Ensaios de tratabilidade de águas residuárias da indústria de piso de madeira por processos oxidativos avançados: ozônio e UV-C.

A indústria moveleira em geral e de piso de madeira é caracterizada por processos a seco. Em decorrência da limpeza e lavagem de maquinário e superfícies gera águas residuárias em baixos volumes porém altamente contaminadas com substâncias recalcitrantes de difícil tratamento. Com o objetivo de oferecer uma alternativa tecnológica de fácil operação (com uso mínimo de reagentes químicos), capaz de tratar tais águas, reduzir toxicidade e aumentar biodegradabilidade do efluente, viabilizando desta forma uma etapa subsequente de tratamento biológico, o presente trabalho conduziu ensaios de tratabilidade baseados em processos oxidativos avançados com águas residuárias provenientes de lavagens em uma indústria de piso de madeira em Nybro, Suécia, com DQO inicial de aproximadamente 45.000 mg/L e pH de 2,3-2,6. Após tratamento primário in situ com redução de 89% de DQO, os seguintes processos geradores de radicais OH foram testados em escala de laboratório: ozonização sem ajuste de pH (Etapa I); ozonização com ajuste de pH (Etapa II); e ozonização + UV-C com ajuste de pH (Etapa III). Os experimentos foram realizados em semi-batelada, utilizando-se um aparato com dois reatores conectados (de O3 e de UV), entre os quais foi mantido fluxo de recirculação em contracorrente com o gás. Para o desenho experimental, utilizou-se a metodologia de planejamento fatorial do tipo Delineamento Composto Central Rotacional (DCCR) utilizando-se como variáveis independentes, (i) vazão de recirculação entre os reatores (VR) com níveis variando de 0,3 a 3L/min; (ii) concentração de O3 na mistura gasosa injetada ([O3]) ou modo de dosagem cujos níveis variaram de 40 a 115 g/Nm3 e; (iii) pH inicial (Etapas II e III) com níveis que variaram de 3 a 11. A quantidade total de O3 fornecida até o final de cada ensaio foi fixada em 2 gramas de O3 para cada grama de DQO inicial (2:1). A eficiência de cada tratamento foi avaliada em função da redução de DQO, da remoção de COT e do consumo de O3. Para ozonização sem ajuste de pH foram alcançadas reduções de DQO e COT de 65 e 31% respectivamente. No tratamento com ajuste de pH sem UV, foram alcançadas reduções de DQO e COT de 85% e 43% com pHinicial = 7,0 enquanto que no tratamento com UV foi alcançada redução de DQO e COT de 93% e 56% respectivamente, com pHi = 9,38. Os resultados de respirometria com os efluentes dos tratamentos indicaram que a ozonização destas águas em pH baixo pode resultar na geração de subprodutos menos biodegradáveis. Entretanto, tais produtos não são gerados quando a ozonização é realizada em pH mais elevado (7,0), mesmo sem aplicação de UV, com doses de O3:DQOinicial menores que 1:1. O tratamento por ozonização pode, portanto, ser aplicado como uma etapa intermediária de tratamento das águas residuárias em questão, inclusive precedendo o tratamento biológico.

A novel short neurotoxin, cobrotoxin c, from monocellate cobra (Naja kaouthia) venom: isolation and purification, primary and secondary structure determination, and tertiary structure modeling

A novel short neurotoxin, cobrotoxin c (CBT C) was isolated from the venom of monocellate cobra (Naja kaouthia) using a combination of ion-exchange chromatography and FPLC. Its primary structure was determined by Edman degradation. CBT C is composed of 61 amino acid residues. It differs from cobrotoxin b (CBT B) by only two amino acid substitutions, Thr/Ala11 and Arg/Thr56, which are not located on the functionally important regions by sequence similarity. However, the LD50 is 0.08 mg/g to mice, i.e. approximately five-fold higher than for CBT B. Strikingly, a structure-function relationship analysis suggests the existence of a functionally important domain on the outside of Loop III of CBT C. The functionally important basic residues on the outside of Loop III might have a pairwise interaction with alpha subunit, instead of gamma or delta subunits of the nicotinic acetylcholine receptor (nAChR). (C) 2002 Elsevier Science Inc. All rights reserved.

