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A methodology for the quantitative analysis of enzymatic removal of biofilms (BF) was developed, based on a quartz crystal microbalance (QCM) under stationary conditions. This was applied to the case of Pseudomonas protegens (PP) BFs, through a series of five enzymes, whose removal activity was screened using the presented methodology. The procedure is based on the following: when BFs can be modeled as rigid materials, QCM can be used as a balance under stationary conditions for determining the BFs mass reduction by enzymatic removal. For considering a BF as a rigid model, energy dissipation effects, associated with viscoelastic properties of the BF, must be negligible. Hence, a QCM system with detection of dissipation (referred to as QCM with dissipation) was used for evaluating the energy losses, which, in fact, resulted in negligible energy losses in the case of dehydrated PP BFs, validating the application of the Sauerbrey equation for the change of mass calculations. The stationary methodology reduces operating times and simplifies data analysis in comparison to dynamic approaches based on flow setups, which requires the incorporation of dissipation effects due to the liquid media. By carrying out QCM, glycosidase-type enzymes showed BF removal higher than 80% at enzyme concentration 50 ppm, reaching removal over 90% in the cases of amylase and cellulase/xylanase enzymes. The highest removal percentage produced a reduction from about 15 to 1 µg in the BF mass. Amylase enzyme was tested from below 50 to 1 ppm, reaching around 60% of removal at 1 ppm. The obtained results were supported by other instrumental techniques such as Raman spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, atomic force microscopy, high performance anion exchange chromatography, thermogravimetric analysis, and differential scanning calorimetry. The removal quantifications obtained with QCM were compared with those obtained by well-established screening techniques (UV-vis spectrophotometry using crystal violet and agar diffusion test). The proposed methodology expands the possibility of using a quartz microbalance to perform enzymatic activity screening.

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Diffusion of additives in polymers is an important issue in the plastics industry since migratory-type molecules are widely used to tune the properties of polymeric composites. Predicting the diffusional behavior of new additives can minimize the need for repetitive experiments. This work presents molecular dynamics simulations at the microsecond time scale and uses the MARTINI force field to estimate self-diffusion coefficients, D, of six monounsaturated amides and their analogs carboxylic acids in polyethylene matrices (PE, MW = 5600 Da). The results are strongly influenced by the glass-forming properties of the PE matrix, which we characterize by three distinct temperatures. The metastability region (T < 325 K), the glass transition temperature (Tg = 256-260 K), and the end of the transition (T ≅ 200 K). Self-diffusion mechanisms are inferred from the results of the dependence of D on the molecular mass of the additive, observing a Rouse-like behavior at high temperatures and deviations from it within the metastability region of the matrix. Interestingly, D values are nonsensitive to the nature of the considered polar head for additives of similar size. The temperature-dependent behavior of D follows, at fixed additive size, a linear Arrhenius pattern at high temperatures and a super Arrhenius trend at lower temperatures, which is well represented with a power law equation as predicted by the Mode Coupling Theory (MCT). We offer a conceptual explanation for the observed super-Arrhenius behavior. This explanation draws on Truhlar and Kohen's interpretation of the available energies at both the initial and the transition states along the diffusion pathway. The matrix's mobility significantly affects solute self-diffusion, yielding equal activation enthalpies for the Arrhenius region or the same power law parameters for the super-Arrhenius regime. Finally, we establish a one-to-one time-equivalence of the self-diffusion processes between CG and all-atom systems for the largest additives and the PE matrix in the high-temperature regime.

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Different strategies were tested to reduce biofilm formation of the model marine bacteria Cobetia marina and Marinobacter hydrocarbonoclasticus on cross-linked polydimethylsiloxane (PDMS) coated aluminum and cellulose acetate surfaces modified by addition of multi-walled carbon nanotubes (MWCNT) or exposure of the surfaces to bromine vapors in the presence and absence of UV irradiation. The three surface modifications explored led to important reductions in biofilm formation for the two marine bacteria, up to 30% in the case of exposure to Br2(g). Biofouling reduction could be correlated to surface properties in all cases through the introduction of a quantitative theoretical model based on an effective roughness parameter, Raeff, that accounted for the different morphological changes observed. The model considers the possibility of bacterial inclusion into large surface wells, as observed by AFM in the case of Br2(g) + UV light treatment. In addition, a linear relationship was observed between biofouling reduction and the Raeff effective roughness parameter.

