Editorial Prof. Dr. Martín Aznar O destaque desta edição, além da justíssima homenagem aos agraciados com o Prêmio de Reconhecimento Acadêmico Zeferino Vaz e com o Prêmio de Reconhecimento Docente pela Dedicação ao Ensino de Graduação, professores Everson Alves Miranda e Maria Alvina Krähenbühl, respectivamente (veja quadro na página 2), é a inauguração do Laboratório de Caracterização de Biomassa, um espaço de 1300 m2, financiado pela Shell Brasil Petróleo, a um custo superior aos 7 milhões de reais. O projeto, idealizado e conduzido pela Profa. Dra. Maria Aparecida Silva, do Departamento de Engenharia de Processos (DEPro), é, nas palavras do Magnífico Reitor, Prof. Dr. José Tadeu Jorge, um exemplo importante dos frutos que a aproximação da universidade com a sociedade pode proporcionar. Na seção “Notas Curtas” reproduzimos uma reportagem do Jornal da UNICAMP sobre a inauguração do laboratório. Em uma reflexão, neste momento em que se cumprem sete anos da existência do Boletim da FEQ, constatamos com prazer que o nosso jornalzinho se consolidou, como era um dos seus objetivos iniciais, como um indicador e um registro, principalmente das atividades de pesquisa e de pós-graduação. Por outro lado, não conseguiu se constituir em um foro de discussão para o debate de questões tanto fundamentais como do nosso dia-a-dia, que era outro dos seus objetivos iniciais. Por isso fica registrado aqui o convite aos docentes, alunos e funcionários da FEQ para que contribuam com o nosso Boletim, na forma de matérias assinadas que expressem opiniões e ideias para o processo de constante evolução da nossa faculdade.

N E S T E N Ú M E R O 1 Editorial

2 Prêmios 2013

3 Artigos publicados em Outubro - Dezembro 2013

11 Teses e dissertações

13 Notas curtas

15 de janeiro de 2014 Ano 8 Número 28

Uma publicação da Faculdade de Engenharia Química da UNICAMP Av. Albert Einstein 500, Campinas-SP, 13083-852 Editor: Prof. Dr. Martín Aznar, maznar@feq.unicamp.br, fone 3521-3962

Boletim da FEQ

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Prêmios 2013

Prêmio Zeferino Vaz O Prof. Dr. Everson Alves Miranda, professor titular do Departamento de Engenharia de Materiais e Bioprocessos (DEMBio), foi agraciado com o Prêmio de Reconhecimento Acadêmico Zeferino Vaz, edição 2013. O prêmio é concedido anualmente aos docentes ativos de cada unidade que mostraram desempenho excepcional nas atividades de docência e pesquisa. O professor Everson possui graduação em Engenharia Química pela Escola de Engenharia da UFMG (1982). Concluiu mestrado em Engenharia Agrícola (1988) e doutorado em Engenharia Química na Michigan State University, USA (1992). Realizou pós-doutoramento na École Superieur de Biotechnologie de Strasbourg, Université Louis Pasteur, França (1993).

Tem experiência em bioprocessos, atuando principalmente na recuperação e purificação de bioprodutos (RPB), também conhecida como biosseparação ou "downstream processing". Desenvolve pesquisas sobre as operações de precipitação e cristalização de proteínas e processos de RPB relacionados à biorrefinaria, tais como recuperação primária de enzimas hidrolíticas em caldos fermentados, reciclo de enzimas após a etapa de hidrólise e produção de óleo em leveduras não-convencionais ("single cell oil"), colaborando com o Laboratório Nacional de Ciência e Tecnologia do Bioetanol – CTBE.

Prêmio de Reconhecimento à Graduação A Profa. Dra. Maria Alvina Krähenbühl, professora titular do Departamento de Desenvolvimento de Processos e Productos (DDPP), foi agraciada com o Prêmio de Reconhecimento Docente pela Dedicação ao Ensino de Graduação, edição 2013. O prêmio destina-se ao reconhecimento e valorização das atividades docentes da graduação. Os critérios básicos utilizados para a premiação incluem: atividade didática total na graduação, orientação de iniciação científica, desempenho na avaliação feita pelo corpo discente, responsabilidade por disciplinas e implantação de novas disciplinas. São critérios complementares a publicação de artigos sobre ensino da graduação e a orientação de alunos em monitoria PAD e PED.

