Electrochemical oxidation of several chlorophenols on diamond electrodes Part I. Reaction mechanism

The electrochemical oxidation of 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol aqueous wastes using boron-doped diamond electrodes was studied. This treatment led to complete mineralization of the wastes regardless of the operating conditions. A simple mechanistic model is consistent with the voltammetric and electrolysis results. According to this model, the electrochemical treatment of chlorophenol aqueous wastes involves the anodic and cathodic release of chlorine followed by the formation of non-chlorinated aromatic intermediates. Subsequent cleavage of the aromatic ring gives rise to non-chlorinated carboxylic acids. Chlorine atoms arising from the hydrodehalogenation of the chlorophenols are converted into more oxidized molecules at the anode. These molecules react with unsaturated C₄ carboxylic acid to finally yield trichloroacetic acid through a haloform reaction. The non-chlorinated organic acids are ultimately oxidized to carbon dioxide and the trichloroacetic acid into carbon dioxide and volatile organo-chlorinated molecules. Both direct and mediated electrochemical oxidation processes are involved in the electrochemical treatment of chlorophenols.     

Field Evaluation of Plant Odor and Pheromonal Combinations for Attracting Plum Curculios

The attractiveness of different synthetic host odors and a synthetic aggregation pheromone (grandisoic acid [GA]) to overwintered adult plum curculios (PCs), Conotrachelus nenuphar (Herbst) (Coleoptera: Curculionidae), was examined using two types of traps (sticky panels and black pyramids) placed in border areas surrounding an unsprayed section of an apple orchard in Massachusetts. In 2001, we evaluated the response of PCs to three synthetic fruit volatiles (benzaldehyde [BEN], ethyl isovalerate [EIV], and limonene [LIM]) assessed alone and in combination with GA, as well as the response to GA alone and a no-odor (control) treatment. BEN was the only host volatile that synergized the response of PCs to GA for both trap types. For both trap types, GA was as attractive to PCs as a single component as when in combination with either EIV or LIM. In 2002, four release rates of BEN (0, 2.5, 10, and 40 mg/day) and two release rates of GA (1 and 2 mg/day) were evaluated for attractiveness to PCs using panel and pyramid traps. For panel traps, an increase in amount of GA released (from 1 to 2 mg/day) was associated with a 35% increase in captures. However, PC captures by pyramid traps were similar regardless of the amount of GA released. For panel traps, 10 and 40 mg/day of BEN were the most attractive release rates regardless of the amount of GA released. For pyramid traps baited with GA. PC captures were enhanced by the presence of BEN, regardless of release rate. In 2003, GA at 1 mg/day + BEN at 80 mg/day of release did not enhance PC captures by panel traps relative to lower release rates of BEN. Pyramid traps releasing GA at 1 mg/day performed best when baited with BEN at 10 mg/day of release; a release rate of 80 mg/day of BEN decreased the attractiveness of the binary combination of BEN + GA. Combined results suggest that BEN at 10 mg/day + GA at 1 mg/day of release constitutes an attractive lure that may improve the effectiveness of monitoring traps for PCs.     

Nutritional recovery of mild and moderately malnourished children under two different treatment approaches (ambulatory versus day-care)

This retrospective analysis was conducted between May 1997 and May 2000 at the Centro de Atención Nutricional Infantil de Antímano, CANIA, in Caracas, Venezuela to assess the efficacy of two treatments (ambulatory versus day-care) of mild and moderate malnourished children. Inclusion criteria were: children under 10 years old with mild and moderate malnourishment, who attended a minimum of 3 control visits during a period of 12 months. One hundred fourteen malnourished children were included: fifty seven in ambulatory treatment and fifty seven in day-care treatment paired per nutritional diagnosis, gender and age (thirty nine mild and eighteen moderate malnourished children). The nutritional recovery criterion was weight for height above tenth percentile. No relation was found between treatment approaches and nutritional recovery at 3 and 6 months of treatment. In the group of mild malnourished children, the percentage of recovered patients at 3 months of treatment, that kept their recovered condition at 6 months was 83% (15/18) in the ambulatory treatment and 82% (18/22) in the day-care treatment Age of children, associated disease, acute morbidity, dietetic risk and mother's education and age were not associated with nutritional recovery at 6 months of treatment (p > 0.05). The day-care approach resulted as effective as ambulatory in mild malnourished children. In moderate malnourished new studies will need to be conducted with greater number of patients.     

