Surface treatment of reinforced concrete in marine environment: Influence on chloride diffusion coefficient and capillary water absorption

There are currently many types of protective materials for reinforced concrete structures and the influence of these materials in the chloride diffusion coefficient still needs more research. The aim of this paper is to study the efficacy of certain surface treatments (such as hydrophobic agents, acrylic coating, polyurethane coating and double systems) in inhibiting chloride penetration in concrete. The results indicated that all tested surface protection significantly reduced the sorptivity of concrete (reduction rate > 70%). However, only the polyurethane coating was highly effective in reducing the chloride diffusion coefficient (reduction rate of 86%). (C) 2008 Elsevier Ltd. All rights reserved.

Model to predict the chloride penetration in concrete with profile forming peak: verification of its precision

Chloride attack in marine environments or in structures where deicing salts are used will not always show profiles with concentrations that decrease from the external surface to the interior of the concrete. Some profiles show an increase in chloride concentrations from when a peak is formed. This type of profile must be analyzed in a different way from the traditional model of Fick`s second law to generate more precise service life models. A model for forecasting the penetration of chloride ions as a function of time for profiles having formed a peak. To confirm the efficiency of this model, it is necessary to observe the behavior of a chloride profile with peak in a specific structure over a period of time. To achieve this, two chloride profiles with different ages (22 and 27 years) were extracted from the same structure. The profile obtained from the 22-year sample was used to estimate the chloride profile at 27 years using three models: a) the traditional model using Fick`s second law and extrapolating the value of C(S)-external surface chloride concentration; b) the traditional model using Fick`s second law and shifting the x-axis to the peak depth; c) the previously proposed model. The results from these models were compared with the actual profile measured in the 27-year sample and the results were analyzed. The model was presented with good precision for this study of case, requiring to be tested with other structures in use.

Efficacy of surface hydrophobic agents in reducing water and chloride ion penetration in concrete

Hydrophobic agents are surface protection materials capable of increasing the angle of contact between the water and the concrete surface. For this reason, hydrophobic agents reduce water (in liquid form) penetration in concrete. Therefore, many European construction regulating agencies recommend this treatment in their maintenance policy. Nonetheless, there continues to be a gap in the understanding about which transport mechanisms of the concrete are modified by the hidrophobic agents. The aim of this study was to fill this gap in regards to reinforced concrete structures inserted in a marine environment. To this end, certain tests were used: Two involving permeability mechanism, one determining capillary absorption, and the last, a migration test used to estimate the chloride diffusion coefficient in saturated condition. Results indicated the efficacy of the hydrophobic agents in cases where capillary suction is the mechanism of water penetration (reduced by 2.12 and 7.0 times, depending of the product). However, when the transport mechanism is permeability this product is not advisable. Moreover, it was demonstrated that the chloride diffusion coefficient (in saturated condition) is reduced by the hydrophobic agents, however, the magnitude of this reduction is minor (reduced by 11% and 17%, depending on the product).

The Penicillium chrysogenum aclA gene encodes a broad-substrate-specificity acyl-coenzyme A ligase involved in activation of adipic acid, a side-chain precursor for cephem antibiotics

Activation of the cephalosporin side-chain precursor to the corresponding CoA-thioester is an essential step for its incorporation into the P-lactam backbone. To identify an acyl-CoA ligase involved in activation of adipate, we searched in the genome database of Penicillium chrysogenum for putative structural genes encoding acyl-CoA ligases. Chemostat-based transcriptome analysis was used to identify the one presenting the highest expression level when cells were grown in the presence of adipate. Deletion of the gene renamed aclA, led to a 32% decreased specific rate of adipate consumption and a threefold reduction of adipoyl-6-aminopenicillanic acid levels, but did not affect penicillin V production. After overexpression in Escherichia coli, the purified protein was shown to have a broad substrate range including adipate. Finally, protein-fusion with cyan-fluorescent protein showed co-localization with microbody-borne acyl-transferase. Identification and functional characterization of aclA may aid in developing future metabolic engineering strategies for improving the production of different cephalosporins. (C) 2009 Elsevier Inc. All rights reserved.