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Anthropogenic activities are increasing the atmospheric carbon dioxide (CO2); around a third of the CO2 emitted by these activities has been taken up by the ocean. Nevertheless, this marine ecosystem service of regulation remains largely invisible to society, and not enough is known about regional differences and trends in sea-air CO2 fluxes (FCO2), especially in the Southern Hemisphere. The objectives of this work were as follows: first to put values of FCO2 integrated over the exclusive economic zones (EEZ) of five Latin-American countries (Argentina, Brazil, Mexico, Peru, and Venezuela) into perspective regarding total country-level greenhouse gases (GHG) emissions. Second, to assess the variability of two main biological factors affecting FCO2 at marine ecological time series (METS) in these areas. FCO2 over the EEZs were estimated using the NEMO model, and GHG emissions were taken from reports to the UN Framework Convention on Climate Change. For each METS, the variability in phytoplankton biomass (indexed by chlorophyll-a concentration, Chla) and abundance of different cell sizes (phy-size) were analyzed at two time periods (2000-2015 and 2007-2015). Estimates of FCO2 at the analyzed EEZs showed high variability among each other and non-negligible values in the context of greenhouse gas emissions. The trends observed at the METS indicated, in some cases, an increase in Chla (e.g., EPEA-Argentina) and a decrease in others (e.g., IMARPE-Peru). Evidence of increasing populations of small size-phytoplankton was observed (e.g., EPEA-Argentina, Ensenada-Mexico), which would affect the carbon export to the deep ocean. These results highlight the relevance of ocean health and its ecosystem service of regulation when discussing carbon net emissions and budgets.

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Here, a mathematical model is presented, which accounts for the dependence of the surface electrical charge density (σ) on pH and the concentration of added salts (Cs), generated when a water drop rolls or slides on the surface of a hydrophobic polymer, a process known as liquid-polymer contact electrification (LPCE). The same model was successfully applied to fit the isotherms of ξ-potential as a function of pH, reported in the literature by other authors for water-poly(tetrafluoroethylene) (PTFE) interfaces. Hence, the dependence of σ and ξ on pH was described using the same concept: acid-base equilibria at the water-polymer interface. Equilibrium constants were estimated by fitting experimental isotherms. The experimental results and the model are consistent with a number of 10-100 acid-base sites/µm2. The model predicts the increase of |σ| and |ξ| with pH in the range of 2-10 and the existence of a zero-charge point at pHzcp ≅ 3 for PTFE (independent of Cs). Excellent fits were obtained with Ka/Kb ∼ 9 × 107, where Ka and Kb are the respective acid and base equilibrium constants. On the other hand, the observed decrease in |σ| and |ξ| with Cs at fixed pH is quantitatively described by introducing an activity factor associated with the quenching of water activity by the salt ions at the polymer-water interface, with quenching constant Kq. Additionally, the quenching predicts a decrease in |σ| and |ξ| at extreme pH, where I > (1/Kq) (I: ionic strength), in agreement with literature reports.

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The objective of this study was to estimate the components of variance and genetic parameters of test-day milk yield in first lactation Girolando cows, using a random regression model. A total of 126,892 test-day milk yield (TDMY) records of 15,351 first-parity Holstein, Gyr, and Girolando breed cows were used, obtained from the Associação Brasileira dos Criadores de Girolando. To estimate the components of (co) variance, the additive genetic functions and permanent environmental covariance were estimated by random regression in three functions: Wilmink, Legendre Polynomials (third order) and Linear spline Polynomials (three knots). The Legendre polynomial function showed better fit quality. The genetic and permanent environment variances for TDMY ranged from 2.67 to 5.14 and from 9.31 to 12.04, respectively. Heritability estimates gradually increased from the beginning (0.13) to mid-lactation (0.19). The genetic correlations between the days of the control ranged from 0.37 to 1.00. The correlations of permanent environment followed the same trend as genetic correlations. The use of Legendre polynomials via random regression model can be considered as a good tool for estimating genetic parameters for test-day milk yield records.(AU)