A professora Maria Alvina possui graduação em Engenharia Química pela UNICAMP (1982), mestrado em Engenharia Química pela UNICAMP (1987) e doutorado em Engenharia Química pela Universität Carl Von Ossietzky Oldenburg, Alemanha (1994). Tem experiência em termodinâmica aplicada à engenharia química, com ênfase em processos orgânicos, atuando principalmente em equilíbrio líquido-vapor, líquido-líquido e sólido-líquido, com determinação de dados experimentais e modelagem termodinâmica de equilíbrio de fases.

Parabéns aos professores Everson e Maria Alvina!

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Artigos Publicados em Revistas Indexadas Outubro - Dezembro 2013

Bases de dados: ISI Web of Knowledge, Sci Finder Scholar, Compendex, SciELO, Scopus, Scirus.

Outubro Behavior of human immunoglobulin G adsorption onto immobilized Cu(II) affinity hollow-fiber membranes Borsoi-Ribeiro, M.; Bresolin, I.T.L.; Vijayalakshmi, M.; Bueno, S.M.A. Journal of Molecular Recognition, 26 (2013), 514-520. ISSN: 1099-1352. FI = 3.006. doi:10.1002/jmr.2296 Iminodiacetic acid (IDA) and tris(2-aminoethyl)amine (TREN) chelating ligands were immobilized on poly(ethylene vinyl alcohol) (PEVA) hollow-fiber membranes after activation with epichlorohydrin or butanediol diglycidyl ether (bisoxirane). The affinity membranes complexed with Cu(II) were evaluated for adsorption of human immunoglobulin G (IgG). The effects of matrix activation and buffer system on adsorption of IgG were studied. Isotherms of batch IgG adsorption onto finely cut membranes showed that neither of the chelates, IDA-Cu(II) or TREN-Cu(II), had a Langmuirean behavior with negative cooperativity for IgG binding. A comparison of equilibrium and dynamic maximum capacities showed that the dynamic capacity for a mini-cartridge in a cross-flow filtration mode (52.5 and 298.4 mg g−1 dry weight for PEVA-TREN-Cu(II) and PEVA-IDA-Cu(II), respectively) was somewhat higher than the equilibrium capacity (9.2 and 73.3 mg g−1 dry weight for PEVA-TREN-Cu(II) and PEVA-IDA-Cu(II), respectively). When mini-cartridges were used, the dynamic adsorption capacity of IDA-Cu(II) was the same for both mini-cartridge and agarose gel. Thermo-economic optimization of integrated first and second generation sugarcane ethanol plant Ensinas, A.V.; Codina, V.; Marechal, F.; Albarelli, J.; Silva, M.A. Chemical Engineering Transactions, 35 (2013), 525-538. ISSN: 1974-9791. Qualis B5. doi:10.3303/CET1335087 The sugarcane industry has been responsible in some countries for the production of most of the sugar and ethanol available in the world for internal and external markets. In this sector, ethanol can be produced by fermentation of sugars obtained directly from sugarcane biomass, commonly called 1st generation ethanol. New processes using the enzymatic hydrolysis technology of lignocellulosic residues like bagasse and sugarcane leaves as feedstock can increase the ethanol production in these plants, reducing the land requirements and the environmental of impact biofuels production in large scale. The lignocellulosic ethanol production using enzymatic hydrolysis technology is one of the most promising alternatives of 2nd generation biofuels, due to its high conversion efficiencies and low environment impact. Some problems like high water consumption and enzymes costs must be overcome in order to reach commercial scale. The process integration and thermo-economic optimization of the process can be important for the design of this process in a sugarcane autonomous distillery aiming at the cost and environmental impact reduction. In this paper a process integration of the sugarcane ethanol distillery model is carried out taking into account 1st and 2nd generation processes in the same site using sugars and bagasse as feedstock respectively. Conflictive objectives such as maximization of the electricity or ethanol production are adopted in a multi-objective optimization technique using evolutionary algorithms, in order to provide a set of candidate solutions considering different configurations of the ethanol production process design. Extended application of radon as a natural tracer in oil reservoirs Pinto, A.M.F.; Barreto, A.A.; Moreira, R.M.; Tambourgi, E.B. EPJ Web of Conferences, 50 (2013), 02003. ISSN: 2100-014X. doi:10.1051/epjconf/20135002003 In the 80's it was a common practice in the study of contamination by NAPL to incorporate a tracer to the medium to be studied. At that time the first applications focused on the use of 222Rn, a naturally occurring radioactive isotope as a natural tracer, appropriate for thermodynamics studies, geology and transport properties in thermal reservoirs. In 1993 the deficit of radon was used to spot and quantify the contamination by DNAPL under the surface. For the first time these studies showed that radon could be used as a partitioning tracer. A methodology that provides alternatives to quantify the oil volume stored

