Production of polyhydroxyalkanoates from oil-containing substrates

Different oil-containing substrates, namely, used cooking oil (UCO), fatty acids-byproduct from biodiesel production (FAB) and olive oil deodorizer distillate (OODD) were tested as inexpensive carbon sources for the production of polyhydroxyalkanoates (PHA) using twelve bacterial strains, in batch experiments. The OODD and FAB were exploited for the first time as alternative substrates for PHA production. Among the tested bacterial strains, Cupriavidus necator and Pseudomonas resinovorans exhibited the most promising results, producing poly-3-hydroxybutyrate, P(3HB), form UCO and OODD and mcl-PHA mainly composed of 3-hydroxyoctanoate (3HO) and 3-hydroxydecanoate (3HD) monomers from OODD, respectively. Afterwards, these bacterial strains were cultivated in bioreactor. C. necator were cultivated in bioreactor using UCO as carbon source. Different feeding strategies were tested for the bioreactor cultivation of C. necator, namely, batch, exponential feeding and DO-stat mode. The highest overall PHA productivity (12.6±0.78 g L-1 day-1) was obtained using DO-stat mode. Apparently, the different feeding regimes had no impact on polymer thermal properties. However, differences in polymer‟s molecular mass distribution were observed. C. necator was also tested in batch and fed-batch modes using a different type of oil-containing substrate, extracted from spent coffee grounds (SCG) by super critical carbon dioxide (sc-CO2). Under fed-batch mode (DO-stat), the overall PHA productivity were 4.7 g L-1 day-1 with a storage yield of 0.77 g g-1. Results showed that SCG can be a bioresource for production of PHA with interesting properties. Furthermore, P. resinovorans was cultivated using OODD as substrate in bioreactor under fed-batch mode (pulse feeding regime). The polymer was highly amorphous, as shown by its low crystallinity of 6±0.2%, with low melting and glass transition temperatures of 36±1.2 and -16±0.8 ºC, respectively. Due to its sticky behavior at room temperature, adhesiveness and mechanical properties were also studied. Its shear bond strength for wood (67±9.4 kPa) and glass (65±7.3 kPa) suggests it may be used for the development of biobased glues. Bioreactor operation and monitoring with oil-containing substrates is very challenging, since this substrate is water immiscible. Thus, near-infrared spectroscopy (NIR) was implemented for online monitoring of the C. necator cultivation with UCO, using a transflectance probe. Partial least squares (PLS) regression was applied to relate NIR spectra with biomass, UCO and PHA concentrations in the broth. The NIR predictions were compared with values obtained by offline reference methods. Prediction errors to these parameters were 1.18 g L-1, 2.37 g L-1 and 1.58 g L-1 for biomass, UCO and PHA, respectively, which indicates the suitability of the NIR spectroscopy method for online monitoring and as a method to assist bioreactor control. UCO and OODD are low cost substrates with potential to be used in PHA batch and fed-batch production. The use of NIR in this bioprocess also opened an opportunity for optimization and control of PHA production process.

Producers’ motivation for collective action for kola production and marketing in Cameroon

Collective action has been used as a strategy to improve the benefits of smallholder producers of kola nuts in Cameroon. Despite demonstrated benefits, not all producers are involved in the collective action. The presented study used a modified Technology Acceptance Model (TAM) namely the Collective Action Behaviour model (CAB model) to analyse kola producers’ motivation for collective action activities. Five hypotheses are formulated and tested using data obtained from 185 farmers who are involved in kola production and marketing in theWestern highlands of Cameroon. Results which were generated using Partial Least Squares (PLS) approach for Structural Equation Modelling (SEM) showed that farmers’ intrinsic motivators and ease of use influenced their behavioural intent to join a group marketing activities. The perceived usefulness that was mainly related to the economic benefits of group activities did not influence farmers’ behavioural intent. It is therefore concluded that extension messages and promotional activities targeting collective action need to emphasise the perceived ease of use of involvement and social benefits associated with group activities in order to increase farmers’ participation.