O objetivo deste estudo foi estimar os componentes de variância e os parâmetros genéticos da produção de leite no dia do teste (TDMY) em vacas Girolando de primeira lactação, usando modelo de regressão aleatória. Foram utilizados 126.892 registros de produção de leite no dia controle de 15.351 vacas primíparas das raças Holandesa, Gir e Girolando, obtidas na Associação Brasileira dos Criadores de Girolando. Para estimar os componentes de (co) variância, as funções genéticas aditivas e de covariância ambiental permanente foram estimadas por regressão aleatória em três funções: Wilmink, polinômios de Legendre (terceira ordem) e polinômios splines lineares (três nós). A função polinomial de Legendre apresentou melhor qualidade de ajuste. As variâncias genéticas e de ambiente permanente para produção de leite no dia do controle variaram de 2,67 a 5,14 e de 9,31 a 12,04, respectivamente. As estimativas de herdabilidade aumentaram gradativamente do início (0,13) para o meio da lactação (0,19). As correlações genéticas entre os dias do controle variaram de 0,37 a 1,00. As correlações de ambiente permanente seguiram a mesma tendência das correlações genéticas. A utilização dos polinômios de Legendre via modelos de regressão aleatória pode ser considerada como uma boa ferramenta para estimação de parâmetros genéticos da produção de leite no dia do teste.(AU)

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Liquid-polymer contact electrification between sliding water drops and the surface of polytetrafluoroethylene (PTFE) was studied as a function of the pH and ionic strength of the drop as well as ambient relative humidity (RH). The PTFE surface was characterized by using SEM, water-contact-angle measurements, FTIR spectroscopy, XPS, and Raman spectroscopy. The charge acquired by the drops was calculated by detecting the transient voltage induced on a specifically designed capacitive sensor. It is shown that water drops become positively charged at pH > pHzch (pHzch being the zero charge point of the polymer) while they become negatively charged for pH < pHzch. The addition of non-hydrolysable salts (NaCl or CaCl2) to water decreases the electrical charge induced in the drop. The charge also decreases with increasing RH. These results suggest proton or hydroxyl transfer from the liquid to the hydrophobic polymer surface. A proposed thermodynamic model for the ion transfer process allows explaining the observed effects of RH, pH and ionic strength.

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This study aimed to establish criteria for eliminating redundant variables, to know the magnitude of the data relationship, and to provide information that helps researchers in the use of the technique to analyze and interpret production data and egg quality. The data used in this work was obtained from four successive generations of the quail lineage developed by the Department of Animal Science of the Federal University of Pelotas. The characteristics were measured from the 42nd day of age, when the egg production period began, until 126 days of production, obtaining three 28 day periods (cycles) in the four successive generations, totaling 545 females. Of the twelve original variables, only seven demonstrated potential to be maintained in future experiments, representing a 42% exclusion. The main philosophy of this study was the analysis of the studied variables and made possible the understanding of the relationship and the correlations.(AU)

O objetivo do presente trabalho foi estabelecer critérios para eliminação de variáveis redundantes, conhecer a magnitude das relações dos dados, além de fornecer informações que auxiliem pesquisadores na utilização da técnica para analisar e interpretar dados de produção e qualidade de ovos de codornas. Os dados utilizados neste trabalho são provenientes de quatro gerações sucessivas da linhagem de codornas de corte desenvolvida pelo Departamento de Zootecnia da Universidade Federal de Pelotas. As características foram mensuradas do 42º dia de idade até o 126º dia de produção, totalizando 545 fêmeas. Das 12 variáveis originais analisadas, apenas sete demonstraram potencial para serem mantidas em experimentos futuros, representando uma exclusão de 42%. A análise de componentes principais foi efetiva para a redução das variáveis estudadas e possibilitou a compreensão da relação e correlação dessas.(au)