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in the porous space of oil reservoirs is under development at CDTN. The methodology here applied, widens up and adapts the knowledge acquired from the use of radon as a tracer to the studies aimed at assessing SOR. It is a postulation of this work that once the radon partition coefficient between oil and water is known, SOR will be determined considering the increased amount of radon in the water phase as compared to the amount initially existent as the reservoir is flooded with water. This paper will present a description of the apparatus used and some preliminary results of the experiments. Adsorption of carotenes and phosphorus from palm oil onto acid activated bleaching earth: equilibrium, kinetics and thermodynamics Silva, S.M.; Sampaio, K.A.; Ceriani, R.; Verhé, R.; Stevens, C.; De Greyt, W.; Meirelles, A.J.A. Journal of Food Engineering, 118 (2013), 341-349. ISSN: 0260-8774. FI = 2.414. Qualis A1. doi:10.1016/j.jfoodeng.2013.04.026 In this work, the adsorption of carotenes and phosphorus from crude palm oil onto acid activated bleaching earth was investigated under bleaching conditions, i.e. high temperature (90, 105 and 115 C) and low pressure (less than 50 mbar). Bleaching earth was added to palm oil in a range of 0.5-3.0 wt%. Results presented in this work suggest that adsorption of β-carotene increases with temperature, while phosphorus adsorption was less affected. Both the pseudo-first-order and the pseudo-second-order kinetic model describe efficiently the β-carotene experimental data. Intra-particle diffusion is involved in β-carotene adsorption mechanism, although it is not the sole rate limiting step in the adsorption onto acid activated bleaching earth. Phosphorus adsorption was too fast resulting in a lack of kinetic data. The equilibrium data were described better by Langmuir and Freundlich models, for β-carotene and phosphorus, respectively. A multi-component Freundlich type isotherm was tested. Its competition coefficients were too low, and it assumed the same form as the monocomponent Freundlich. A thermodynamic study demonstrated that β-carotene and phosphorus adsorption is spontaneous, endothermic and an entropy-driven process. Isosteric heat values suggest that the interactions between adsorbate and adsorbent are heterogeneous.

Novembro Microfluidic devices for continuous production of pDNA/cationic liposome complexes for gene delivery and vaccine therapy Balbino, T.A.; Azzoni, A.R.; De la Torre, L.G. Colloids and Surfaces B: Biointerfaces, 111 (2013), 203-210. ISSN: 0927-7765. FI = 3.456. Qualis A1. doi:10.1016/j.colsurfb.2013.04.003 To evaluate the process parameters for the production of plasmid DNA/cationic liposome (pDNA/CL) complexes in microfluidic systems, we studied two microfluidic devices: one with simple straight hydrodynamic flow focusing (SMD) and a second one with barriers in the mixing microchannel (patterned walls, PMD). A conventional bulk mixing method was used as a comparison to microfluidic mixing. The CL and the pDNA were combined at a molar positive/negative charge ratio of 6. The results showed that incorporating pDNA into the liposomal structures was different for the two microfluidic devices and that the temperature influenced the average size of complexes produced by the simple microfluidic device, while it did not influence the average complex size in the patterned wall device. Differences were also observed in pDNA probe accessibility in the complexes. The SMD yielded a similar quantity of non-electrostatic bound pDNA as that provided by the bulk mixing method. The complexes produced by the PMD had their pDNA probe accessibility decreased in 40% and achieved lower in vitro transfection levels in HeLa cells than the bulk mixing and simple microfluidic complexation methods. These differences are most likely due to different degrees of association between pDNA and CL, as controlled by the microfluidic devices. This study contributes to the development of rational strategies for controlling the formation of pDNA/CL complexes for further applications in gene and vaccine therapy. Drying of milk–blackberry pulp mixture in spouted bed Braga, M.B.; Rocha, S.C.S. The Canadian Journal of Chemical Engineering, 91 (2013), 1786-1792. ISSN: 1939-019X. FI = 1.003. Qualis A2. doi:10.1002/cjce.21918 Spouted bed drying of a paste mixture of milk and blackberry pulp using inert beads of polystyrene and polypropylene was analysed in this work. Atomisation and dripping of the paste were compared as feeding modes. The experimental design used atomisation feeding to analyse the effects of air temperature, paste feeding flow rate and paste atomisation pressure on the drying performance. The best results were