The relationship between diffuse spectral reflectance of the soil and its cation exchange capacity is scale-dependent

Diffuse reflectance spectroscopy (DRS) is increasingly being used to predict numerous soil physical, chemical and biochemical properties. However, soil properties and processes vary at different scales and, as a result, relationships between soil properties often depend on scale. In this paper we report on how the relationship between one such property, cation exchange capacity (CEC), and the DRS of the soil depends on spatial scale. We show this by means of a nested analysis of covariance of soils sampled on a balanced nested design in a 16 km × 16 km area in eastern England. We used principal components analysis on the DRS to obtain a reduced number of variables while retaining key variation. The first principal component accounted for 99.8% of the total variance, the second for 0.14%. Nested analysis of the variation in the CEC and the two principal components showed that the substantial variance components are at the > 2000-m scale. This is probably the result of differences in soil composition due to parent material. We then developed a model to predict CEC from the DRS and used partial least squares (PLS) regression do to so. Leave-one-out cross-validation results suggested a reasonable predictive capability (R2 = 0.71 and RMSE = 0.048 molc kg− 1). However, the results from the independent validation were not as good, with R2 = 0.27, RMSE = 0.056 molc kg− 1 and an overall correlation of 0.52. This would indicate that DRS may not be useful for predictions of CEC. When we applied the analysis of covariance between predicted and observed we found significant scale-dependent correlations at scales of 50 and 500 m (0.82 and 0.73 respectively). DRS measurements can therefore be useful to predict CEC if predictions are required, for example, at the field scale (50 m). This study illustrates that the relationship between DRS and soil properties is scale-dependent and that this scale dependency has important consequences for prediction of soil properties from DRS data

Relationships between gluten rheological properties and hearth loaf characteristics

The rheological properties of fresh gluten in small amplitude oscillation in shear (SAOS) and creep recovery after short application of stress was related to the hearth breadbaking performance of wheat flours using the multivariate statistics partial least squares (PLS) regression. The picture was completed by dough mixing and extensional properties, flour protein size distribution determined by SE-HPLC, and high molecular weight glutenin subunit (HMW-GS) composition. The sample set comprised 20 wheat cultivars grown at two different levels of nitrogen fertilizer in one location. Flours yielding stiffer and more elastic glutens, with higher elastic and viscous moduli (G' and G") and lower tan 8 values in SAOS, gave doughs that were better able to retain their shape during proving and baking, resulting in breads of high form ratios. Creep recovery measurements after short application of stress showed that glutens from flours of good breadmaking quality had high relative elastic recovery. The nitrogen fertilizer level affected the protein size distribution by an increase in monomeric proteins (gliadins), which gave glutens of higher tan delta and flatter bread loaves (lower form ratio).

Dielectric properties of process cheese from 0.3 to 3 Ghz

Dielectric properties of 16 process cheeses were determined over the frequency range 0.3-3 GHz. The effect of temperature on the dielectric properties of process cheeses were investigated at temperature intervals of 10 degrees C between 5 and 85 degrees C. Results showed that the dielectric constant decreased gradually as frequency increased, for all cheeses. The dielectric loss factor (epsilon") decreased from above 125 to below 12 as frequency increased. epsilon' was highest at 5 degrees C and generally decreased up to a temperature between 55 and 75 degrees C. epsilon" generally increased with increasing temperature for high and medium moisture/fat ratio cheeses. epsilon" decreased with temperature between 5 and 55 degrees C and then increased, for low moisture/fat ratio cheese. Partial least square regression models indicated that epsilon' and epsilon" could be used as a quality control screening application to measure moisture content and inorganic salt content of process cheese, respectively. (c) 2005 Elsevier Ltd. All rights reserved..