Investigation of the mass transfer processes during the desalination of water containing phenol and sodium chloride by electrodialysis

Oxidation processes are used in wastewater treatment when conventional processes are not effective due to the presence of recalcitrant organic contaminants, like phenol. However, the presence of ionic compounds associated with organic pollutants may retard the oxidation. In this work the transport of species contained in an aqueous solution of phenol containing sodium chloride was evaluated in an electrodialysis (ED) system. An experimental study was carried out in which the influence of the process variables on the phenol loss and sodium chloride removal was investigated. Experiments were also performed without current, in order to determine the phenol transfer due to diffusion. The phenol and salt concentration variations in the ED compartments were measured over time, using dedicated procedures and an experimental design to determine the global characteristic parameters. A phenomenological approach was used to relate the phenol, salt and water fluxes with the driving forces (concentration and electric potential gradients). Under ED conditions, two contributions were pointed out for the phenol transport, i.e. diffusion and convection, this latter coming from the water flux due to electroosmosis related to the migration of salts. The fitting of the parameters of the transport equations resulted in good agreement with the experimental results over the range of conditions investigated. (c) 2008 Elsevier B.V. All rights reserved.

Investigation of the corrosion behaviour of AA 2024-T3 in low concentrated chloride media

Aluminium alloy (AA) 2024-T3 is an important engineering material due to its widespread use in the aerospace industry. However, it is very prone to localized corrosion attack in chloride containing media, which has been mainly associated to the presence of coarse intermetallics (IMs) in its microstructure. In this work the corrosion behaviour of AA 2024-T3 in low concentrated chloride media was investigated using microscopy and electrochemical methods. TEM/EDS observations on non-corroded samples evidenced the heterogeneous composition within the IMs. In addition, SEM observations showed that intermetallics with the same nominal composition present different reactivity, and that both types of coarse IMs normally found in the alloy microstructure are prone to corrosion. Moreover, EDS analyses showed important compositional changes in corroded IMs, evidencing a selective dissolution of their more active constituents, and the onset of an intense oxygen peak, irrespective to the IM nature, indicating the formation of corrosion products. On the other hand, the results of the electrochemical investigations, in accordance with the SEM/EDS observations, evidenced that IMs corrosion dominates the electrochemical response of the alloy during the first hours of immersion in the test electrolyte. (c) 2008 Elsevier Ltd. All rights reserved.

Thermodynamics of aqueous solutions of polyelectrolytes: Experimental results for the activity of water in aqueous solutions of (a single synthetic polyelectrolyte and sodium chloride)

Experimental results for the activity of water in aqueous solutions of 10 single, synthetic polyelectrolytes (polysodium acrylate, polysodium methacrylate, polyammonium acrylate, polysodium ethylene sulfonate, and polysodium styrene sulfonate) and sodium chloride at 298.2 K are presented. The experimental work was performed by applying the isopiestic method with sodium chloride as a reference substance. As expected, the activity of water decreases when the concentration of a polyelectrolyte and/or sodium chloride increases. At constant concentration of a polyelectrolyte and sodium chloride, the activity of water depends on the monomer unit and the molecular mass of the polyelectrolyte. The new data are to be used in future work to develop and test models for the Gibbs excess energy of aqueous solutions of polyelectrolytes.

Long-Chain Acyl-Homoserine Lactones from Methylobacterium mesophilicum: Synthesis and Absolute Configuration

The acyl-homoserine lactones (acyl-HSLs) produced by Methylobacterium mesophilicum isolated from orange trees infected with the citrus variegated chlorosis (CVC) disease have been studied, revealing the occurrence of six long-chain acyl-HSLs, i.e., the saturated homologues (S)-N-dodecanoyl (1) and (S)-N-tetradecanoyl-HSL (5), the uncommon odd-chain N-tridecanoyl-HSL (3), the new natural product (S)-N-(2E)-dodecenoyl-HSL (2), and the rare unsaturated homologues (S)-N-(7Z)-tetradecenoyl (4) and (S)-N-(2E,7Z)-tetradecadienyl-HSL (6). The absolute configurations of all HSLs were determined as 3S. Compounds 2 and 6 were synthesized for the first time. Antimicrobial assays with synthetic acyl-HSLs against Gram-positive bacterial endophytes co-isolated with M. mesophilicum from CVC-infected trees revealed low or no antibacterial activity.