Characterization of vertical Mo/diamond Schottky barrier diode from non-ideal I-V and C-V measurements based on MIS model

In this study, we investigated non-ideal characteristics of a diamond Schottky barrier diode with Molybdenum (Mo) Schottky metal fabricated by Microwave Plasma Chemical Vapour Deposition (MPCVD) technique. Extraction from forward bias I-V and reverse bias C- 2-V measurements yields ideality factor of 1.3, Schottky barrier height of 1.872 eV, and on-resistance of 32.63 mö·cm2. The deviation of extracted Schottky barrier height from an ideal value of 2.24 eV (considering Mo workfunction of 4.53 eV) indicates Fermi level pinning at the interface. We attributed such non-ideal behavior to the existence of thin interfacial layer and interface states between metal and diamond which forms Metal-Interfacial layer-Semiconductor (MIS) structure. Oxygen surface treatment during fabrication process might have induced them. From forward bias C-V characteristics, the minimum thickness of the interfacial layer is approximately 0.248 nm. Energy distribution profile of the interface state density is then evaluated from the forward bias I-V characteristics based on the MIS model. The interface state density is found to be uniformly distributed with values around 1013 eV - 1·cm- 2. © 2013 Elsevier B.V.

Multi-electron processes in 4.15-11.08 keV/u(13)C(6+) on argon collisions

The relative partial cross sections for C-13(6+)-Ar collisions at 4.15-11.08 keV/u incident energy are measured. The cross-section ratios sigma(2E)/sigma(SC), sigma(3E)/sigma(SC), sigma(4E)/sigma(SC) and sigma(5E)/sigma(SC) are approximately the constants of 0.51 +/- 0.05, 0.20 +/- 0.03, 0.06 +/- 0.03 and 0.02 +/- 0.01 in this region. The significance of the multi-electron process in highly charged ions (HCIs) with argon collisions is demonstrated (sigma(ME)/sigma(SC) as high as 0.79 +/- 0.06). In multi-electron processes, it is shown that transfer ionization is dominant while pure electron capture is weak and negligible. For all reaction channels, the cross-sections are independent of the incident energy in the present energy region, which is in agreement with the static characteristic of classic models, i.e. the molecular Coulomb over-the-barrier model (MCBM), the extended classical over-the-barrier (ECBM) and the semiempirical scaling laws (SL). The result is compared with these classical models and with our previous work of C-13(6+)-Ne collisions

Multi-electron processes in C-13(6+) ions with neon collisions in energy region 4.15-11.08 keV/u

The cross-section ratios of double-, triple-, quadruple-, and the total multi-electron processes to the single electron capture process sigma(DE)/sigma(SC), sigma(TE)/sigma(SC), sigma(QE)/sigma(SC) and sigma(ME)/sigma(SC)) as well as the relative ratios among reaction channels in double-electron active, triple-electron active and quadruple- electron active are measured in C-13(6+) -Ne collision in the energy region of 4.15-11.08 keV/u by employing position-sensitive and time-of-flight coincident techniques. It is determined that the cross-section ratios sigma(DE)/sigma(SC), sigma(TE)/sigma(SC), sigma(QE)/sigma(SC) and sigma(ME)/sigma(SC) are approximately the constants of 0.20 +/- 0.03, 0.16 +/- 0.04, 0.06 +/- 0.02 and 0.42 +/- 0.05. These values are obviously smaller than the predictions of the molecular Coulomb over-the-barrier model (MCBM) [J. Phys. B 23 (1990) 4293], the extended classical over-the-barrier model (ECBM) [J. Phys. B 19 (1986) 2925] and the semiempirical scaling laws (SL) [Phys. Rev. A 54 (1996) 4127]. However, the relative ratios among partial processes of DE, TE and QE are found to depend on collision energy, which suggests that the collision dynamics depends on the collision velocity. The limitation of velocity-independent character of ECBM, MCBM and SL is undoubtedly shown.