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This study aimed to establish criteria for eliminating redundant variables, to know the magnitude of the data relationship, and to provide information that helps researchers in the use of the technique to analyze and interpret production data and egg quality. The data used in this work was obtained from four successive generations of the quail lineage developed by the Department of Animal Science of the Federal University of Pelotas. The characteristics were measured from the 42nd day of age, when the egg production period began, until 126 days of production, obtaining three 28 day periods (cycles) in the four successive generations, totaling 545 females. Of the twelve original variables, only seven demonstrated potential to be maintained in future experiments, representing a 42% exclusion. The main philosophy of this study was the analysis of the studied variables and made possible the understanding of the relationship and the correlations.(AU)

O objetivo do presente trabalho foi estabelecer critérios para eliminação de variáveis redundantes, conhecer a magnitude das relações dos dados, além de fornecer informações que auxiliem pesquisadores na utilização da técnica para analisar e interpretar dados de produção e qualidade de ovos de codornas. Os dados utilizados neste trabalho são provenientes de quatro gerações sucessivas da linhagem de codornas de corte desenvolvida pelo Departamento de Zootecnia da Universidade Federal de Pelotas. As características foram mensuradas do 42º dia de idade até o 126º dia de produção, totalizando 545 fêmeas. Das 12 variáveis originais analisadas, apenas sete demonstraram potencial para serem mantidas em experimentos futuros, representando uma exclusão de 42%. A análise de componentes principais foi efetiva para a redução das variáveis estudadas e possibilitou a compreensão da relação e correlação dessas.(au)

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In this work we study, by means of ab initio calculations, the structural, electronic and magnetic properties of Y-doped BiFeO3 compounds. We determine that there is a morphotropic phase boundary at an yttrium concentration of [Formula: see text], where the structure changes from R3c to Pnma. This structural transition is driven by the chemical pressure induced by the dopant. By analyzing the evolution of the oxygen octahedral tilts we find an enhanced antiferrodistortive distortion when increasing the Y-doping, together with a reduction of the ferroelectric distorsion, that gives rise to a smaller value of the electric polarization. These cooperative effects should lead to a larger canting of the Fe magnetic moments and to a larger ferromagnetic response in the R3c phase, as it is observed in the experiments.

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Two methods, the first physical and the other chemical, were investigated to modify the surface roughness of polydimethylsiloxane (PDMS) films. The physical method consisted of dispersing multi-walled carbon nanotubes (MWCNTs) and magnetic cobalt ferrites (CoFe2O4) prior to thermal cross-linking, and curing the composite system in the presence of a uniform magnetic field H. The chemical method was based on exposing the films to bromine vapours and then UV-irradiating. The characterizing techniques included scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), Fourier transform infrared (FTIR) spectroscopy, optical microscopy, atomic force microscopy (AFM) and magnetic force microscopy (MFM). The surface roughness was quantitatively analyzed by AFM. In the physical method, the random dispersion of MWCNTs (1% w/w) and magnetic nanoparticles (2% w/w) generated a roughness increase of about 200% (with respect to PDMS films without any treatment), but that change was 400% for films cured in the presence of H perpendicular to the surface. SEM, AFM and MFM showed that the magnetic particles always remained attached to the carbon nanotubes, and the effect on the roughness was interpreted as being due to a rupture of dispersion randomness and a possible induction of structuring in the direction of H. In the chemical method, the increase in roughness was even greater (1000%). Wells were generated with surface areas that were close to 100 µm² and depths of up to 500 nm. The observations of AFM images and FTIR spectra were in agreement with the hypothesis of etching by Br radicals generated by UV on the polymer chains. Both methods induced important changes in the surface roughness (the chemical method generated the greatest changes due to the formation of surface wells), which are of great importance in superficial technological processes.

