Aromatic amines sources, environmental impact and remediation

Aromatic amines are widely used industrial chemicals as their major sources in the environment include several chemical industry sectors such as oil refining, synthetic polymers, dyes, adhesives, rubbers, perfume, pharmaceuticals, pesticides and explosives. They result also from diesel exhaust, combustion of wood chips and rubber and tobacco smoke. Some types of aromatic amines are generated during cooking, special grilled meat and fish, as well. The intensive use and production of these compounds explains its occurrence in the environment such as in air, water and soil, thereby creating a potential for human exposure. Since aromatic amines are potential carcinogenic and toxic agents, they constitute an important class of environmental pollutants of enormous concern, which efficient removal is a crucial task for researchers, so several methods have been investigated and applied. In this chapter the types and general properties of aromatic amine compounds are reviewed. As aromatic amines are continuously entering the environment from various sources and have been designated as high priority pollutants, their presence in the environment must be monitored at concentration levels lower than 30 mg L1, compatible with the limits allowed by the regulations. Consequently, most relevant analytical methods to detect the aromatic amines composition in environmental matrices, and for monitoring their degradation, are essential and will be presented. Those include Spectroscopy, namely UV/visible and Fourier Transform Infrared Spectroscopy (FTIR); Chromatography, in particular Thin Layer (TLC), High Performance Liquid (HPLC) and Gas chromatography (GC); Capillary electrophoresis (CE); Mass spectrometry (MS) and combination of different methods including GC-MS, HPLC-MS and CE-MS. Choosing the best methods depend on their availability, costs, detection limit and sample concentration, which sometimes need to be concentrate or pretreated. However, combined methods may give more complete results based on the complementary information. The environmental impact, toxicity and carcinogenicity of many aromatic amines have been reported and are emphasized in this chapter too. Lately, the conventional aromatic amines degradation and the alternative biodegradation processes are highlighted. Parameters affecting biodegradation, role of different electron acceptors in aerobic and anaerobic biodegradation and kinetics are discussed. Conventional processes including extraction, adsorption onto activated carbon, chemical oxidation, advanced oxidation, electrochemical techniques and irradiation suffer from drawbacks including high costs, formation of hazardous by-products and low efficiency. Biological processes, taking advantage of the naturally processes occurring in environment, have been developed and tested, proved as an economic, energy efficient and environmentally feasible alternative. Aerobic biodegradation is one of the most promising techniques for aromatic amines remediation, but has the drawback of aromatic amines autooxidation once they are exposed to oxygen, instead of their degradation. Higher costs, especially due to power consumption for aeration, can also limit its application. Anaerobic degradation technology is the novel path for treatment of a wide variety of aromatic amines, including industrial wastewater, and will be discussed. However, some are difficult to degrade under anaerobic conditions and, thus, other electron acceptors such as nitrate, iron, sulphate, manganese and carbonate have, alternatively, been tested.

Zebrafish embryos as in vivo model for toxicity evaluation: screening of nanoparticle formulations DODAB:MO and DODAC:MO

Dissertação de mestrado em Molecular Genetics

Bacterial nanocellulose as a structured platform for conductive biopolymers

[Exert] Since the discovery that polyacetylene could be doped to the metallic state more than 3 decades ago, an ever-growing body of a multidisciplinary approach to material design, synthesis, and system integration has been evidenced. The present chapter will primarily review the emerging field of intrinsically conducting polymer and conductive polymer blends, with polyaniline and polypyrrole as the major representatives of conducting polymers. This survey will also address some of the potential areas for applications of such conductive polymer blends. Also, current results concerning the chemical polymerization of conducting polymers on bacterial nanocellulose (BNC) will be presented, including brief remarks on the rationale for the use of conductive BNC blends. This will be followed by a discussion on their properties and potential applications (...).