Boletim da FEQ Página 5obtained for drip feeding on polystyrene beads, yielding powder production efficiency >60%, low final moisture content of the powder and <15% anthocyanin degradation. Molecular structure-based methods of property prediction in application to lipids: a review and refinement Cunico, L.P.; Hukkerikar, A.S.; Ceriani, R.; Sarup, B.; Gani, R. Fluid Phase Equilibria, 357 (2013), 2-18. ISSN: 0378-3812. FI = 2.139. Qualis A1. doi:10.1016/j.fluid.2013.04.004 The paper is a review of the combined group contribution (GC) – atom connectivity index (CI) approach for prediction of physical and thermodynamic properties of organic chemicals and their mixtures with special emphasis on lipids. The combined approach employs carefully selected datasets of different pure component properties to develop simultaneously two parallel models, one based on group contribution and another based on atom connectivity, for each property. The lipids present in the database are regarded as a separate class, for which special models for pure component properties, primary and temperature dependent, have been developed. For mixtures, properties related to phase equilibria are modeled with GE-based models (UNIQUAC, UNIFAC, NRTL, and combined UNIFAC-CI method). The collected phase equilibrium data for VLE and SLE have been tested for thermodynamic consistency together with a performance evaluation of the GE- models. The paper also reviews the role of the databases and the mathematical and thermodynamic consistency of the measured/estimated data and the predictive nature of the developed models. Blood protein adsorption on sulfonated chitosan and κ-carrageenan films Lima, P.H.L.; Pereira, S.V.A.; Rabello, R.B.; Rodríguez-Castellón, E.; Beppu, M.M.; Chevallier, P.; Mantovani, D.; Vieira, R.S. Colloids and Surfaces B: Biointerfaces, 111 (2013), 719-725. ISSN: 0927-7765. FI = 3.554. Qualis A1. doi:10.1016/j.colsurfb.2013.06.002 Many strategies have been reported to improve compatibility of biopolymers using chemical and physical modifications. One possibility is the introduction of sulfonate groups (R-SO3−) in the chitosan chain. Another biopolymer with similar characteristics to those of heparin is κ-carrageenan. This study proposed to investigate the application of these two polymers, based on their potential for globular protein adsorption (BSA and fibrinogen). Polymeric films of chitosan and κ-carrageenan were prepared; all films were characterized by elemental analyses, FTIR, XPS and SEM. Characterization techniques showed that the chitosan chain was modified and confirmed the existence of sulfonate groups, as well as in the κ-carrageenan chain, indicating surfaces with similar chemical properties to those of heparin. The effect of charge density was observed for each adsorption condition (BSA at pH 5.0 and 7.4). A more pronounced adsorption rate was observed at pH 5.0 than at pH 7.4 and equilibrium adsorption was achieved, in both cases, after approximately 20 min. The equilibrium data indicate a lower adsorption rate for the sulfonated chitosan film, in comparison to the other films. These results confirm the potential of modified chitosan for use in applications in which globular protein adsorption should be avoided. Study of kinetic parameters in a mechanistic model for enzymatic hydrolysis of sugarcane bagasse subjected to different pretreatments Moreira Neto, J.; Garcia, D.R.; Rueda, S.M.G.; Costa, A.C. Bioprocess and Biosystems Engineering, 36 (2013), 1579-1590. ISSN: 1615-7591. FI = 1.869. Qualis A1. doi:10.1007/s00449-013-0930-6 The goal of this work is to evaluate the influence of different pretreatments in the kinetics of enzymatic hydrolysis of sugarcane bagasse and to propose a reliable methodology to easily perform sensitivity analysis and updating kinetic parameters whenever necessary. A kinetic model was modified to represent the experimental data of the batch enzymatic hydrolysis of sugarcane bagasse pretreated with alkaline hydrogen peroxide. The simultaneous estimation of kinetic parameters of the mathematical model was performed using the Pikaia genetic algorithm using batch hydrolysis experimental data obtained with different enzymatic loads. Subsequently, Plackett–Burman designs were used to identify the kinetic parameters with the higher influence on the dynamic behavior of the process variables, which were re-estimated to describe experimental data of the hydrolysis of bagasse pretreated with phosphoric acid + sodium hydroxide. The methodology was accurate and straightforward and can be used whenever there are changes in pretreatment conditions and/or fluctuations in biomass composition in different harvests.