Effect of blending Jersey and Holstein-Friesian milk on Cheddar cheese processing, composition and quality

The aim of this study was to investigate the effects of numerous milk compositional factors on milk coagulation properties using Partial Least Squares (PLS). Milk from herds of Jersey and Holstein- Friesian cattle was collected across the year and blended (n=55), to maximise variation in composition and coagulation. The milk was analysed for casein, protein, fat, titratable acidity, lactose, Ca2+, urea content, micelles size, fat globule size, somatic cell count and pH. Milk coagulation properties were defined as coagulation time, curd firmness and curd firmness rate measured by a controlled strain rheometer. The models derived from PLS had higher predictive power than previous models demonstrating the value of measuring more milk components. In addition to the well-established relationships with casein and protein levels, CMS and fat globule size were found to have as strong impact on all of the three models. The study also found a positive impact of fat on milk coagulation properties and a strong relationship between lactose and curd firmness, and urea and curd firmness rate, all of which warrant further investigation due to current lack of knowledge of the underlying mechanism. These findings demonstrate the importance of using a wider range of milk compositional variables for the prediction of the milk coagulation properties, and hence as indicators of milk suitability for cheese making.

A quantum chemical study on a set of non-imidazole H(3) antihistamine molecules

Molecular orbital calculations were carried out on a set of 28 non-imidazole H(3) antihistamine compounds using the Hartree-Fock method in order to investigate the possible relationships between electronic structural properties and binding affinity for H3 receptors (pK(i)). It was observed that the frontier effective-for-reaction molecular orbital (FERMO) energies were better correlated with pK(i) values than highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy values. Exploratory data analysis through hierarchical cluster (HCA) and principal component analysis (PCA) showed a separation of the compounds in two sets, one grouping the molecules with high pK(i) values, the other gathering low pK(i) value compounds. This separation was obtained with the use of the following descriptors: FERMO energies (epsilon(FERMO)), charges derived from the electrostatic potential on the nitrogen atom (N(1)), electronic density indexes for FERMO on the N(1) atom (Sigma((FERMO))c(i)(2)). and electrophilicity (omega`). These electronic descriptors were used to construct a quantitative structure-activity relationship (QSAR) model through the partial least-squares (PLS) method with three principal components. This model generated Q(2) = 0.88 and R(2) = 0.927 values obtained from a training set and external validation of 23 and 5 molecules, respectively. After the analysis of the PLS regression equation and the values for the selected electronic descriptors, it is suggested that high values of FERMO energies and of Sigma((FERMO))c(i)(2), together with low values of electrophilicity and pronounced negative charges on N(1) appear as desirable properties for the conception of new molecules which might have high binding affinity. 2010 Elsevier Inc. All rights reserved.

Viagem ao centro da denúncia: explorando as “camadas” que influenciam as denúncias de fraudes nas organizações

As fraudes contábeis representam uma grande perda para a economia global tanto na esfera pública quanto privada, destacando, assim, os prejuízos sociais ocasionados por elas. Nesta perspectiva, diversas pesquisas têm demonstrado que as denúncias são um dos principais mecanismos de detecção de fraudes nas organizações. Inspirado em Taylor e Curtis (2010), o presente trabalho tem como objetivo identificar a influência das “camadas” pessoal, organizacional, profissional na intenção individual em denunciar uma situação fraudulenta que o mesmo tenha conhecimento. Ressalta-se, porém, a inclusão de uma “camada social”, bem como a consideração de aspectos peculiares da cultura brasileira na elaboração e análise das hipóteses. Para operacionalização das camadas foram utilizadas variáveis latentes coletadas por meio de um questionário respondido por 124 contabilistas. Para mensuração da influência na intenção em denunciar foi utilizado um Modelo de Equação Estrutural (SEM) estimado pelo método dos Mínimos Quadrados Parciais (PLS). Os resultados obtidos confirmaram a importância das camadas de influência no comportamento do eventual denunciante. Destaca-se, principalmente, a importância da camada social, a qual, além de influenciar diretamente de forma significativa a Intenção de Denunciar, também media o impacto da camada profissional. A camada organizacional não afeta de forma significante a intenção de denunciar. Nota-se, também o grande impacto causado pela camada pessoal. Tais fatos corroboram alguns dos principais traços da cultura brasileira, como a prevalência de relações informais e pessoais em detrimento de relações formais, além de identificar os traços da ambiguidade moral.

