Application of a fast and cost‐effective in situ derivatization method prior to gas chromatography with mass spectrometry to monitor endocrine disruptors in water matrices

This work deals with the optimization of a rapid, cost‐effective, and eco‐friendly gas chromatography with mass spectrometry method for the simultaneous determination of four endocrine disruptor compounds in water matrices: estrone, 17β‐estradiol, 17α‐ethinylestradiol, and bisphenol A, that are currently considered to be of main concern in the field of water policy and that could became candidates for future regulations. The method involves simultaneous derivatization and extraction of compounds by dispersive liquid–liquid microextraction followed by gas chromatography with mass spectrometry analysis. Derivatization and extraction parameters were optimized with the aid of experimental design approach. An excellent linear response was achieved for all analytes (r² ≥ 0.999). Limits of detection and quantification are 0.003–0.005 and 0.0094–0.0164 μg/L, respectively. Intraday precision ranged between 1.1 and 12.6%, whereas interday precision ranged between 0.5 and 14.7%. For accuracy, bias values varied between –15.0 and 13.7%. Recoveries at three concentration levels ranged from 86.4 to 118.2%. The proposed method can be applied to the routine analysis of groundwater, river, sea, tap, and mineral water samples with excellent sensitivity, precision, and accuracy.     

Biofouling in water systems

The paper describes the mechanisms in the development of biofouling layers (initial surface conditioning, microbial transport and attachment, mass transfer of nutrients to the biofilm surface and through the microbial layer, cell metabolism, and detachment of cells and of larger parts of the biofilm) and summarizes the effects of several factors on the buildup and stability of biofilms (nutrient availability, fluid velocity and turbulence, temperature, surface condition, and nonliving particles). Mass transfer within biofilms is treated in more detail. A biofouling model applied to the development of biofilms in heat exchangers is presented. Finally, references are made to biofouling control methods (biocide and the proper design and operation of heat exchangers) and to future research needs in this area.     

Optical Fiber Communications: Recent Contributions in Photonic Device Technology

The current status of the research and development as well as the recent contributions in optical communications at INESC Porto is reviewed. This review includes all the work carried out in the last few years in optical fiber communications, namely the development of passive and active optical devices. Some of the passive structures that have been studied and developed are: add-drop multiplexers, multiplexer/demultiplexer based on Bragg grating technology, dispersion compensators, and optical cross-connects. Active photonic devices such as wavelength converters, fiber lasers, and fiber amplifiers have also been studied. New ideas are being continuously developed and tested.     

Catalyst concentration distribution in fluidized bed by gamma-ray absorption

Summary The axial and radial distribution of the catalyst concentration, in the riser of an EMC - experimental cold model of a fluid catalytic cracking type unit, was measured by gamma-absorption. The solid concentration in the circulating fluidized bed was determined by measurements with a ²⁴¹Am gamma-source and a NaI(Tl) detector. The operation, instrumental measurements and data acquisition system of the cold unit were automated. The catalyst concentration measurements were carried out in static experiments and in the circulating fluidized bed. A calibration of the distribution concentration was made with experimental data from gas velocity and pressure drop along the riser that gave the best multi-regression model. A spatial resolution of 5.0 ^. 10^-3 m by scanning the riser and a catalyst density resolution of 5.0±0.8 kg/m³ were obtained. The axial catalyst concentration distribution, in the 5-13 kg/m ³ interval, showed a predicted pattern according to the literature. The radial distribution was in an annular configuration for this diluted catalyst concentration.     

Temperature dependence of ultra-exothermic charge recombinations.

We measured the temperature dependence (from +32 to -50 degrees C) of charge-recombination rates between contact radical ion pairs in isopropyl ether. In the systems selected for this study, aromatic hydrocarbon cations are the electron acceptors and the fumaronitrile anion is the electron donor. Nearly quantitative electron transfers occur at all temperatures. The charge recombinations have excess exothermicities of -60 kcal mol(-1) and exhibit a very weak temperature dependence. Our observations emphasize the absence of solvent effects and the relevance of nuclear tunneling in charge recombinations.     

Ultrafast dephasing of localized surface plasmons in colloidal silver nanoparticles: the influence of stabilizing agents

Localized surface plasmon dephasing times for aqueous colloidal silver nanoparticles (NPs) stabilized with three different capping agents (trisodium citrate??TSC, poly(vinylpyrrolidone)??PVP, and poly(vinylalcohol)?? PVA) were measured using the persistent spectral hole burning technique. The results obtained by fitting a theoretical curve to the experimental data show that the dephasing times are dependent on the chosen stabilizer (3.0, 2.3, and 1.8?fs for TSC, PVP, and PVA, respectively), and the differences are attributed to changes in the electronic density of states due to the interaction between the NPs and the capping agents. The results are supported by ab initio calculations for the chemisorbate and metallic cluster interaction.     

Synthesis of chiral spiropyrazoline-β-lactams and spirocyclopropyl-β-lactams from 6-alkylidenepenicillanates

Chiral spiropyrazolinepenicillanates were obtained in a stereoselective fashion via 1,3-dipolar cycloaddition reactions of 6-alkylidenepenicillanates with diphenyldiazomethane, phenyldiazomethane, and diazomethane. Microwave-induced ring contraction of spiro-1-pyrazoline-β-lactams leading to chiral spirocyclopropylpenicillanates is also described.     

Two linear approximation algorithms for convex mixed integer nonlinear programming

We present two new algorithms for convex Mixed Integer Nonlinear Programming (MINLP), both based on the well known Extended Cutting Plane (ECP) algorithm proposed by Weterlund and Petersson. Our first algorithm, Refined Extended Cutting Plane (RECP), incorporates additional cuts to the MILP relaxation of the original problem, obtained by solving linear relaxations of NLP problems considered in the Outer Approximation algorithm. Our second algorithm, Linear Programming based Branch-and-Bound (LP-BB), applies the strategy of generating cuts that is used in RECP, to the linear approximation scheme used by the LP/NLP based Branch-and-Bound algorithm. Our computational results show that RECP and LP-BB are highly competitive with the most popular MINLP algorithms from the literature, while keeping the nice and desirable characteristic of ECP, of being a first-order method.

     

Kinetic and thermodynamic parameters,and partial characterization of the crude extract of tannase produced by Saccharomyces cerevisiae CCMB 520

Tannase can be used in different industrial sectors such as in food (juices and wine) and pharmaceutical production (trimethoprim) because it catalyses the hydrolysis of hydrolysable tannins. The aim of the current study is to assess the tannase found in the crude extract of Saccharomyces cerevisiae CCMB 520, and to set its catalytic and thermodynamic properties. The enzyme was optimally active at pH 6.0 and temperature 30 °C. Tannase was activated by Na⁺, Ca²⁺, K⁺ at 5 × 10^?3 mol/L. The half-life at 30 °C was 3465.7 min. The activation energy was 40.32 kJ/mol. The Gibbs free energy, enthalpy and entropy at 30 °C were 85.40, 48.10 and ?0.12 kJ/mol K, respectively. Our results suggest that the tannase found in the crude extract of S. cerevisiae is an attractive enzyme for industrial applications, such as for beverage manufacturing and gallic acid production, due its catalytic and thermodynamic properties (heat-stable and resistant to metal ions).