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Nanostructured membranes based on cellulose acetate obtained by electrospinning. Part II. Controlled release profile and microbiological behavior Nista, S.V.G.; d’Ávila, M.A.; Martinez, E.F.; Silva, A.S.F.; Innocentini Mei, L.H. Journal of Applied Polymer Science, 130 (2013), 2772-2779. ISSN: 0021-8995. FI = 1.289. Qualis A1. doi:10.1002/app.39362 Nanofiber membranes of cellulose acetate (CA) were produced with four mixtures of solvents, that is, acetic acid/water, acetone/water, dimethylacetamide (DMAc)/acetone, and DMAc/acetone/water, with the incorporation of the drug gentamicin sulfate at two concentrations. We evaluated the influence of the drug concentration in the electrospinning process. The best membrane produced in this stage was the membrane electrospun with the DMAc/acetone/water solvent mixture, whose process was shown to be viable and did not alter the membrane diameter or aspect with the variation of the drug concentration. Membranes prepared in this way and loaded with 50% of the drug were used for the studies of the release kinetics. Comparisons between the release profiles of the same membranes coated with hydroxypropyl methylcellulose, Eudragit L100, and electrospun CA nanofibers were carried out. The best results on the drug-release profile were obtained with the membrane coated with nanofibers of CA, which caused a decrease of 9 h in the burst effect. Fractionation and characterization of a petroleum residue by molecular distillation process Rocha, E.R.L.; Lopes, M.S.; Wolf-Maciel, M.R.; Maciel Filho, R.; Medina, L.C. Industrial & Engineering Chemistry Research, 52 (2013), 15488-15493. ISSN: 1520-5045. FI = 2.206. Qualis A1. doi:10.1021/ie400669k In this work, an atmospheric petroleum residue was fractionated using a falling film molecular distillation pilot plant with molecular distillation temperatures ranging from 190 to 320 °C. The process produced four distillate cuts and four residues that were characterized in order to evaluate the efficiency of the technique. The results showed a gain of 11.7% in distillate yield in the highest molecular distillation temperature studied. Physicochemical characterization of the fractions demonstrated that complex compounds were separated of the distillate cuts and were concentrated in the residues which have compounds with features of resins and asphaltenes. Furthermore, data from molecular distillation experiments were used to extend the true boiling point curve of the crude oil up to 662 °C with continuity and good agreement with the ASTM curves. Production of biodiesel from castor oil using sub and supercritical ethanol: effect of sodium hydroxide on the ethyl ester production Rodríguez-Guerrero, J.K.; Maciel Filho, R.; Rosa, P.T.V. Journal of Supercritical Fluids, 83 (2013), 124-132. ISSN: 0896-8446, FI = 2.732. Qualis A1. doi:10.1016/j.supflu.2013.08.016 The biodiesel obtained by the reaction of castor oil with ethanol under sub and supercritical condition (200C to 350C at endogenous pressure) using small amounts of sodium hydroxide (NaOH) as catalyst was studied. The influence of the operating variables such as temperature, reaction time, ethanol:oil molar ratio and catalyst concentration (when used) on the reaction yield was evaluated using an statistical design of experiments along with the surface response methodology for both the catalytic and non-catalytic processes. It was observed that using only 0.1% wt of NaOH for the catalytic process, amount smaller than the necessary to neutralize the castor oil, it was possible to obtain high yields. The maximum ethyl ester yield reached was 98.9% for the catalytic process and 56.2% for the non-catalytic process. Additionally, the reaction kinetic was determined and it was found that a pseudo first order model represents the overall reaction. Activation energies were calculated from the Arrhenius equation for both processes. Characterization of blend properties of castor biodiesel and bioethanol Silva, N.L.; Garcia-Santander, C.M.; Gomez-Rueda, S.M.; Wolf-Maciel, M.R.; Maciel Filho, R. Industrial & Engineering Chemistry Research, 52 (2013), 15504–15508. ISSN: 1520-5045. FI = 2.206. Qualis A1. doi:10.1021/ie400680t Some important properties of biodiesel such as viscosity, melting point, thermal stability, and cetane index can be directly related to the chemical composition of the biomass source used. However, the viscosity of castor oil ethyl ester (COEE) is about four times greater than the biodiesel viscosity specification, and this fact restricts the uses of this biofuel. The main goal of this work is to investigate the physical–chemical properties of COEE in ethanol blends and present an option to decrease the castor oil biodiesel viscosity specification. COEE viscosity is 14.413 mm2/s. The results show an evident decrease