Desenvolvimento de membranas poliméricas baseadas em Poli(fluoreto de vinilideno) para a filtração de materiais biológicos

Dissertação de mestrado em Biofísica e Bionanossistemas

Laccase immobilization on bacterial nanocellulose membranes: antimicrobial, kinetic and stability properties

This work studied the physical immobilization of a commercial laccase on bacterial nanocellulose (BNC) aiming to identify the laccase antibacterial properties suitable for wound dressings. Physico-chemical analysis demonstrates that the BNC structure is manly formed by pure crystalline I cellulose. The pH optimum and activation energy of free laccase depends on the substrate employed corresponding to pH 6, 7, 3 and 57, 22, 48 kJ mol1 for 2,6-dimethylphenol (DMP), catechol and 2,2 -azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), respectively. The Michaelis-Menten constant (Km) value for the immobilized laccase (0.77 mM) was found to be almost double of that of the free enzyme (0.42 mM). However, the specific activities of immobilized and free laccase are similar suggesting that the cage-like structure of BNC allows entrapped laccase to maintain some flexibility and favour substrate accessibility. The results clearly show the antimicrobial effect of laccase in Gram-positive (92%) and Gram-negative (26%) bacteria and cytotoxicity acceptable for wound dressing applications.

In-line rheo-optical microstructural characterization of complex polymer systems

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos.

Desarrollo de sistemas nano/micro-particulados con aplicación en la fotodegradación selectiva de contaminantes orgánicos en solución. Development of nano / micro-particles systems with application to selective photodegradation of organic pollutants in solution.

IDENTIFICACIÓN DEL PROBLEMA DE ESTUDIO. Las sustancias orgánicas solubles en agua no biodegradables tales como ciertos herbicidas, colorantes industriales y metabolitos de fármacos de uso masivo son una de las principales fuentes de contaminación en aguas subterráneas de zonas agrícolas y en efluentes industriales y domésticos. Las reacciones fotocatalizadas por irradiación UV-visible y sensitizadores orgánicos e inorgánicos son uno de los métodos más económicos y convenientes para la descomposición de contaminantes en subproductos inocuos y/o biodegradables. En muchas aplicaciones es deseable un alto grado de especificidad, efectividad y velocidad de degradación de un dado agente contaminante que se encuentra presente en una mezcla compleja de sustancias orgánicas en solución. En particular son altamente deseables sistemas nano/micro -particulados que formen suspensiones acuosas estables debido a que estas permiten una fácil aplicación y una eficaz acción descontaminante en grandes volúmenes de fluidos. HIPÓTESIS Y PLANTEO DE LOS OBJETIVOS. El objetivo general de este proyecto es desarrollar sistemas nano/micro particulados formados por polímeros de impresión molecular (PIMs) y foto-sensibilizadores (FS). Un PIMs es un polímero especialmente sintetizado para que sea capaz de reconocer específicamente un analito (molécula plantilla) determinado. La actividad de unión específica de los PIMs en conjunto con la capacidad fotocatalizadora de los sensibilizadores pueden ser usadas para lograr la fotodescomposición específica de moléculas “plantilla” (en este caso un dado contaminante) en soluciones conteniendo mezclas complejas de sustancias orgánicas. MATERIALES Y MÉTODOS A UTILIZAR. Se utilizaran técnicas de polimerización en mini-emulsión para sintetizar los sistemas nano/micro PIM-FS para buscar la degradación de ciertos compuestos de interés. Para caracterizar eficiencias, mecanismos y especificidad de foto-degradación en dichos sistemas se utilizan diversas técnicas espectroscópicas (estacionarias y resueltas en el tiempo) y de cromatografía (HPLC y GC). Así mismo, para medir directamente distribuciones de afinidades de unión y eficiencia de foto-degradación se utilizaran técnicas de fluorescencia de molécula/partícula individual. Estas determinaciones permitirán obtener resultados importantes al momento de analizar los factores que afectan la eficiencia de foto-degradación (nano/micro escala), tales como cantidad y ubicación de foto- sensibilizadores en las matrices poliméricas y eficiencia de unión de la plantilla y los productos de degradación al PIM. RESULTADOS ESPERADOS. Los estudios propuestos apuntan a un mejor entendimiento de procesos foto-iniciados en entornos nano/micro-particulados para aplicar dichos conocimientos al diseño de sistemas optimizados para la foto-destrucción selectiva de contaminantes acuosos de relevancia social; tales como herbicidas, residuos industriales, metabolitos de fármacos de uso masivo, etc. IMPORTANCIA DEL PROYECTO. Los sistemas nano/micro-particulados PIM-FS que se propone desarrollar en este proyecto se presentan como candidatos ideales para tratamientos específicos de efluentes industriales y domésticos en los cuales se desea lograr la degradación selectiva de compuestos orgánicos. Los conocimientos adquiridos serán indispensables para construir una plataforma versátil de sistemas foto-catalíticos específicos para la degradación de diversos contaminantes orgánicos de interés social. En lo referente a la formación de recursos humanos, el proyecto propuesto contribuirá en forma directa a la formación de 3 estudiantes de postgrado y 2 estudiantes de grado. En las capacidades institucionales se contribuirá al acondicionamiento del Laboratorio para Microscopía Óptica Avanzada (LMOA) en el Dpto. de Química de la UNRC y al montaje de un sistema de microscopio de fluorescencia que permitirá la aplicación de técnicas avanzadas de espectroscopia de fluorescencia de molecula individual. Water-soluble organic molecules such as certain non-biodegradable herbicides, industrial dyes and metabolites of widespread use drugs are a major source of pollution in groundwater from agricultural areas and in industrial and domestic effluents. Photo-catalytic reactions by UV-visible irradiation and organic sensitizers are one of the most economical and convenient methods for the decomposition of pollutants into harmless byproducts. In many applications it is highly desirable a high degree of specificity, effectiveness and speed of degradation of specific pollutants present in a complex mixture. In particular nano/micro-particles systems that form stable aqueous suspensions are highly desirable because they allow for easy application and effective decontamination of large volumes of fluids. Herein we propose the development of nano/micro particles composed by molecularly imprinted polymers (MIP) and photo-sensitizers (PS). The specific binding of MIP and the photo-catalytic ability of the sensitizers are used to achieve the photo-decomposition of specific "template" molecules in complex mixtures. Mini-emulsion polymerization techniques will be used to synthesize nano/micro MIP-FS systems. Spectroscopy (steady-state and time resolved) and chromatography (GC and HPLC) will be used to characterize efficiency, mechanisms and specificity of photo-degradation in these systems. In addition single molecule/particle fluorescence spectroscopy techniques will be used to directly measure distributions of binding affinities and photo-degradation efficiency in individual particles. The proposed studies point to a more detailed understanding of the factors affecting the photo-degradation efficiency in nano/micro-particles and to apply that knowledge in the design of optimized systems for photo-selective destruction of socially relevant aqueous pollutants.