Dietary evaluation of pregnant adolescents during first, second and third trimester

In order to identify risk of inadequate intake of calories and nutrients during pregnancy, 75 pregnant adolescents (14 to 18 years old) apparently healthy, from low socioeconomic level, in their first prenatal control (12 weeks) were studied by two 24 hour recalls and a food frequency questionnaire at each trimester. Nutritional status was assessed by body mass index (pregestation weight/height) and classified according to American Medicine Institute reference. Paired t-test, frequency distribution and ANOVA were used for statistical analysis. Low weight was found in 34.6% of adolescent at the first visit and 5.3% were overweight. Even though, caloric intake was below recommendation, significant increases were observed between first and second trimester for energy, carbohydrates, niacin and zinc (p < 0.001) and for fat, proteins, riboflavin, thiamin, vitamin C, calcium and iron (p < 0.05). From second to third trimester, differences (p < 0.05) were significant only for vitamin A. Between first and third trimester, differences were significant (p < 0.05) for energy, proteins, carbohydrates, niacin, riboflavin, zinc and for thiamin, vitamin A and calcium (p < 0.05). A high proportion of pregnant adolescent did not reach recommendations for energy, folate, calcium and zinc. Food intake pattern did not change significantly among trimesters. Mean total weight gain was 9.2 kg and 0.412 +/- 0.4 g/week. Newborn's mean weight was 3.221 +/- 418 grams. It is concluded that adolescents are at high nutritional risk and deficiency of dietary intake should be followed. Attention should be addressed from the preconceptional period to postpartum in order to improve maternal and fetal conditions.     

Synthesis and ex-situ evaluation of quaternized polysulfone as an anion exchange ionomer for AEM technologies

Anion exchange ionomer (AEI) is a critical component used on anion exchange membrane fuel cell (AEMFC) and alkaline water electrolyzer (AWE). In this work, quaternized polysulfone with different functionalization degree were used as an ionomer to evaluate the performance in the oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR), both implied in the operation of AEMFC and AWE. The synthesized ionomer exhibited a better performance in both reactions in comparison to the commercial AEI Aemion®. PSf-130 exhibited better performance, since IEC and surface area increases twice regarding the same parameters in the PSf-60. The PSf-130 conductivity increases three times regarding the value exhibited by PSf-60. Finally, the J_lim and J_k increases 67% and 100% for ORR. On the other hand, the same catalytic parameter increased 44% and 35% for HOR comparing both polysulfone-based ionomers. The Tafel slope values do not showed drastically changes for different ionomers indicating the same rate determining step (RDS) and the same mechanism in both reactions for all the ionomers.     

Thiol-ene emulsion polymerization using a semi-continuous approach

The thermally initiated thiol-ene emulsion polymerization of diallyl phthalate (DAP) diene and ethylenedioxy diethanthiol (EDDT) dithiol monomers in batch and semibatch emulsion polymerization is investigated. The batch process leads to larger and broader particle sizes than when the polymerization is carried out in semibatch. The evolution of the particle size and the final particle size distribution indicate that the stability of the latexes is limited and, hence, aggregation phenomena occurred in both processes. In particular, the evolution of the particle size distribution (PSD) in the semibatch process indicates nucleation, growth, and aggregation occurring simultaneously that produced a bimodal particle size. When the diene monomer was changed to diallyl terephthalate (DATP), the semibatch polymerization yielded smaller particles and narrow distribution without any indication of aggregation. The partial substitution of the dithiol by a trithiol monomer that is substantially more water insoluble affected nucleation of the particles, yielding for both systems smaller particles. The polythioether polymers synthesized present low glass transition temperatures (~ −30/−40°C) and those containing the therephthalate yield crystalline films. The potential application of the polymers as pressure sensitive adhesives (PSAs) was preliminarily assessed.     