Franchisor-franchisee relationship and performance: influence of personality traits, entrepreneurial drive, and time of relationship

A literatura em franchising tem virtualmente ignorado o papel de aspectos psicologicos nos resultados interorganizacionais das empresas, a despeito de sua influencia nos resultados das organizações e da qualidade de relacionamento. Este estudo, portanto, tem por objetivo analisar a influência da personalidade e do potencial empreendedor na qualidade de relacionamento e desempenho financeiro na relação franqueador-franqueado, ao longo do tempo, sob a perspectiva dos franqueados. Este estudo analisa também o papel do tempo de relacionamento sobre a qualidade de relacionamento e o desempenho financeiro. Foi utilizado neste estudo um questionário de auto-preenchimento, enviado por e-mail, com o objetivo de recolher dados de uma amostra de 342 franqueados de 3 redes de franquias. A personalidade foi mensurada por meio dos “Cinco Grandes” traços de personalidade (escalas IPIP-B5): extroversão, agradabilidade, consciencia, estabilidade emocional e imaginação. O potencial empreendedor foi mensurado por meio do índice CEI (Carland Entrepreneurship Index). A qualidade do relacionamento foi estruturada como um constructo de segunda ordem, composto por 23 itens (incorporando confiança, comprometimento e satisfação com o relacionamento), e o desempenho financeiro foi representado por meio de uma escala de mensuração de crescimento de vendas e de rentabilidade. O tempo de relacionamento foi medido por meio dos meses de relacionamento entre franqueado e franqueador. As hipoteses foram testadas por meio de modelagem por equações estruturais, com a utilização do método de mínimos quadrados parciais (PLS), análise de regressão e análise de médias. Três das cinco dimensões da personalidade apresentaram o efeito previsto sobre as variáveis qualidade do relacionamento – agradabilidade (positivamente), estabilidade emocional (positivamente), e imaginação (positivamente). O desempenho financeiro foi influenciado, como previsto por consciência (positivamente), estabilidade emocional (positivamente), e imaginação (positivamente). Como esperado, a qualidade do relacionamento apresentou efeito positivo e significativo em relação ao desempenho financeiro. O potencial empreendedor apresentou o efeito positivo previsto apenas sobre desempenho. O tempo de relacionamento teve o efeito positivo esperado sobre o relacionamento franqueador-franqueado, em relação à qualidade do relacionamento e o desempenho financeiro, mas as diferenças entre as fases de relacionamento propostas foram apenas parcialmente confirmadas, uma vez que em somente duas fases (rotina e estabilização) a análise de médias mostrou diferenças significativas. Os resultados indicam que a personalidade influencia a qualidade de relacionamento e o desempenho, mas a meneira pela qual isso ocorre é diferente no contexto brasileiro, onde esta pesquisa foi realizada, dos achados da pesquisa conduzida na Austrália, sugerindo que fatores como cultura e estabilidade de mercado podem ter influencia sobre a relação entre traços de personalidade e qualidade de relacionamento, e traços de personalidade e desempenho financeiro. O potencial empreendedor parece influenciar positivamente o desempenho do franqueado, mas a sua influência não foi significativa em relação à qualidade do relacionamento. Os resultados também indicam a importância do tempo no desenvolvimento da qualidade de relacionamento e desempenho. Além disso, os relacionamentos de longo prazo estão relacionados a melhores avaliações de qualidade de relacionamento e desempenho financeiros por parte dos franqueados. As limitações do trabalho e sugestões para estudos futuros também são discutidos.