Interfacial supramolecular self-assembled monolayers of C-60 by thiolated beta-cyclodextrin on gold surfaces via monoanionic C-60

The supramolecular self-assembled monolayers (SAMs) of C-60 by thiolated beta-cyclodextrin (CD) on gold surfaces were constructed for the first time using C-60 monoanion. The results indicate that monoanionic C-60 plays a crucial role in the formation of the C-60-containing self-assembled monolayers. The generation of C-60 monoanion and the formation process of C-60 SAMs were monitored in-situ by UV-visible and near-IR spectroscopy. The resulting C-60 SAMs were fully characterized by spectroscopic ellipsometry (SE), cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and water contact angle measurements. After the immobilization of C-60 by the SAMs of thiolated beta-CD, the film thickness increased by approximately 1 nm from 0.8 to 1.8 nm as determined by SE, demonstrating the formation of the supramolecular self-assembled monolayers of thiolated beta-CD/C-60. The new C-60 SAMs exhibited one quasi-reversible redox couple at half wave potential of -0.57 V vs SCE in aqueous solution containing 0.1 M KCl. The surface coverage of C-60 on the gold surfaces was estimated to be 1.1 x 10(-10) mol cm(-2). The XPS showed the assembly of C-60 over the thiolated beta-CD SAMs.

Crystallization and characterization of substoichiometric compound (W0.5Al0.5)C-0..5 obtained by solid-state reaction

(W0.5Al0.5)C-0.5 substoichiometric compound is synthesized by a combination of mechanical milling and high-pressure reactive sintering. X-ray diffraction is used to monitor the phase changes and crystallization of (W0.5Al0.5) C-0.5 during the whole reaction process. As a result, (W0.5Al0.5) C-0.5 is identified as the hexagonal WC-type belonging to the P-6m2 space group (No. 187), and the lattice parameters of (W0.5Al0.5)C-0.5 are calculated to be a = 2.907 (1) angstrom, c = 2.838 (1) angstrom, which are very similar to those of WC even if there are approximately 50 pct carbon vacancies in the cell of (W0.5Al0.5)C-0.5 as compared with WC. The substoichiometric (W0.5Al0.5)C-0.5 compound has a Vickers microhardness of 2385 +/- 70 kg mm(-2), which is as high as that of WC, while its density is far lower than that of WC.

PHYSICAL AGING OF HIGH-PERFORMANCE THERMOPLASTICS - ENTHALPY RELAXATION IN PEK-C AND PES-C

The developments of physical aging in phenolphthalein poly(aryl-ether-ketone) (PEK-C) and poly(aryl-ether-sulfone) (PES-C) with time at two aging temperatures up to 20 K below their respective glass transition temperatures (T-g = 495 and 520 K) have been studied using differential scanning calorimetry (DSC). Substantial relaxation within the aging course of several hours were observed by detecting T-g decreasing during physical aging process at the two aging temperatures. The relaxation processes of both polymers are extremely nonlinear and self-retarding. The time dependencies of their enthalpies during the initial stages of annealing were approximately modeled using the Narayanaswamy-Tool model. The structure relaxation parameters obtained from this fitting were used to predict the possibility of physical aging occurring at their respective using temperatures. (C) 1995 John Wiley and Sons, Inc.

The Obduction of Equatorial 13 degrees C Water in the Pacific Identified by a Simulated Passive Tracer

The obduction of equatorial 13 degrees C Water in the Pacific is investigated using a simulated passive tracer of the Consortium for Estimating the Circulation and Climate of the Ocean (ECCO). The result shows that the 13 degrees C Water initialized in the region 8 degrees N-8 degrees S, 130 degrees-90 degrees W enters the surface mixed layer in the eastern tropical Pacific, mainly through upwelling near the equator, in the Costa Rica Dome, and along the coast of Peru. Approximately two-thirds of this obduction occurs within 10 years after the 13 degrees C Water being initialized, with the upper portion of the water mass reaching the surface mixed layer in only about a month. The obduction of the 13 degrees C Water helps to maintain a cool sea surface temperature year-round, equivalent to a surface heat flux of about -6.0 W m(-2) averaged over the eastern tropical Pacific (15 degrees S-15 degrees N, 130 degrees W-eastern boundary) for the period of integration (1993-2006). During El Nino years, when the thermocline deepens as a consequence of the easterly wind weakening, the obduction of the 13 degrees C Water is suppressed, and the reduced vertical entrainment generates a warming anomaly of up to 10 W m(-2) in the eastern tropical Pacific and in particular along the coast of Peru, providing explanations for the warming of sea surface temperature that cannot be accounted for by local winds alone. The situation is reversed during La Nina years.