Formação das castas no gênero Melípona (Illiger, 1806)

The present work is destinated to prove that the castes : workers and queens, in Melipona bees are due to genetic factors and not to differences in food. 2) Material used: Hives of Melipona quadri-fasciata anthidioides (Lep. 1836), M. schenki schenki (Gribodo, 1893), M. fasciata rufiventris (Lep. 1836), M. quadri-fasciata vicina (Lep. 1836), M. marginata marginata (Lep. 1836), Apis mellifera (L. 1758). 3) It should be pointed out that in Melipona bees there are no royal cells for the queens, but all the cells are of the same size independently of being destinated for workers, queens or drones. The numerous queens which are born are killed soon after emerging from their cells. 4) Changes of feeding in quality and in quantity caused no variation of castes. The only variable factor is the size, which becomes bigger when the bee is well nourished. 5) The offsprings of 5 hives were examined : 3 of M. quadri-fasciata anthidioides (n.o 1, n.o 2 and n.o 3), 1 of M. quadri-fasciata vicina (n.o 4) and 1 of M. marginata marginata (n.o 5). Combs of about 40 cells were taken into laboratory and the type of bee registered immediately after emerging. The results of the counts were: BOX COMB WORKER QUEEN PERCENTAGE Σ X2 to 12,5% Nº 1 1th 69 8 10,4% 0, 3139 " 1 2nd 144 18 11,1% 0, 2856 " 2 1th 52 8 13,3% 0, 0384 " 3 1th 45 10 18,2% 1, 6736 " 4 1th 56 4 6,7% 1, 8686 " 4 2nd 29 4 12,1% 0,00432 Σ X2 to 25% " 5 1th 34 14 29,2% 0,44444 "5 2nd 83 27 24,5% 0, 0121 In the 4 first boxes there is a percentage of 11,63% queens and in the last there is a percentage of 25,95%. 6) These percentages are very near two genetical ratios: 12,5% or 7:1, and 25% or 3:1, which correspond to a trifactorial and a bifactorial back-cross. Carrying out a X² test no significant deviations were found ( X² to 12,5% and to 25% and table 1 to 4). 7) We suppose that the formula for the queen in the first case (11,65%) is: AaBbCc. Since the Melipona bees are arrhenotokous hymenopteres, the drones are haploid and may have any one of the following eight formulas, corresponding to the gonic segregation of the queem : ABC, ABc, Abc, Abc, AbC, aBC, aBc, abC, abc. Anyone combination of these males with the queen will give a segregation of 7 workers to 1 queen, since there is always only one triple heterozygote among the eight possible segregates (table 5). 8) In order to explain the second case, it is suffient to assume that in this species there are only two pairs of factors, the queen being the double heterozygote : AaBb, while the drones may have any one of the following constitutions: AB, Ab, aB and ab. Workers are again all diploids which are homozygous for one or both factors, for instance: AABB, AABb, AaBB, aaBb, AAbb, etc. (table 6). 9) It is suggested that the genus Melipona is an intermediary type between the solitary bees, where all females are fertile independently of their feeding, and the genera Apis and Trigona, where without special feeding all females are born sterile, while only specially fed females develop into fertile queens. 10) No speculations are put forward with regards to the evolutionary mechanism which may have been responsible for the development of the genetical determination of castes in Melipona, since it seems advisable point to extend the studies to other insects with complicated caste systems.