Evaluation of the composition of continuously-cultivated Arthrospira (Spirulina) platensis using ammonium chloride as nitrogen source

This work is focused on the influence of dilution rate (0.08 <= D <= 0.32 d(1)) on the continuous cultivation and biomass composition of Arthrospira (Spirulina) platensis using three different concentrations of ammonium chloride (c(No) = 1.0, 5.0 and 10 mol m (3)) as nitrogen source. At c(No) = 1.0 and 5.0 mol m (3) the biomass protein content was an increasing function of D, whereas, when using c(No) = 10 mol m (3), the highest protein content (72.5%) was obtained at D = 0.12 d (1). An overall evaluation of the process showed that biomass protein content increased with the rate of nitrogen supply (D c(No)) up to 72.5% at D c(No) = 1.20 mol m (3) d (1). Biomass lipid content was an increasing function of D only when the nitrogen source was the limiting factor for the growth (D c(No) <= 0.32 mol m (-3) d (1)), which occurred solely with c(No), = 1.0 mol m (3). Under such conditions, A. platensis reduced its nitrogen reserve in the form of proteins, while maintaining almost unvaried its lipid content. The latter was affected only when the concentration of nitrogen was extremely low (c(No) = 1.0 mol m (3)). The most abundant fatty acids were the palmitic (45.8 +/- 5.20%) and the gamma-linolenic (20.1 +/- 2.00%) ones. No significant alteration in the profiles either of saturated or unsaturated fatty acids was observed with c(No) <= 5.0 mol m (3), prevailing those with 16 and 18 carbons. (C) 2010 Elsevier Ltd. All rights reserved.

Fed-batch cultivation of Arthrospira (Spirulina) platensis: Potassium nitrate and ammonium chloride as simultaneous nitrogen sources

Arthrospira platensis was cultivated in minitanks at 13 klux, using a mixture of KNO(3) and NH(4)Cl as nitrogen source. Fed-batch daily supply of NH(4)Cl at exponentially-increasing feeding rate allowed preventing ammonia toxicity and nitrogen deficiency, providing high maximum cell concentration (X(m)) and high-quality biomass (21.85 mg chlorophyll g cells(-1); 20.5% lipids; 49.8% proteins). A central composite design combined to response surface methodology was utilized to determine the relationships between responses (X(m), cell productivity and nitrogen-to-cell conversion factor) and independent variables (KNO(3) and NH(4)Cl concentrations). Under optimum conditions (15.5 mM KNO3; 14.1 mM NH(4)Cl), X(m) was 4327 mg L(-1), a value almost coincident with that obtained with only 25.4 mM KNO(3), but more than twice that obtained with 21.5 mM NH(4)Cl. A 30%-reduction of culture medium cost can be estimated when compared to KNO(3)-batch runs, thus behaving as a cheap alternative for the commercial production of this cyanobacterium. (C) 2010 Elsevier Ltd. All rights reserved.

Influence of ammonium chloride feeding time and light intensity on the cultivation of Spirulina (Arthrospira) platensis

This study dealt with the influence of both the feeding time and light intensity on the fed-batch culture of the cyanobacterium Spirulina (Arthrospira) platensis using ammonium chloride as a nitrogen source. For this purpose, a 2 2 plus star central composite experimental design combined with response surface methodology was employed, and the maximum cell concentration (X-m), the cell productivity (P-X), and the yield of biomass on nitrogen (Y-X/N) were selected as the response variables. The optimum values of X-m (1,833 mgL(-1)) and Y-X/N (5.9 gg(-1)) estimated by the model at light intensity of 13 klux and feeding time of 17.2 days were very close to those obtained experimentally under these conditions (X-m = 1,771 +/- 41 mg L-1; Y-X/N = 5.7 +/- 0.17 gg(-1)). The cell productivity was a decreasing function of the ammonium chloride feeding time and a quadratic function of the light intensity. The protein and lipid contents of dry biomass collected at the end of cultivations were shown to decrease with increasing light intensity.

Manufacture of low-sodium Minas fresh cheese: Effect of the partial replacement of sodium chloride with potassium chloride

We investigated the effect of sodium reduction by partial substitution of sodium chloride (NaCl) with potassium chloride (KCl) on the manufacture of Minas fresh cheese during 21 d of refrigerated storage. Four treatments of low-sodium Minas fresh cheese were manufactured, with partial replacement of NaCl by KCl at 0, 25, 50, and 75% (wt/wt), respectively. The cheeses showed differences in the content of moisture, ash, protein, salt, and lipid contents, as well as on the extent of proteolysis and hardness throughout the storage period. However, no difference was observed among treatments within each storage day tested. The partial substitution of NaCl by KCl decreased up to 51.8% the sodium concentration of the cheeses produced. The consumer test indicated that it is possible to manufacture a low-sodium Minas fresh cheese that is acceptable to consumers by partial substitution of NaCl by KCl at 25% (wt/wt) in the salting step.