Origin and Pathway of Equatorial 13 degrees C Water in the Pacific Identified by a Simulated Passive Tracer and Its Adjoint

The origin and pathway of the thermostad water in the eastern equatorial Pacific Ocean, often referred to as the equatorial 13 degrees C Water, are investigated using a simulated passive tracer and its adjoint, based on circulation estimates of a global general circulation model. Results demonstrate that the source region of the 13 degrees C Water lies well outside the tropics. In the South Pacific, some 13 degrees C Water is formed northeast of New Zealand, confirming an earlier hypothesis on the water's origin. The South Pacific origin of the 13 degrees C Water is also related to the formation of the Eastern Subtropical Mode Water (ESTMW) and the Sub-Antarctic Mode Water (SAMW). The portion of the ESTMW and SAMW that eventually enters the density range of the 13 degrees C Water (25.8 < sigma(theta) < 26.6 kg m(-3)) does so largely by mixing. Water formed in the subtropics enters the equatorial region predominantly through the western boundary, while its interior transport is relatively small. The fresher North Pacific ESTMW and Central Mode Water (CMW) are also important sources of the 13 degrees C Water. The ratio of the southern versus the northern origins of the water mass is about 2 to 1 and tends to increase with time elapsed from its origin. Of the total volume of initially tracer-tagged water in the eastern equatorial Pacific, approximately 47.5% originates from depths above sigma(theta) = 25.8 kg m(-3) and 34.6% from depths below sigma(theta) = 26.6 kg m(-3), indicative of a dramatic impact of mixing on the route of subtropical water to becoming the 13 degrees C Water. Still only a small portion of the water formed in the subtropics reaches the equatorial region, because most of the water is trapped and recirculates in the subtropical gyre.

Correction to the pathogenic alternative splicing, caused by the common GNB3 c.825C>T allele, using a novel, antisense morpholino

The very common GNB3 c.825C>T polymorphism (rs5443), is present in approximately half of all human chromosomes. Significantly the presence of the GNB3 825T allele has been strongly associated, with predisposition to essential hypertension. Paradoxically the presence of the GNB3 825T allele, in exon 10, introduces a pathogenic alternative RNA splice site into the middle of exon 9. To attempt to correct this pathogenic aberrant splicing, we therefore bioinformatically designed, using a Gene Tools® algorithm, a GNB3 specific, antisense morpholino. It was hoped that this morpholino would behave in vitro as either a potential “ splice blocker and/or exon skipper, to both bind and inhibit/reduce the aberrant splicing of the GNB3, 825T allele. On transfecting a human lymphoblast cell line homozygous for the 825T allele, with this antisense morpholino, we encouragingly observed both a significant reduction (from ~58% to ~5%) in the production of the aberrant smaller GNB3 transcript, and a subsequent increase in the normal GNB3 transcript (from ~42% to ~95%). Our results demonstrate the potential use of a GNB3 specific antisense morpholino, as a pharmacogenetic therapy for essential hypertension.

Later Life Consequences of Developmental Mitochondrial DNA Damage in C. elegans

Mitochondria are responsible for producing the vast majority of cellular ATP, and are therefore critical to organismal health [1]. They contain thir own genomes (mtDNA) which encode 13 proteins that are all subunits of the mitochondrial respiratory chain (MRC) and are essential for oxidative phosphorylation [2]. mtDNA is present in multiple copies per cell, usually between 103 and 104 , though this number is reduced during certain developmental stages [3, 4]. The health of the mitochondrial genome is also important to the health of the organism, as mutations in mtDNA lead to human diseases that collectively affect approximately 1 in 4000 people [5, 6]. mtDNA is more susceptible than nuclear DNA (nucDNA) to damage by many environmental pollutants, for reasons including the absence of Nucleotide Excision Repair (NER) in the mitochondria [7]. NER is a highly functionally conserved DNA repair pathway that removes bulky, helix distorting lesions such as those caused by ultraviolet C (UVC) radiation and also many environmental toxicants, including benzo[a]pyrene (BaP) [8]. While these lesions cannot be repaired, they are slowly removed through a process that involves mitochondrial dynamics and autophagy [9, 10]. However, when present during development in C. elegans, this damage reduces mtDNA copy number and ATP levels [11]. We hypothesize that this damage, when present during development, will result in mitochondrial dysfunction and increase the potential for adverse outcomes later in life.

