths are replaced by Wiener sausages with radius \(r>0\). We establish that, for \(d=1\) and all choices of t, no percolation occurs, whereas for \(d\ge 2\), there is a non-trivial percolation transition in t, provided \(\lambda \) and r are chosen properly. The last statement means that \(\lambda \) has to be chosen to be strictly smaller than the critical percolation parameter for the occupied set at time zero (which is infinite when \(d\in \{2,3\}\), but finite and dependent on r when \(d\ge 4\)). We further show that for all \(d\ge 2\), the unbounded cluster in the supercritical phase is unique. Along the way a finite box criterion for non-percolation in the Boolean model is extended to radius distributions with an exponential tail. This may be of independent interest. The present paper settles the basic properties of the model and should be viewed as a springboard for finer results.     

The index of a plane curve and green’s formula

In this paper we compute the line integral of a complex function on a rectifiable cycle homologous to zero obtaining a Green’s formula with multiplicities that involves the of the function and the index of the cycle. We consider this formula in several settings and we obtain a sharp version in terms of the Lebesgue integrability properties of the partial derivatives of the function. This result depends on the proven fact that the index of a rectifiable cycle is square integrable with respect to the planar Lebesgue measure. The work of both authors is partially supported by grants 2000SGR-00059, 2001SGR 00172 of Generalitat de Catalunya and BFM 2002-04072-C02-02 of Ministerio de Ciencia y Tecnologia     

Search for missing baryon resonances via associated strangeness photoproduction

Differential cross-section and single polarization observables in the process γp→K ⁺ Λ are investigated within a constituent-quark model and a dynamical coupled-channel formalism. The effects of two new nucleon resonances and of the K ^*(892)- and K1(1270)-exchanges are briefly presented.