Boletim da FEQ Página 7in biodiesel viscosity with the addition of ethanol. Samples with 30, 40, and 50 vol % of ethanol present the following viscosities 5.316, 4.044, and 3.136 mm2/s, respectively. These results are in agreement with Brazilian National Agency of Petroleum, Natural gas and Biodiesel (ANP), and European (EN 14214) specifications. Three correlations that describe the decrease in viscosity and density with ethanol concentration, and the variation of viscosity with the density in COEE ethanol blends were obtained. The behavior of COEE ethanol blends with diesel also were analyzed. The increase in solubility of ethanol in commercial diesel was verified because COEE acts as a cosolvent in an ethanol–diesel mixture.

Dezembro Determination of the solubility parameters of biodiesel from vegetable oils Batista, M.M.; Guirardello, R.; Krähenbühl, M.A. Energy & Fuels, 27 (2013), 7497-7509. ISSN: 1520-5029. FI = 2.853. Qualis A1. doi:10.1021/ef401690f The fatty acid methyl esters of vegetable oils and animal fats, more commonly known as biodiesel, represent a renewable, biodegradable, non-inflammable and low toxicity alternative to diesel. In this study, the Hansen solubility parameters (HSPs) and the interaction radius of the solute sphere (R0) were determined for the biodiesel derived from soybean oil, coconut oil, palm oil and castor oil, using 45 solvents and solvent mixtures. The values for the HSPs and R0 obtained for the different biodiesels were soybean (15.03, 3.69, 8.92 and 11.33) (MPa(1/2)); coconut (15.12, 3.99, 9.25 and 10.92) (MPa(1/2)); palm (15.43, 5.28, 6.61 and 10.54) (MPa(1/2)) and castor (16.10, 6.72, 9.11 and 11.78) (MPa(1/2)). The HSPs of four biofuels were also determined using the average values of the fatty esters of each oil, calculated using group contribution methods. Subsequently, the solubilities of the biofuels were predicted using the van Krevelen-Hoftyzer, Greenhalgh and Bagley approaches. Isolation and purification of bromelain from waste peel of pineapple for therapeutic application Bresolin, I.R.A.P.; Bresolin, I.T.L.; Silveira, E.; Tambourgi, E.B.; Mazzola, P.G. Brazilian Archives of Biology and Technology, 56 (2013), 971-979. ISSN: 1516-8913. FI = 0.473. Qualis B2. doi:10.1590/S1516-89132013000600012 The aim of this work was to isolate and purify bromelain extracted from the pineapple peel by ammonium sulfate precipitation (40-80%), followed by desalting and freeze-drying with a 75% activity recovery and 2.2 fold increased specific activity. Ion exchange chromatography on DEAE-Sepharose was able to separate the polysaccharides from the enzyme, which was recovered in the elution step, maintaining its enzymatic activity. The batch adsorption of bromelain was evaluated in terms of total protein and enzymatic activity using Langmuir and Langmuir-Freundlich models. Results showed that the process could be suitable for the recovery and purification of the enzyme, maintaining its specific activity. Evaluation of the antimicrobial potential of alginate and alginate/chitosan films containing potassium sorbate and natamycin Da Silva, M.A.; Iamanaka, B.T.; Taniwaki, M.H.; Kieckbusch, T.G. Packaging Technology and Science, 26 (2013), 479-492. ISSN: 1099-1522. Fi = 1.013. Qualis B1. doi:10.1002/pts.2000 The antimicrobial potential of alginate films (AFs) and alginate/chitosan composite films with two different mass proportions of the biopolymers, 82.5:17.5 (CF1) and 65:35 (CF2), containing potassium sorbate (KS) or natamycin was evaluated. At the practical limit of KS addition (0.17 g KS per gram of alginate) for pure AFs, no inhibition zones were observed against Debaromyces hansenii, Penicillium commune and Penicillium roqueforti by the agar diffusion test. Above this concentration, films became opaque, brittle and showed a whitish precipitate over their surface, making them not suitable for use. However, alginate and alginate/chitosan composite films containing natamycin were able to inhibit the growth of the three microorganisms listed above. Natamycin was effective at concentrations as low as 0.005 g per gram of biopolymer for AF and 0.01 g per gram of biopolymer for both composite films, alginate/chitosan 65:35 (CF1) and alginate/chitosan 82.5:17.5 (CF2) against all microorganisms tested. The inhibitory zone diameter increased as concentration of natamycin increased. Active films containing 0.04 g natamycin per gram of biopolymer obtained in the present study exhibited suitable functional attributes and showed excellent perspectives as active antimicrobial films intended for food protection applications.