To test this hypothesis, 1st larval stage (L1) C. elegans are exposed to 3 doses of 7.5J/m2 ultraviolet C radiation 24 hours apart, leading to the accumulation of mtDNA damage [9, 11]. After exposure, many mitochondrial endpoints are assessed at multiple time points later in life. mtDNA and nucDNA damage levels and genome copy numbers are measured via QPCR and real-time PCR , respectively, every 2 day for 10 days. Steady state ATP levels are measured via luciferase expressing reporter strains and traditional ATP extraction methods. Oxygen consumption is measured using a Seahorse XFe24 extra cellular flux analyzer. Gene expression changes are measured via real time PCR and targeted metabolomics via LC-MS are used to investigate changes in organic acid, amino acid and acyl-carnitine levels. Lastly, nematode developmental delay is assessed as growth, and measured via imaging and COPAS biosort.

I have found that despite being removed, UVC induced mtDNA damage during development leads to persistent deficits in energy production later in life. mtDNA copy number is permanently reduced, as are ATP levels, though oxygen consumption is increased, indicating inefficient or uncoupled respiration. Metabolomic data and mutant sensitivity indicate a role for NADPH and oxidative stress in these results, and exposed nematodes are more sensitive to the mitochondrial poison rotenone later in life. These results fit with the developmental origin of health and disease hypothesis, and show the potential for environmental exposures to have lasting effects on mitochondrial function.

Lastly, we are currently working to investigate the potential for irreparable mtDNA lesions to drive mutagenesis in mtDNA. Mutations in mtDNA lead to a wide range of diseases, yet we currently do not understand the environmental component of what causes them. In vitro evidence suggests that UVC induced thymine dimers can be mutagenic [12]. We are using duplex sequencing of C. elegans mtDNA to determine mutation rates in nematodes exposed to our serial UVC protocol. Furthermore, by including mutant strains deficient in mitochondrial fission and mitophagy, we hope to determine if deficiencies in these processes will further increase mtDNA mutation rates, as they are implicated in human diseases.

An electrochemical study of PCl3 and POCl3 in the room temperature ionic liquid [C(4)mpyrr][N(Tf)(2)]

Voltammetric studies of PCl3 and POCl3 have not been reported in the literature to date, probably due to the instability of these molecules in conventional aprotic solvents giving unstable and irreproducible results. From a previous study [Amigues et al. Chem. Commun. 2005, 1-4], it was found that ionic liquids have the ability to offer a uniquely stable solution phase environment for the study of these phosphorus compounds. Consequently, the electrochemistry of PCl3 and POCl3 has been studied by cyclic voltammetry on a gold microelectrode in the ionic liquid [C(4)mpyrr][N(Tf)(2)] (1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide). For both compounds, reduction and oxidation waves were observed and a tentative assignment of the waves is given. For PCl3, the reduction was thought to proceed via the following mechanism: PCl3 + e(-) h reversible arrow PCl3-, PCl3- reversible arrow Cl- + (PCl2)-Cl-center dot, (and) Cl- + PCl3 h PCl4-. For POCl3, the suggested reduction mechanism was analogous to that of PCl3: POCl3 + e(-) reversible arrow POCl3-, POCl3- reversible arrow Cl- + (POCl2)-O-center dot, and Cl- + POCl3 h POCl4-. In both cases (PCl2)-Cl-center dot and (POCl2)-O-center dot are likely to engage in further reactions. Potential step microdisk chronoamperometry was carried out on the reductive waves of PCl3 and POCl3 to measure diffusion coefficients and number of electrons transferred. It was found that the diffusion of PCl3 was unusually slow (3.1 x 10(-12) m(2) s(-1)): approximately 1 order of magnitude less than that for POCl3 (2.2 x 10(-11) m(2) s(-1)). For both PCl3 and POCl3, a