The electrochemistry of gold in acid aqueous solutions containing chloride ions

Results obtained with differently prepared gold electrodes in acid solutions containing chloride ion at temperatures ranging from 22 to 65°C are reported. Potentiostatic techniques and rotating disc electrodes were employed. The anodic dissolution, the onset of passivity and the cathodic deposition of the metal are investigated under different experimental conditions. The anodic dissolution of Au is discussed in terms of possible reaction mechanisms involving the participation of different adsorbed species. The onset of passivation is related to the depletion of chloride ion at the reaction interface. The experimental voltammograms can be reporduced by means of an equation which considers the diffusion of chloride ion, the activation polarization related to the dissolution of Au and the establishment of passivity.     

Upconverted emission from pyrene and di-tert-butylpyrene using Ir(ppy)3 as triplet sensitizer

Metal-to-ligand charge-transfer sensitized upconverted fluorescence in noncovalent triplet energy transfer assemblies is investigated using Ir(ppy)3 as the sensitizer (ppy=2-phenylpyridine) and pyrene or 3,8-di-tert-butylpyrene as the triplet acceptor/annihilator. Upconverted singlet fluorescence from pyrene or 3,8-di-tert-butylpyrene resulting from triplet-triplet annihilation (TTA) is observed following selective excitation of Ir(ppy)3 in deaerated dichloromethane solutions using 450-nm laser pulses. In both systems, the TTA process is confirmed by the near quadratic dependence of the upconverted fluorescence intensity on incident light power, measured by integrating the upconverted delayed fluorescence kinetic traces as a function of incident excitation power. At the relatively high concentrations of pyrene that were utilized, pyrene excimer formation was detected by its characteristic broad emission centered near 470 nm. In essence, selective excitation of Ir(ppy)3 ultimately resulted in the simultaneous sensitization of both singlet pyrene and pyrene excimers, and the latter degrades the energy stored in the pyrene singlet excited state. Furthermore, in the case of di-tert-butylpyrene/Ir(ppy)3, the formation of excimers is successfully blocked because of the presence of the sterically hindering tert-butyl groups. The current work demonstrates that sensitized TTA is indeed accessible to chromophore systems beyond those previously reported, suggesting the generality of the approach.     

Mean-Field Analysis of the q-Voter Model on Networks

We present a detailed investigation of the behavior of the nonlinear q-voter model for opinion dynamics. At the mean-field level we derive analytically, for any value of the number q of agents involved in the elementary update, the phase diagram, the exit probability and the consensus time at the transition point. The mean-field formalism is extended to the case that the interaction pattern is given by generic heterogeneous networks. We finally discuss the case of random regular networks and compare analytical results with simulations.     

CDS volatility: the key signal of credit quality

This paper investigates the role of CDS volatility in providing information concerning the credit quality of a company. In Castellano and D’Ecclesia (J. Financ. Decis. Mak. 2:27, 2011) a first analysis of how CDS quotes respond to rating announcements is provided and it showed that market participants do not rely much on Rating Agencies, especially during periods characterized by very high volatility, i.e. during a financial crisis. Here, a more accurate analysis of the CDS’s ability to provide timely information on the creditworthiness of reference entities is performed, estimating the volatility of CDS quotes by using Exponential GARCH(1,1) models. The event study methodology is applied to a sample of CDS quotes for US and European markets, over the period 2004–2009. Results provide an accurate understanding of market behavior in the presence of news released by Rating Agencies. Overall, market participants seem to provide timely reactions around the event date and we show that the key element of signaling is represented by the changing volatility in CDS quotes, before and after the rating event.     

Influence of Amide Connectivity on the Hydrogen-Bond-Directed Self-Assembly of [n.n]Paracyclophanes

Reported here is the synthesis and self-assembly characterization of [n.n]paracyclophanes ( [n.n]pCps , n=2, 3) equipped with anilide hydrogen bonding units. These molecules differ from previous self-assembling [n.n]paracyclophanes ( [n.n]pCps ) in the connectivity of their amide hydrogen bonding units (C-centered/carboxamide vs. N-centered/anilide). This subtle change results in a ≈30-fold increase in the elongation constant for the [2.2]pCp -4,7,12,15-tetraanilide ( [2.2]pCpNTA ) compared to previously reported [2.2]pCp -4,7,12,15-tetracarboxamide ( [2.2]pCpTA ), and a ≈300-fold increase in the elongation constant for the [3.3]pCp -5,8,14,17-tetraanilide ( [3.3]pCpNTA ) compared to previously reported [3.3]pCp -5,8,14,17-tetracarboxamide ( [3.3]pCpTA ). The [n.n]pCpNTA monomers also represent the reversal of a previously reported trend in solution-phase assembly strength when comparing [2.2]pCpTA and [3.3]pCpTA monomers. The origins of the assembly differences are geometric changes in the association between [n.n]pCpNTA monomers—revealed by computations and X-ray crystallography—resulting in a more favorable slipped stacking of the intermolecular π-surfaces ( [n.n]pCpNTA vs. [n.n]pCpTA ), and a more complementary H-bonding geometry ( [3.3]pCpNTA vs. [2.2]pCpNTA ).     