Hydrophobization of hair to improve the interfacial adhesion between hair and high-density polyethylene

Concerned about environmental pollution, and aware of the comfort that polyethylene provides for daily human life, this work sought to replace a percentage of high-density polyethylene (HDPE) with human or bovine hair. Hair is natural, abundant, light weight, non-toxic, and disposed of as garbage. The main disadvantage of natural composites is the interfacial adhesion. To increase the interfacial adhesion between hair and HDPE, stearic acid or oleic acid was chemically anchored on the hair surface, which leads to an improved contact angle hysteresis and hydrophobicity. Dynamic-mechanical properties of the composites were investigated focusing on the type of carboxylic acid used (stearic or oleic acid), hair length, hair type (human or bovine) and amount of hair used in the composite. Taking 40°C as a reference, using 15% of hair with a length of 1 ± 0.15 mm, the highest storage modulus value was obtained with HDPE with human hair modified with oleic acid, exceeding the value of the storage modulus of HDPE by 67.64%. Increasing storage modulus on composites indicates of interfacial interaction and chemical affinity improvement between hair and polyethylene.     

Preparation and characterization of acrylic acid/itaconic acid hydrogel coatings containing silver nanoparticles

Hydrogel silver nanocomposites have been used in applications with excellent antibacterial performance. Acrylic acid (AA)/itaconic acid (IA) hydrogels silver nanocomposites were prepared and applied as a coating on a textile substrate. Hydrogel matrices were synthesized first by the polymerization of an AA/IA aqueous (80/20 v/v) solution and mixed with 2‐2‐azobis(2‐methylpropionamide) diclorohydrate and N,N′‐methylene bisacrylamide until the hydrogel was formed. Silver nanoparticles were generated throughout the hydrogel networks with an in situ method via the incorporation of the silver ions and subsequent reduction with sodium borohydride. Cotton (C) and cotton/polyester (CP) textile fibers were then coated with these hydrogel silver nanocomposites. The influence of these nanocomposite hydrogels on the properties of the textile fiber were investigated by infrared spectroscopy (attenuated total reflectance), scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, and antibacterial tests against Pseudomona aeruginosa and Staphylococcus aureus. The better conditions, in which no serious aggregation of the silver nanoparticles occurred, were determined. It was proven that the textiles coated with hydrogels containing nanosilver had an excellent antibacterial abilities. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2713–2721, 2013     

Phytal: A Candidate Sex Pheromone Component of the Moroccan Locust Dociostaurus maroccanus

Outbreaks of locusts cause enormous economic losses to agriculture in many countries. To develop environmentally friendly strategies for their control, much research has been focused on the factors that influence locust biology, particularly infochemical‐mediated interactions. We present herein the identification and synthesis of both Z and E isomers of phytal (3,7,11,15‐tetramethylhexadec‐2‐enal, 1 ), which are involved in chemical communication and behaviour of the Moroccan locust, Dociostaurus maroccanus, a serious agricultural pest. The compound was identified by comparison of its chromatographic and spectrometric features and microchemical reactions with those of a synthetic sample. The natural compound was shown to have the R,R configuration by chiral HPLC analysis, and its structure is unique as an insect pheromone component. Both isomers of phytal are produced by sexually mature adult males and elicit electroantennographic responses in antennae of both sexes. In two‐choice olfactometer bioassays, males and females significantly preferred the stream enriched with racemic phytal to the control. In contrast, hydrogenated phytal was behaviourally inert. Both isomers of phytal are specific to D. maroccanus as they are absent in the closely related, habitat‐sharing species Dociostaurus jagoi and Calliptamus wattenwylianus. Legs and wings are the main release sites of the compound: approximately 90 % of that emitted by living individuals. In biosynthetic studies, phytal appears to proceed from oxidation of phytol ( 2 ) after injection of deuterated phytol into the abdomen of the insect or after administration in the diet. Our results demonstrate that phytal is a candidate sex pheromone component of the Moroccan locust; it is produced by mature males, and might be eavesdropped upon by conspecific males.