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A constitutive model for the anisotropic magnetoresistivity in structured elastomer composites (SECs) is proposed. The SECs considered here are oriented pseudo-chains of conductive-magnetic inorganic materials inside an elastomer organic matrix. The pseudo-chains are formed by fillers which are simultaneously conductive and magnetic dispersed in the polymer before curing or solvent evaporation. The SEC is then prepared in the presence of a uniform magnetic field, referred to as Hcuring. This procedure generates the pseudo-chains, which are preferentially aligned in the direction of Hcuring. Electrical conduction is present in that direction only. The constitutive model for the magnetoresistance considers the magnetic pressure, Pmag, induced on the pseudo-chains by an external magnetic field, H, applied in the direction of the pseudo-chains. The relative changes in conductivity as a function of H are calculated by evaluating the relative increase of the electron tunnelling probability with Pmag, a magneto-elastic coupling which produces an increase of conductivity with magnetization. The model is used to adjust experimental results of magnetoresistance in a specific SEC where the polymer is polydimethylsiloxane, PDMS, and fillers are microparticles of magnetite-silver (referred to as Fe3O4[Ag]). Simulations of the expected response for other materials in both superparamagnetic and blocked magnetic states are presented, showing the influence of the Young's modulus of the matrix and filler's saturation magnetization.

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Structured elastomeric composites (SECs) with electrically conductive fillers display anisotropic piezoresistivity. The fillers do not form string-of-particle structures but pseudo-chains formed by grouping micro-sized clusters containing nanomagnetic particles surrounded by noble metals (e.g. silver, Ag). The pseudo-chains are formed when curing or preparing the composite in the presence of a uniform magnetic field, thus pseudo-chains are aligned in the direction of the field. The electrical conduction through pseudo-chains is analyzed and a constitutive model for the anisotropic reversible piezoresistivity in SECs is proposed. Several effects and characteristics, such as electron tunnelling, conduction inside the pseudo-chains, and chain-contact resistivity, are included in the model. Experimental results of electrical resistance, R, as a function of the normal stress applied in the direction of the pseudo-chains, P, are very well fitted by the model in the case of Fe3O4[Ag] microparticles magnetically aligned while curing in polydimethylsiloxane, PDMS. The cross sensitivity of different parameters (like the potential barrier and the effective distance for electron tunnelling) is evaluated. The model predicts the presence of several gaps for electron tunnelling inside the pseudo-chains. Estimates of those parameters for the mentioned experimental system under strains up to 20% are presented. Simulations of the expected response for other systems are performed showing the influence of Young's modulus and other parameters on the predicted piezoresistivity.

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Avaliaram-se os efeitos dos tipos de suplementação sobre o desempenho produtivo e o comportamento ingestivo diurno de cordeiros mestiços Santa Inês mantidos em pastagem de capim-aruana (Panicum maximum cv. Aruana) sobressemeado com aveia branca (Avena sativa L.) e azevém (Lolium multiflorum Lam.), em um delineamento inteiramente ao acaso, com três tratamentos e três repetições. Os cordeiros foram distribuídos aleatoriamente em três sistemas alimentares, com seis animais cada, sendo: PAST - cordeiros mantidos exclusivamente a pasto; SIL - cordeiros mantidos em pastagem recebendo suplementação (1,0% do peso vivo) com silagem de milho; CONC - cordeiros mantidos em pastagem recebendo suplementação (1,0% do peso vivo) com concentrado. Os cordeiros suplementados com concentrado apresentaram ganho de peso médio diário 37,5% superior aos mantidos em pastagem, mas não diferiram da suplementação com silagem de milho. O tempo de pastejo foi superior para os animais não suplementados quando comparados aos animais suplementados. Cordeiros mantidos a pasto e suplementados com silagem de milho ou concentrado ganham mais peso do que os cordeiros não suplementados.(AU)

The aim of this work was to evaluate the types of supplementation on performance and the diurnal feeding behavior of crossbred Santa Inês lambs maintained in aruana (Panicum maximum cv. Aruana) pasture grass overseeding with oat (Avena sativaL.) and Italian ryegrass (Lolium multiflorum Lam.) pasture in a completely randomized design with three treatments and three replications. The lambs were randomly assigned to three food systems of six animals each, PAST - lambs fed only pasture; SIL - lambs fed pasture and supplemented (1% of live weight) with corn silage; CONC - lambs fed pasture and supplemented with concentrate. Animals supplemented with concentrate presented average daily gain 37,5% higher, but did not differ from supplementation with corn silage. Grazing time was higher for non-supplemented animals compared with supplemented animals. Lambs maintained in pasture and supplemented with corn silage or concentrate gain more weight than non-supplemented lambs.(AU)