Effectuation e causation: um estudo sobre o processo decisório empreendedor em redes de micros e pequenos supermercados

Este estudo analisa a contribuição da centralidade em redes de negócios, na elevação da complexidade da estrutura organizacional de supermercados e os possíveis efeitos dessa mudança no processo decisório empreendedor. Causation e Effectuation são processos decisórios distintos que possuem sua hora adequada de utilização. Porém, faltam estudos sobre quando os empreendedores utilizam tais processos em ambientes de redes interorganizacionais. Para preencher esse gap, a pesquisa centra-se na tipologia de rede de cooperação associativa (BALESTRIN; VARGAS, 2004; BALESTRIN; VERSCHOORE, 2008). O referencial teórico foi construído a partir dos conceitos de centralidade (FREEMAN, 1979; WASSERMAN; FAUST, 1994), laços relacionais (BURT, 1992; GRANOVETTER, 1973), complexidade da estrutura organizacional (HALL, 2004), e dos processos decisórios de Causation e Effectuation (SARASVATHY, 2001a). Inicialmente, os dados foram coletados de forma indutiva em seis casos de micros e pequenos supermercados em redes de negócios no estado do Ceará. Após analisar o conteúdo de cada caso, o pesquisador procedeu uma Análise Qualitativa Comparativa (Qualitative Comparative Analysis – QCA). As condições necessárias à adoção dos processos decisórios foram: a) a centralidade contribui para elevar a complexidade da estrutura organizacional e/ou adoção de mecanismos de controle gerencial, quando as relações são conduzidas mais por laços sociais do que por laços estratégicos; b) empreendedores adotam Effectuation e Causation independentemente da complexidade da estrutura organizacional dos supermercados. Um novo achado foi que, além dos empreendedores novatos, os experientes também variam o uso de Effectuation e Causation no início dos novos empreendimentos. Mas ao longo do tempo, ao implementarem mecanismos de controle gerencial, eles tendem a reduzir a utilização de algumas práticas efetuais, como as capacidades de experimentar e aceitar riscos e perdas. Dados complementares foram coletados e testes foram realizados por meio de Modelagem de Equações Estruturais (MEE) baseada em partial least squares (PLS). Os resultados confirmaram que: c) os laços sociais exercem mais influência que os estratégicos, na transformação da estrutura organizacional dos supermercados; d) essa transformação influencia positivamente na implantação de mecanismos de controle gerencial; e) supermercados com mecanismos de controle gerencial terão empreendedores mais propensos a adotarem o processo de Causation, e menos propensos a experimentar e aceitar riscos e perdas. Os resultados contribuem para entender quando as relações geradas em redes de cooperação, afetam a fundação e o crescimento de pequenas empresas, e onde ocorre a evolução do comportamento decisório empreendedor no tempo. De forma prática, a pesquisa demonstra aos micros e pequenos empreendedores que eles não precisam gerar muitas relações para desenvolverem seus negócios, ou seja, a posição relativa do supermercado na rede não é importante, desde que os laços sociais estejam ativos e haja engajamento nas atividades das associações. Também ensina que os empreendedores tendem a desenvolver o raciocínio causal em redes de negócios.

Construção de modelos multivariados para determinação de lipídios totais e unidade em leite em pó comercial utilizando espectroscopia no infravermelho próximo

In this work calibration models were constructed to determine the content of total lipids and moisture in powdered milk samples. For this, used the near-infrared spectroscopy by diffuse reflectance, combined with multivariate calibration. Initially, the spectral data were submitted to correction of multiplicative light scattering (MSC) and Savitzsky-Golay smoothing. Then, the samples were divided into subgroups by application of hierarchical clustering analysis of the classes (HCA) and Ward Linkage criterion. Thus, it became possible to build regression models by partial least squares (PLS) that allowed the calibration and prediction of the content total lipid and moisture, based on the values obtained by the reference methods of Soxhlet and 105 ° C, respectively . Therefore, conclude that the NIR had a good performance for the quantification of samples of powdered milk, mainly by minimizing the analysis time, not destruction of the samples and not waste. Prediction models for determination of total lipids correlated (R) of 0.9955, RMSEP of 0.8952, therefore the average error between the Soxhlet and NIR was ± 0.70%, while the model prediction to content moisture correlated (R) of 0.9184, RMSEP, 0.3778 and error of ± 0.76%

