Methylene Blue/Multiwall Carbon Nanotube Modified Electrode for the Amperometric Determination of Hydrogen Peroxide

A novel amperometric sensor based on the incorporation of multiwalled carbon nanotubes (MWCNT) into a poly(methylene blue) (PMB) film immobilized on carbon composite electrodes is described. Cyclic voltammetry indicated that at a surface covered by a MWCNT/PMB layer the cathodic reduction of hydrogen peroxide is facilitated and occurs already at 0.0 V versus SCE. The effect of the order of deposition of PMB and MWCNT, as well as its loading, on electrochemical behaviour was evaluated by cyclic voltammetry and electrochemical impedance spectroscopy. The influence of the various immobilised platforms on the electrocatalytic performance towards hydrogen peroxide was also examined.     

In‐line preconcentration capillary zone electrophoresis for the analysis of haloacetic acids in water

Two in‐line enrichment procedures (large volume sample stacking (LVSS) and field amplified sample injection (FASI)) have been evaluated for the CZE analysis of haloacetic acids (HAAs) in drinking water. For LVSS, separation on normal polarity using 20 mM acetic acid–ammonium acetate (pH 5.5) containing 20% ACN as BGE was required. For FASI, the optimum conditions were 25 s hydrodynamic injection (3.5 kPa) of a water plug followed by 25 s electrokinetic injection (?10 kV) of the sample, and 200 mM formic acid–ammonium formate buffer at pH 3.0 as BGE. For both FASI and LVSS methods, linear calibration curves (r²>0.992), limit of detection on standards prepared in Milli‐Q water (49.1–200 μg/L for LVSS and 4.2–48 μg/L for FASI), and both run‐to‐run and day‐to‐day precisions (RSD values up to 15.8% for concentration) were established. Due to the higher sensitive enhancement (up to 310‐fold) achieved with FASI‐CZE, this method was selected for the analysis of HAAs in drinking water. However, for an optimal FASI application sample salinity was removed by SPE using Oasis WAX cartridges. With SPE‐FASI‐CZE, method detection limits in the range 0.05–0.8 μg/L were obtained, with recoveries, in general, higher than 90% (around 65% for monochloroacetic and monobromoacetic acids). The applicability of the SPE‐FASI‐CZE method was evaluated by analyzing drinking tap water from Barcelona where seven HAAs were found at concentration levels between 3 and 13 μg/L.     

Polybenzoxazines from renewable diphenolic acid

The novel benzoxazine monomers, DPA‐Bz and MDP‐Bz from renewable diphenolic acid (DPA), which mimics the structure of bisphenol A (BPA), were synthesized by traditional approaches. The structure and purity of the monomers was confirmed by FTIR, ¹H NMR, and ¹³C NMR spectra. The thermally activated polymerization of the MDP‐Bz and DPA‐Bz afforded thermosetting polybenzoxazines with higher T_g's, 270 °C and 208 °C respectively, and higher crosslinking density compared to BPA‐Bz, due to the transesterification or esterification reactions occurred during curing process. These reactions are in accordance with the number of independent reactions determined analyzing by SVD the chemical rank of the IR spectra data matrices recorded along the homopolymerization reactions monitored at 200 °C. Spectral and concentration profiles of the active chemical species involved in these processes were obtained by MCR‐ALS. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Polyterephthalates made from Ethylene glycol, 1,4‐cyclohexanedimethanol,and isosorbide

Three series of terephthalate polyesters (copolyesters and terpolyesters) containing 70, 80, and 90 mol % of ethylene glycol respectively, 1,4‐cyclohexanedimethanol (CHDM) and isosorbide in varying ratios, were synthesized by melt polycondensation. It was found that only ～75 mol % of the feeding isosorbide was incorporated in the resulting polyesters and that their content in diethylene glycol oscillated between 2 and 4 mol %. The polyesters had weight‐average molecular weights in the 25,000–33,000 g mol^?1 range and polydispersities between 2 and 2.5. The combined ¹H and ¹³C NMR analysis revealed that the microstructure of all these polyesters was at random. They showed good thermal stability with decomposition temperatures above 400 °C. Their glass‐transition temperatures were observed to increase with the content in cyclic diols, this effect being more pronounced when isosorbide was the replacing comonomer. Only the series containing 90 mol % of ethylene terephthalate units was able to crystallize upon cooling from the melt. Compared isothermal crystallizations revealed that isosorbide was more effective than CHDM in repressing the crystallizability of PET. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Majolica ware in the New Spain: an evaluation through NAA

The results of a study about Majolica ceramics recovered from three sites located in Mexico City are here presented. The set of 83 samples includes several local ceramic-types dating from the Colonial Period, the nineteenth century and the present day, plus some foreign specimens and clay samples from the Puebla area. Fourteen chemical elements present in the samples were analyzed and measured by means of neutron activation, and statistically the following groups were established: two groups that were presumably manufactured in Mexico City, two from Puebla, one from outside the Mexican boundaries, most probably Sevilla-Triana pottery, plus three more groups from unidentified origins. It was also found out that botijas were both imported and produced domestically. These results are discussed against the relevant literature on known provenance, chronology and manufacture standards of this kind of pottery.     

Transiting the molecular potential energy surface along low energy pathways: The TRREAT algorithm

The Transition Rapidly exploring Random Eigenvector Assisted Tree (TRREAT) algorithm is introduced to perform searches along low curvature pathways on a potential energy surface (PES). The method combines local curvature information about the PES with an iterative Rapidly exploring Random Tree algorithm (LaValle, Computer Science Department, Iowa State University, 1998, TR98–11) that quickly searches high‐dimensional spaces for feasible pathways between local minima. Herein, the method is applied to identifying conformational changes of molecular systems using Cartesian coordinates while avoiding a priori definition of collective variables. We analyze the pathway identification problem for alanine dipeptide, cyclohexane and glycine using nonreactive and reactive forcefields. We show how TRREAT‐identified pathways can be used as valuable input guesses for double‐ended methods such as the Nudged Elastic Band when ascertaining transition state energies. This method can be utilized to improve/extend the reaction databases that lie at the core of automatic chemical reaction mechanism generator software currently developed to build kinetic models of chemical reactions. © 2013 Wiley Periodicals, Inc.     

Multiple cation binding by bola-amphiphilic crown ethers: Assessment by fast atom bombardment mass spectrometry

Abstract

Bola-amphiphiles having two aza-18-crown-6 ether rings attached by a covalent spacer (O—O) and an analogous tris (macrocycle) (O—O—O) have been prepared and their cation complexation behavior has been assessed by fast atom bombardment and collisionally activated dissociation tandem mass spectrometry; the key finding is that two cations may simultaneously be complexed by a two- or three-crown system and that this complexation may also involve an anion.