A column‐switching HPLC‐MS/MS method for mucopolysaccharidosis type I analysis in a multiplex assay for the simultaneous newborn screening of six lysosomal storage disorders

Lysosomal storage disorders comprise a group of rare genetic diseases in which a deficit of specific hydrolases leads to the storage of undegraded substrates in lysosomes. Impaired enzyme activities can be assessed by MS/MS quantification of the reaction products obtained after incubation with specific substrates. In this study, a column‐switching HPLC‐MS/MS method for multiplex screening in dried blood spot of the lysosomal enzymes activities was developed. Mucopolysaccharidosis type I, Fabry, Gaucher, Krabbe, Niemann–Pick A/B and Pompe diseases were simultaneously assayed. Dried blood spots were incubated with substrates and internal standards; thereafter, supernatants were collected with minor manipulations. Samples were injected, trapped into an online perfusion column and, by a six‐port valve, switched online through the C₁₈ analytical column to perform separation of metabolites followed by MS/MS analysis. A total of 1136 de‐identified newborn screening samples were analyzed to determine references for enzymes activity values. As positive controls, we analyzed dried blood spots from three patients with Pompe, one with Fabry, one with Krabbe disease and two with MPS I, and in all cases the enzyme activities were below the cutoff values measured for newborns, except for an MPS I patient after successful hematopoietic stem cell transplantation. Copyright © 2014 John Wiley & Sons, Ltd.     

GC‐FID determination and pharmacokinetic studies of oleanolic acid in human serum

Analytical interest of OA determination in human serum has increased owing to the increasing interest in pharmaceutical research by pharmaceutical properties. A simple, specific, precise and accurate GC method with flame ionization detector (FID) developed and validated for the determination of oleanolic acid (OA) in human serum (HS). To an aliquot of HS, internal standard was added and a combination of liquid–liquid extraction with a mixture of diethyl ether‐isopropyl alcohol, filtration and consecutive GC resulted in separation and quantification of OA. The organic phase was analyzed using a GC system equipped with a 30 × 0.25 mm i.d. Rtx‐65TG capillary column and FID detection. Total chromatographic time was 10 min and no interfering peaks from endogenous components in blank serum were observed. The OA/internal standard peak area ratio was linearly fitted to the OA concentration (r = 0.992) over the range 10–1500 ng/mL. The mean serum extraction recovery of OA was 96.7 ± 1.0% and the lower limit of quantification based on 5 mL of serum was 10.7 ng/mL. The intra‐day coefficient of variation ranged from 1.3 to 3.6% and inter‐day varied from 1.4 to 4.5%. The developed method was used to study the pharmacokinetics of OA after oral administration in humans. The assay was simple, sensitive, precise and accurate for the use in the study of the mechanisms of absorption and distribution of OA in humans. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization of two new zinc(II) complexes with saccharinate and imidazole or benzimidazole as ligands

The crystal structure of the complexes [Zn(sac)₂(im)₂] (1) and [Zn(sac)₂(bzim)₂]₂2Et-OHH₂O (2) (sac = saccharinate anion; im = imidazole; bzim = benzimidazole; EtOH = ethanol) was determined by single crystal X-ray diffractometry. Complex 1 crystallizes in the monoclinic P2 ₁/n space group with a = 9.1585(5), b = 16.4409(6), c = 15.0249(5) Å, = 94.079(1)°, and Z = 4, whereas complex 2 belongs to the triclinic space group P1 with a = 10.8500(2), b = 12.4860(2), c = 13.5640(3) Å, = 115,696(1), = 100.086(1), = 102.169(1)°, and Z = 1. In both complexes, the Zn(II) cations are in a slightly distorted tetrahedral ZnN₄ environment, coordinated to two saccharinate anions and to two imidazole (1) and to two benzimidazole (2) molecules. The complexes were also characterized by means of infrared spectroscopy and their thermal behavior investigated by means of thermogravimetric and differential thermal analytical techniques.