Uso da espectroscopia do infravermelho próximo e técnicas multivariadas para diferenciar escherichia coli e salmonella enteritidis inoculadas em polpa de fruta (abacaxi)

Aiming to consumer s safety the presence of pathogenic contaminants in foods must be monitored because they are responsible for foodborne outbreaks that depending on the level of contamination can ultimately cause the death of those who consume them. In industry is necessary that this identification be fast and profitable. This study shows the utility and application of near-infrared (NIR) transflectance spectroscopy as an alternative method for the identification and classification of Escherichia coli and Salmonella Enteritidis in commercial fruit pulp (pineapple). Principal Component Analysis (PCA), Independent Modeling of Class Analogy (SIMCA) and Discriminant Analysis Partial Least Squares (PLS-DA) were used in the analysis. It was not possible to obtain total separation between samples using PCA and SIMCA. The PLS-DA showed good performance in prediction capacity reaching 87.5% for E. coli and 88.3% for S. Enteritides, respectively. The best models were obtained for the PLS-DA with second derivative spectra treated with a sensitivity and specificity of 0.87 and 0.83, respectively. These results suggest that the NIR spectroscopy and PLS-DA can be used to discriminate and detect bacteria in the fruit pulp

Multivariate quality control studies applied to Ca(II) and Mg(II) determination by a portable method

A portable or field test method for simultaneous spectrophotometric determination of calcium and magnesium in water using multivariate partial least squares (PLS) calibration methods is proposed. The method is based on the reaction between the analytes and methylthymol blue at pH 11. The spectral information was used as the X-block, and the Ca(II) and Mg(II) concentrations obtained by a reference technique (ICP-AES) were used as the Y-block. Two series of analyses were performed, with a month's difference between them. The first series was used as the calibration set and the second one as the validation set. Multivariate statistical process control (MSPC) techniques, based on statistics from principal component models, were used to study the features and evolution with time of the spectral signals. Signal standardization was used to correct the deviations between series. Method validation was performed by comparing the predictions of the PLS model with the reference Ca(II) and Mg(II) concentrations determined by ICP-AES using the joint interval test for the slope and intercept of the regression line with errors in both axes. (C) 1998 John Wiley & Sons, Ltd.

Escherichia coli phylogenetic group determination and its application in the identification of the major animal source of fecal contamination

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Analyzing the effect of homogeneous frustration in protein folding

The energy landscape theory has been an invaluable theoretical framework in the understanding of biological processes such as protein folding, oligomerization, and functional transitions. According to the theory, the energy landscape of protein folding is funneled toward the native state, a conformational state that is consistent with the principle of minimal frustration. It has been accepted that real proteins are selected through natural evolution, satisfying the minimum frustration criterion. However, there is evidence that a low degree of frustration accelerates folding. We examined the interplay between topological and energetic protein frustration. We employed a Cα structure-based model for simulations with a controlled nonspecific energetic frustration added to the potential energy function. Thermodynamics and kinetics of a group of 19 proteins are completely characterized as a function of increasing level of energetic frustration. We observed two well-separated groups of proteins: one group where a little frustration enhances folding rates to an optimal value and another where any energetic frustration slows down folding. Protein energetic frustration regimes and their mechanisms are explained by the role of non-native contact interactions in different folding scenarios. These findings strongly correlate with the protein free-energy folding barrier and the absolute contact order parameters. These computational results are corroborated by principal component analysis and partial least square techniques. One simple theoretical model is proposed as a useful tool for experimentalists to predict the limits of improvements in real proteins. © 2013 Wiley Periodicals, Inc.