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An XPS study of chromate and vanadate sorption mechanism by chitosan membrane containing copper nanoparticles Godoi, F.C.; Rodríguez-Castellón, E.; Guibal, E.; Beppu, M.M. Chemical Engineering Journal, 234 (2013), 423-429. ISSN: 1385-8947. FI = 3.691. Qualis A1. doi:10.1016/j.cej.2013.09.006 Chitosan (CHI) membrane containing copper nanoparticles (Cu-NPs) is a potential sorbent for chromate and vanadate removal from aquatic environment. X-ray photo-electron spectroscopy (XPS) was employed to investigate the influence of Cu-NPs on Cr(VI) and V(V) sorption processes. XPS is a powerful technique to understand the mechanisms involved in metal binding to the polymer. X-ray Diffraction (XRD) and Transmission electron microscopy (TEM) confirmed the Cu-NPs presence inside CHI membrane. XPS spectra obtained after sorption showed that Cr(VI) and V(V) ions interact differently with CHI membrane containing Cu-NPs, although both species have similar reduction potentials: Cr(VI)/Cr(II), E0 = +1.33 V and V(V)/V(IV), E0 = +1.00 V against Cu(II)/Cu(I), E0 = +0.16 V. Cr(VI) was reduced to Cr(III) while Cu(I) was oxidized to Cu(II). On the other side, in the case of vanadate sorption, the interactions between vanadate species and CHI amine groups were more significant than the redox reactions involving copper. Biocomposite membranes of sodium alginate and silk fibroin fibers for biomedical applications Moraes, M.A.; Beppu, M.M. Journal of Applied Polymer Science, 130 (2013), 3451-3457. ISSN: 1097-4628. FI = 1.395. Qualis A1. doi:10.1002/app.39598 Biocomposite membranes from biodegradable and biocompatible natural polymers were prepared from sodium alginate solution reinforced with silk fibroin fibers in several fiber content by casting and solvent evaporation. The properties of these biocomposites were investigated by scanning electron microscopy, swelling test, water vapor transmission, mechanical and thermal analyses, and cytotoxicity test. A biocomposite with uniform fiber dispersion and good fiber–matrix interaction was obtained through the incorporation of fibroin fibers in the alginate membrane, even though the fibers were used without any surface treatment to enhance the interfacial adhesion. The incorporation of fibroin fibers improved the tensile strength and also provided a new property to the alginate, that is, the resistance to tear. Moreover, the use of silk fibroin fibers in polymeric composites can result in a material with adequate characteristics for application in the biomaterial field, especially as wound dressings, because of its nontoxic effect to cells, flexibility, and resistance to tear. Chitosan and alginate biopolymer membranes for remediation of contaminated water with herbicides Moraes, M.A.; Cocenza, D.S.; Vasconcellos, F.C.; Fraceto, L.F.; Beppu, M.M. Journal of Environmental Management, 131 (2013), 222-227. ISSN: 0301-4797. FI = 3.057. Qualis A1. doi:10.1016/j.jenvman.2013.09.028 This study investigated the adsorption behavior of the herbicides diquat, difenzoquat and clomazone on biopolymer membranes prepared with alginate and chitosan (pristine and multi-layer model) for contaminated water remediation applications. Herbicides, at concentrations ranging from 5 µM to 200 µM, were adsorbed in either pure alginate, pure chitosan or a bilayer membrane composed of chitosan/alginate. No adsorption of clomazone was observed on any of the membranes, probably due to lack of electrostatic interactions between the herbicide and the membranes. Diquat and difenzoquat were only adsorbed on the alginate and chitosan/alginate membranes, indicating that this adsorption takes place in the alginate layer. At a concentration of 50 µM, diquat adsorption reaches ca. 95% after 120 min on both the alginate and chitosan/alginate membranes. The adsorption of difenzoquat, at the same concentration, reaches ca. 62% after 120 min on pure alginate membranes and ca. 12% on chitosan/alginate bilayer membranes. The adsorption isotherms for diquat and difenzoquat were further evaluated using the isotherm models proposed by Langmuir and by Freundlich, where the latter represented the best-fit model. Results indicate that adsorption occurs via coulombic interactions between the herbicides and alginate and is strongly related to the electrostatic charge, partition coefficients and dissociation constants of the herbicides. Biopolymer based membranes present novel systems for the removal of herbicides from contaminated water sources and hold great promise in the field of environmental science and engineering.