Observações preliminares sôbre caponização de frangos "Leghorn" com estrogênios

The effect of "Capastrol", pellets of diethilstilbestrol at 0,015 g., in 12 weeks S. C. W. Leghorn cockerels, was studied. The results secured are in accordance with those obtained by other authors and can be resumed as follows: 1) paleness and shrunken of the comb, whose size is reduced, in comparison with the controls; 2) no differences in the total weight gain between control and treated lot; 3) size of testis greatly reduced in treated males; 4) improvement of meat by fat deposition in chickens that received treatment.

Almeirão, quicúio e grama seda como alimento verde para pintos em crescimento

The author studied in this paper effect of chicory (Chicorium intybus L.), kikuyugrass (Pennisetum clandestinum Hoahst) and a variety of Bermuda grass (Cynodon dactilon Pers.) named "Grama seda" as green feeds in growth of White Leghorn chickens (0-8 weeks). Males and females were se-pareted by feathering and development of comb. The results obtained can be summarized as follows : a) - Without separation of sex, the chickens that received green feeds showed better development than that did not receive green suplements. b) - The chicory showed to be something better that kikuyugrass and Bermuda grass, which had a similar effect. c) - The green feeds used had little influence in development of males. d) - The females in the lots suplemented by green feeds showed to be superior to the females in the lots that did not receive it. e) - The author think that the presence of some priciples having action in the female hormony function is responsable for the better growth in the lot that received green feeds.

Novos táxons de Hemilophini (Coleoptera, Cerambycidae, Lamiinae) das Américas

Descreve-se o gênero Mexicoscylus para incluir M. rosae sp. nov., do México, espécie-tipo do gênero, e M. bivittatus (Gahan, 1892), comb. nov. Acrescenta-se chave para as espécies de Mexicoscylus. Mais três espécies são descritas: Cotycuara villosa sp. nov., da Costa Rica; Phoebe parvimacula sp. nov., da Bolívia e Adesmus beruri sp. nov., do Brasil (Amazonas). Todas as espécies novas são ilustradas.

Establishment of a new genus for Parastenocaris itica (Copepoda, Harpacticoida) from El Salvador, Central America, with discussion of the Parastenocaris fontinalis and P. proserpina groups

A new genus of Parastenocarididae is described from the Neotropical region. Iticocaris gen. nov. is established to include Parastenocaris itica Noodt, 1962. Iticocaris gen. nov. is defined by the following characters: 1) male leg 3 with 2-segmented exopod; 2) first exopodal segment short and rectangular; 3) thumb hypertrophic, longer than the second exopodal segment and inserted on the distal edge of exopod segment 1, occupying the whole distal margin; 4) exopod 2 or apophysis strongly sclerotized, articulated with the exopod segment 1 on its inner margin and curved against the thumb, forming a strong forceps; 5) leg 4 endopod without dimorphism in shape and size vs. minor dimorphism in ornamentation; 6) leg 5 with three setae and 7) lack of the anterolateral furcal seta II. The new genus is monotypic, represented by Iticocaris itica (Noodt, 1962) comb. nov., from El Salvador, Central America. A close relationship is hypothesized between I. itica and the genus Brasilibathynellocaris Jakobi, 1972, the males of which both share the forceps-like elongated apophysis.

