Determination of priority polybrominated diphenyl ethers by isotope dilution gas chromatography(electron ionization)MS using 81Br-labeled standards

A mixture of (81)Br-labeled polybrominated diphenyl ethers (PBDEs), previously synthesized in our laboratory, was separated by liquid chromatography for the individual isolation of different (81)Br-labeled PBDEs containing from 3 to 6 bromine atoms. The different fractions were collected, and a mixed labeled standard was then prepared adequate for the determination of priority PBDEs (congeners 28, 47, 99, 100, 153, and 154) in environmental samples. The spike mixture was then characterized using gas chromatography(electron ionization)MS (GC(EI)MS) both in isotope composition and concentration in combination with multiple least-squares. Contamination from natural abundance BDEs 153 and 154 was detected in the spike mixture, and a new isotope dilution equation was developed to take into account the natural abundance contribution from the spike. The spike mixture was shown to be stable during at least 4 months, and no isotope exchange between natural abundance and labeled PBDEs was detected during this period of time. Finally, the (81)Br-labeled PBDEs standard was used for the determination of congeners 28 (+33), 47, 49, 99, 100, 153, and 154 in a standard reference material (Lake Michigan fish tissue SRM 1947) using three different sample to spike ratios. No methodological calibration needed to be prepared, as no isotopic effects were detected using this labeling mode. Concentrations found were in agreement with the certified concentrations (recoveries between 89% and 116%), and reproducibility was always below 7% RSD. Kragten procedure was used to calculate expanded uncertainties. Very low limits of detection were obtained for all compounds (between 0.02 and 0.9 ng·g(-1)) using the procedure developed here.     

Cryptosporidium spp. and Giardia duodenalis in two areas of Galicia (NW Spain)

The aim of the present study was to investigate the environmental dispersal of Cryptosporidium spp. and Giardia duodenalis in two distinct areas (coastal and inland) in Galicia (NW Spain). Faecal samples were collected from healthy asymptomatic domestic (cows and sheep) and wild animals (deer and wild boars) in the selected areas. In each of the selected areas, samples of untreated water (influent) and of treated water (final effluent) were collected from each of the 12 drinking water treatments plants (DWTPs) and 12 wastewater treatment plants (WTPs) under study. Analysis of a single sample from each of the 635 (coastal) and 851 (inland) domestic and wild animals selected at random revealed that the prevalences of cryptosporidiosis and giardiosis in coastal area were 9.2% and 15.9% respectively, and in inland area, 13.7% and 26.7% respectively. In the coastal area, Cryptosporidium spp. oocysts were detected in influent and effluent samples from 2/12 (16.6%) DWTPs and 8/12 (66.6%) WTPs, while G. duodenalis cysts were detected in influent and effluent samples from 3/12 (25.0%) DWTPs and 12/12 (100%) WTPs. The concentrations were notably higher in WTPs; the mean parasite concentrations in the final treated effluent were 10 oocysts per litre and 137.8 cysts per litre for Cryptosporidium and Giardia, respectively. The mean concentration of G. duodenalis cysts per litre was significantly higher (P < 0.05) than the mean concentration of Cryptosporidium spp. oocysts per litre in both the influent and the effluent samples from all the treatment plants. In the coastal area, C. parvum, C. hominis and G. duodenalis assemblages A (I and II) and E were most repeatedly detected. In the inland area, C. parvum, C. andersoni and G. duodenalis assemblages A (I and II), B and E were most frequently identified.     

Characterization of the Main Semiconductor Laser Static and Dynamic Working Parameters From CW Optical Spectrum Measurements

We present a complete characterization of the work parameters of several types of semiconductor lasers. Static parameters as: power, linewidth and linewidth enhancement factor and also dynamic parameters such as: relaxation oscillations, relative intensity noise and damping rates are calculated using measurements of the optical spectrum of the lasers operated in continuous-wave mode. Methods for the calculation of these parameters are described and applied to the lasers under test by means of a single general setup and a single set of measurements     

Tuning the pKa of the antihistaminic drug chlorpheniramine maleate by supramolecular interactions with water-soluble polymers

The interaction of the pharmacologically important chlorpheniramine maleate (CPM) with polyanions containing sulfonate groups such as poly(sodium 4-styrenesulfonate) (PSS), poly(sodium vinylsulfonate) (PVS), and the more hydrophobic poly(sodium 2-(N-acrylamido)-2-methyl-propanesulfonate) (PAMPS) has been studied by ¹H NMR. It was found that the pK_a of the low-molecular weight molecule (LMWM) may be modified by its interaction with the polyanions, changing from 3 to 5, due to electric charge compensation. Interestingly, the interaction of CPM with PSS produces changes in CPM resonances, such as a general broadening and upfield shifts of the signals, and NOE effects between the LMWM and the water-soluble polymer (WSP) that indicate the presence of π-π interactions.     

Rational approximation via selective modal analysis

We describe a recently developed framework for exploring the structure of linear time-invariant models of large systems, and for constructing interpretable or physically-based, reduced-order models that reproduce selected modes of the original systems to a desired accuracy. Application of this framework to constructing lumped approximations for interconnections of lumped and distributed systems is briefly explored.Support for this work has come partially from the Electric Power Research Institute, Palo Alto, California, under Contract RP 1764-8 monitored by Dr. Neal Balu, and for the second author from the I.T.P. Foundation, Madrid, Spain.     

A structural optimization approach in process synthesis—II : Heat recovery networks

Several formulations of the transshipment model from Operations Research are proposed for the optimal synthesis of heat exchanger networks. The linear programming versions are used for predicting the minimum utility cost, and can handle restricted matches and multiple utilities. The mixed-integer programming version yields minimum utility cost networks in which the number of units is minimized, while allowing stream splitting and selection of most preferred matches. It is shown that the transshipment models can also be incorporated easily within a mixed-integer programming approach for synthesizing chemical processing systems. Several numerical examples are presented which show that the proposed models are computationally very efficient.     

A structural optimization approach in process synthesis—III : Total processing systems

A strategy based on mixed-integer programming is proposed for the optimal synthesis of total processing systems that consist of a chemical plant, with its heat recovery network and utility system. A mixed-integer programming model for the chemical plant is presented which is shown to be compatible with the models developed in previous papers for the utility system and heat recovery network. The strategy accounts explicitly for the interactions among the three components, and its application is illustrated with a large example problem.     

Influence of the acidity level on the electropolymerization of N-vinylcarbazole: Electrochemical study and characterization of poly(3,6-N-vinylcarbazole)

Poly(3,6-N-vinylcarbazole) films were prepared by electrochemical oxidation of N-vinylcarbazole on a Pt electrode using acetonitrile as solvent and tetraethylammonium tetrafluoroborate as electrolyte. The electrosynthesis was carried out by electrical potential cycling in the presence of two different bases: tetraethylammonium benzoate (Bz⁻) and tetraethylammonium phthalate (Ph⁻). These salts were expected to modify the acidity level of the electrolyte since they can act as scavengers for the protons released during the polymerization, when the reaction takes place in the carbazole unit.Products were characterized by cyclic voltammetry, scanning electron microscopy, FTIR spectroscopy, thermogravimetric analysis, differential scanning calorimetry, absorption spectroscopy and four-probe electrical conductivity measurements. Both bases influenced significantly the chemical structure and morphology of the deposited materials. The presence of Ph⁻ in the electrolyte decreases the cross-linking of the electrodeposited polymer, leading to a poly(3,6-N-vinylcarbazole) bearing a more uniform morphology, higher thermal stability and electrical conductivity compared to those of the polymers obtained in the presence of Bz⁻ and without acidity control.