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Avaliaram-se os efeitos dos tipos de suplementação sobre o desempenho produtivo e o comportamento ingestivo diurno de cordeiros mestiços Santa Inês mantidos em pastagem de capim-aruana (Panicum maximum cv. Aruana) sobressemeado com aveia branca (Avena sativa L.) e azevém (Lolium multiflorum Lam.), em um delineamento inteiramente ao acaso, com três tratamentos e três repetições. Os cordeiros foram distribuídos aleatoriamente em três sistemas alimentares, com seis animais cada, sendo: PAST - cordeiros mantidos exclusivamente a pasto; SIL - cordeiros mantidos em pastagem recebendo suplementação (1,0% do peso vivo) com silagem de milho; CONC - cordeiros mantidos em pastagem recebendo suplementação (1,0% do peso vivo) com concentrado. Os cordeiros suplementados com concentrado apresentaram ganho de peso médio diário 37,5% superior aos mantidos em pastagem, mas não diferiram da suplementação com silagem de milho. O tempo de pastejo foi superior para os animais não suplementados quando comparados aos animais suplementados. Cordeiros mantidos a pasto e suplementados com silagem de milho ou concentrado ganham mais peso do que os cordeiros não suplementados.

The aim of this work was to evaluate the types of supplementation on performance and the diurnal feeding behavior of crossbred Santa Inês lambs maintained in aruana (Panicum maximum cv. Aruana) pasture grass overseeding with oat (Avena sativaL.) and Italian ryegrass (Lolium multiflorum Lam.) pasture in a completely randomized design with three treatments and three replications. The lambs were randomly assigned to three food systems of six animals each, PAST - lambs fed only pasture; SIL - lambs fed pasture and supplemented (1% of live weight) with corn silage; CONC - lambs fed pasture and supplemented with concentrate. Animals supplemented with concentrate presented average daily gain 37,5% higher, but did not differ from supplementation with corn silage. Grazing time was higher for non-supplemented animals compared with supplemented animals. Lambs maintained in pasture and supplemented with corn silage or concentrate gain more weight than non-supplemented lambs.

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Magnetorheological elastomers, MREs, based on elastic organic matrices displaying anisotropic magnetoresistance and piezoresistivity at room temperature were prepared and characterized. These materials are dispersions of superparamagnetic magnetite forming cores of aggregated nanoparticles inside silver microparticles that are dispersed in an elastomeric polymer (poly(dimethylsiloxane), PDMS), curing the polymer in the presence of a uniform magnetic field. In this way, the elastic material becomes structured as the application of the field induces the formation of filaments of silver-covered inorganic material agglomerates (needles) aligned in the direction of the field (parallel to the field). Because the magnetic particles are covered with silver, the MREs are not only magnetic but also electrical conductors. The structuration induces elastic, magnetic, and electrical anisotropic properties. For example, with a low concentration of particles in the elastic matrix (5% w/w) it is possible to obtain resistances of a few ohms when measured parallel to the needles or several megaohms in the perpendicular direction. Magnetite nanoparticles (Fe(3)O(4) NP) were synthesized by the coprecipitation method, and then agglomerations of these NPs were covered with Ag. The average size of the obtained magnetite NPs was about 13 nm, and the magnetite-silver particles, referred to as Fe(3)O(4)@Ag, form micrometric aggregates (1.3 µm). Nanoparticles, microparticles, and the MREs were characterized by XRD, TEM, SEM, EDS, diffuse reflectance, voltammetry, VSM, and SQUID. At room temperature, the synthesized magnetite and Fe(3)O(4)@Ag particles are in a superparamagnetic state (T(B) = 205 and 179 K at 0.01 T as determined by SQUID). The elastic properties and Young's modulus of the MREs were measured as a function of the orientation using a texture analysis device. The magnetic anisotropy in the MRE composite was investigated by FMR. The electrical conductivity of the MRE (σ) increases exponentially when a pressure, P, is applied, and the magnitude of the change strongly depends on what direction P is exerted (anisotropic piezoresistivity). In addition, at a fixed pressure, σ increases exponentially in the presence of an external magnetic field (H) only when the field H is applied in the collinear direction with respect to the electrical flux, J. Excellent fits of the experimental data σ versus H and P were achieved using a model that considers the intergrain electron transport where an H-dependent barrier was considered in addition to the intrinsic intergrain resistance in a percolation process. The H-dependent barrier decreases with the applied field, which is attributed to the increasing match of spin-polarization in the silver covers between grains. The effect is anisotropic (i.e., the sensitivity of the magnetoresistive effect is dependent on the relative orientation between H and the current flow J). In the case of Fe(3)O(4)@ Ag, when H and J are parallel to the needles in the PDMS matrix, we obtain changes in σ up to 50% for fields of 400 mT and with resistances on the order of 1-10 Ω. Magnetoresistive and magnetoelastic properties make these materials very interesting for applications in flexible electronics, electronic skins, anisotropic pressure, and magnetic field sensors.