Enantioselective analysis of mirtazapine and its two major metabolites in human plasma by liquid chromatography-mass spectrometry after three-phase liquid-phase microextraction

A three-phase liquid-phase microextraction (LPME) method using porous polypropylene hollow fibre membrane with a sealed end was developed for the extraction of mirtazapine (MRT) and its two major metabolites, 8-hydroxymirtazapine (8-OHM) and demethylmirtazapine (DMR), from human plasma. The analytes were extracted from 1.0 mL of plasma, previously diluted and alkalinized with 3.0 mL 0.5 mol L-1 pH 8 phosphate buffer solution and supplemented with 15% sodium chloride (NaCl), using n-hexyl ether as organic solvent and 0.01 moL L-1 acetic acid solution as the acceptor phase. Haloperidol was used as internal standard. The chromatographic analyses were carried out on a chiral column, using acetonitrile-methanol-ethanol (98:1:1, v/v/v) plus 0.2% diethylamine as mobile phase, at a flow rate of 1.0 mL min(-1). Multi-reaction monitoring (MRM) detection was performed by mass spectrometry (MS-MS) using a triple-stage quadrupole and electrospray ionization interface operating in the positive ion mode. The mean recoveries were in 18.3-45.5% range with linear responses over the 1.25-125 ng mL(-1) concentration range for all enantiomers evaluated. The quantification limit (LOQ) was 1.25 ng mL(-1). Within-day and between-day assay precision and accuracy (2.5, 50 and 100 ng mL(-1)) showed relative standard deviation and the relative error lower than 11.9% for all enantiomers evaluated. Finally, the method was successfully used for the determination of mirtazapine and its metabolite enantiomers in plasma samples obtained after single drug administration of mirtazapine to a healthy volunteer. (c) 2007 Elsevier B.V. All rights reserved.

Hollow fiber-based liquid-phase microextraction (HF-LPME) of isradipine and its main metabolite followed by chiral HPLC analysis: application to an in vitro biotransformation study

An enantioselective liquid chromatographic method using two-phase hollow fiber liquid-phase microextraction (HF-LPME-HPLC) was developed for the determination of isradipine (ISR) enantiomers and its main metabolite (pyridine derivative of isradipine, PDI) in microsomal fractions isolated from rat liver. The analytes were extracted from 1 mL of microsomal medium using a two-phase HF-LPME procedure with hexyl acetate as the acceptor phase, 30 min of extraction, and sample agitation at 1,500 rpm. For the first time, ISR enantiomers and PDI were resolved. For this separation, a ChiralpakA (R) AD column with hexane/2-propanol/ethanol (94:04:02, v/v/v) as the mobile phase at a flow rate of 1.5 mL min(-1) was used. The column was kept at 23 A +/- 2 A degrees C. The drug and metabolite detection was performed at 325 nm and the internal standard oxybutynin was detected at 225 nm. The recoveries were 23% for PDI and 19% for each ISR enantiomer. The method presented quantification limits (LOQ) of 50 ng mL(-1) and was linear over the concentration range of 50-5,000 and 50-2,500 ng mL(-1) for PDI and each ISR enantiomer, respectively. The validated method was employed to an in vitro biotransformation study of ISR using rat liver microsomal fraction showing that (+)-(S)-ISR is preferentially biotransformed.

Comparative effects of lantadene A and its reduced metabolite on mitochondrial bioenergetics

Lantana (Lantana camara Linn.) is a noxious weed to which certain medicinal properties have been attributed, but its ingestion has been reported to be highly toxic to animals and humans, especially in the liver. The main hepatotoxin in lantana leaves is believed to be the pentacyclic triterpenoid lantadene A (LA), but the precise mechanism by which it induces hepatotoxicity has not yet been established. This work addressed the action of LA and its reduced derivative (RLA) on mitochondrial bioenergetics. At the concentration range tested (5-25 mu M), RLA stimulated state-4 respiration, inhibited state-3 respiration, circumvented oligomycin-inhibited state-3 respiration, dissipated membrane potential and depleted ATP in a concentration-dependent manner. However. LA did not stimulate state-4 respiration, nor did it affect the other mitochondrial parameters to the extent of its reduced derivative. The lantadenes didn`t inhibit the CCCP-uncoupled respiration but increased the ATPase activity of intact coupled mitochondria. The ATPase activity of intact uncoupled or disrupted mitochondria was not affected by the compounds. We propose, therefore, that RLA acts as a mitochondrial uncoupler of oxidative phosphorylation, a property that arises from the biotransformation (reduction) of LA, and LA acts in other mitochondrial membrane components rather than the ATP synthase affecting the mitochondrial bioenergetics. Such effects may account for the well-documented hepatoxicity of lantana. (C) 2010 Elsevier Ltd. All rights reserved.