Neurolysis using a carbohydrate polymer gel for the treatment of postoperative neuropathic pain.

Perineural and intraneural fibrosis is thought to be the main cause of failure of the many surgical treatments of neuropathic pain. We have used Adcon-T/N carbohydrate polymer gel for prevention of perineural fibrosis in several parts of the body. In this retrospective study, 54 patients who presented with postoperative neuropathic pain had microsurgical epineural neurolysis and relocation of a terminal neuroma. In 19 of them, the carbohydrate gel was applied at the same time. The mean follow-up was four years and the nerve distribution varied. Postoperative improvement in pain scores (visual analogue scale (VAS) and neuropathic pain scale inventory (NPSI)), sensitivity, overall improvement and satisfaction were equivalent in the two groups, with pain relief in about 80% of the patients. There was no significant beneficial effect in the carbohydrate gel group. Patients treated with this device had a higher infection rate (21 compared with 0, p = 0.01) and delayed wound healing (31.6 compared with 11.8, p = 0.2). We conclude that good long-term pain relief is obtained postoperatively independently of the addition of carbohydrate gel. There was a slight but not significant trend towards profound pain relief with the gel.

Synthesis of medium-chain-length polyhydroxyalkanoates in arabidopsis thaliana using intermediates of peroxisomal fatty acid beta-oxidation.

Polyhydroxyalkanoate (PHA) is a family of polymers composed primarily of R-3-hydroxyalkanoic acids. These polymers have properties of biodegradable thermoplastics and elastomers. Medium-chain-length PHAs (MCL-PHAs) are synthesized in bacteria by using intermediates of the beta-oxidation of alkanoic acids. To assess the feasibility of producing MCL-PHAs in plants, Arabidopsis thaliana was transformed with the PhaC1 synthase from Pseudomonas aeruginosa modified for peroxisome targeting by addition of the carboxyl 34 amino acids from the Brassica napus isocitrate lyase. Immunocytochemistry demonstrated that the modified PHA synthase was appropriately targeted to leaf-type peroxisomes in light-grown plants and glyoxysomes in dark-grown plants. Plants expressing the PHA synthase accumulated electron-lucent inclusions in the glyoxysomes and leaf-type peroxisomes, as well as in the vacuole. These inclusions were similar to bacterial PHA inclusions. Analysis of plant extracts by GC and mass spectrometry demonstrated the presence of MCL-PHA in transgenic plants to approximately 4 mg per g of dry weight. The plant PHA contained saturated and unsaturated 3-hydroxyalkanoic acids ranging from six to 16 carbons with 41% of the monomers being 3-hydroxyoctanoic acid and 3-hydroxyoctenoic acid. These results indicate that the beta-oxidation of plant fatty acids can generate a broad range of R-3-hydroxyacyl-CoA intermediates that can be used to synthesize MCL-PHAs.

Peroxisomal polyhydroxyalkanoate biosynthesis is a promising strategy for bioplastic production in high biomass crops.

Polyhydroxyalkanoates (PHAs) are bacterial carbon storage polymers with diverse plastic-like properties. PHA biosynthesis in transgenic plants is being developed as a way to reduce the cost and increase the sustainability of industrial PHA production. The homopolymer polyhydroxybutyrate (PHB) is the simplest form of these biodegradable polyesters. Plant peroxisomes contain the substrate molecules and necessary reducing power for PHB biosynthesis, but peroxisomal PHB production has not been explored in whole soil-grown transgenic plants to date. We generated transgenic sugarcane (Saccharum sp.) with the three-enzyme Ralstonia eutropha PHA biosynthetic pathway targeted to peroxisomes. We also introduced the pathway into Arabidopsis thaliana, as a model system for studying and manipulating peroxisomal PHB production. PHB, at levels up to 1.6%-1.8% dry weight, accumulated in sugarcane leaves and A. thaliana seedlings, respectively. In sugarcane, PHB accumulated throughout most leaf cell types in both peroxisomes and vacuoles. A small percentage of total polymer was also identified as the copolymer poly (3-hydroxybutyrate-co-3-hydroxyvalerate) in both plant species. No obvious deleterious effect was observed on plant growth because of peroxisomal PHA biosynthesis at these levels. This study highlights how using peroxisomal metabolism for PHA biosynthesis could significantly contribute to reaching commercial production levels of PHAs in crop plants.