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A specially designed electronic nose was coupled to an air-lift bioreactor in order to perform on-line monitoring of released vapors. The sensor array was placed at the top of the bioreactor sensing the headspace in equilibrium with the evolving liquor at any time without the need of aspiration and pumping of gases into a separated sensor chamber. The device was applied to follow the off-gas of a bioreactor with Acidithiobacillus thiooxidans grown on beds of elemental sulfur under aerobic conditions. Evolution was monitored by acid titration, pH and optical density measurements. The electronic nose was capable to differentiate each day of reactor evolution since inoculation within periods marked off culture medium replacements using multivariate data analysis. Excellent discrimination was obtained indicating the potentiality for on-line monitoring in non-perturbed bioreactors. The prospects for electronic nose/bioreactor merging are valuable for whatever the bacterial strain or consortium used in terms of scent markers to monitor biochemical processes.

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The successful analysis by ultraviolet matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (UV-MALDI-TOF MS) of native and hydrolyzed high-methoxylated pectin samples is described. In order to find the optimal conditions for UV-MALDI-TOF MS analysis several experimental variables were studied such as: different UV-MALDI matrices (nor-harmane, 2,5-dihydroxybenzoic acid), sample preparation methods (mixture, sandwich), inorganic salt addition (doping salts, NaCl, KCl, NH(4)Cl), ion mode (positive, negative), linear and reflectron mode, etc. nor-Harmane has never been used as a UV-MALDI matrix for the analysis of pectins but its use avoids pre-treatment of the sample, such as an enzymatic digestion or an acid hydrolysis, and there is no need to add salts, making the analysis easier and faster. This study suggested an alternative way of analyzing native high-methoxylated pectins, with UV-MALDI-TOF MS, by using nor-harmane as the matrix in negative ion mode. The analysis by (1)H and (13)C nuclear magnetic resonance (NMR) spectroscopy of the native and hydrolyzed pectin is also briefly described.

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Electronic nose methodology was used for discriminating between samples of n-primary alcohols and phenol in water. An electronic nose device developed at our laboratory was applied to detect the vapors from the samples. The device consists of 10 nonspecific gas sensors based on tin-dioxide, whose electrical conductivity change when exposed to the vapors. The whole set of responses constitutes a fingerprint associated with the sample for the particular array of sensors. Using this method, we could differentiate among n-primary alcohols, pure phenol, and aqueous dilutions of phenol. Dilutions of primary alcohols and phenol of 1, 3, 5, and 10% (v/v) were assayed. The fingerprints of the dilutions are similar to that of the respective pure (not diluted) alcohol, but with lower signal intensities. Principal component analysis and cluster analysis were performed in order to explore the feasibility of discriminating among the samples. Dilutions of phenol were successfully discriminated from those of primary alcohols. Discrimination of n-octanol and n-decanol from the other alcohols, including phenol, was also achieved. The results suggest that it is possible to discriminate among dilutions of phenol in water and to give an approximate gross estimation of phenol concentration in water.

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