Boletim da FEQ Página 9 Effect of plasma fluorination variables on the deposition and growth of partially fluorinated polymer over PMMA films Padilha, G.S.; Giacon, V.M.; Bartoli, J.R. Polímeros, 23 (2013), 585-589. ISSN: 0104-1428. FI = 0.493. Qualis A2. doi:10.4322/polimeros.2013.093 In this work, an investigation was made of the modification of film surface of Poly(methylmethacrylate) (PMMA) using the plasma polymerization technique. PMMA films 10 µm thick were obtained by Spin-Coating starting from a chloroform solution (15.36% w/w). The films were exposed to the plasma of CHF3 at different gas pressures and exposure times to increase the thickness of fluorinated polymers onto PMMA films. The plasma fluorinated optical films were characterized by gravimetry, FTIR-ATR, contact angle of wetting, SEM and AFM. The surface fluorination of PMMA films can be inferred by the increase in contact angle under all experimental conditions, and confirmed with FTIR-ATR analysis. Gravimetry showed an increase of the fluorinated polymer layer over PMMA films, being 1.55 µm thick at 0.7 torr and 40 minutes of plasma exposure. The SEM analysis showed a well-defined layer of fluorinated polymer, with fluorine being detected in the EDS analysis. The film roughness for the fluorinated polymers was around of 200 Å, quite satisfactory for a 1.55 µm cladding. Hardfats as crystallization modifiers of cocoa butter Ribeiro, A.P.B.; Basso, R.C.; Santos, A.O.; Andrade, G.C.; Cardoso, L.P.; Kieckbusch, T.G. European Journal of Lipid Science and Technology, 115 (2013), 1462-1473. ISSN: 1438-9312. FI = 2.266. doi:10.1002/ejlt.201300052 Hardfats, or fully hydrogenated oils, consist of materials with homogeneous composition, composed of high melting point triacylglycerol. Hardfats are regarded as relatively new materials, and remain unexplored in lipid technology, notwithstanding being low-cost industrial products. They can behave as modulators of the crystallization process, acting as preferential nuclei for ordering the crystal lattice and inducing specific polymorphic habits, with great potential for use in crystallization processes. This work evaluated the influence of the addition of different hardfats on the crystallization patterns of cocoa butter (CB). Fully hydrogenated oils with significantly different chemical composition, obtained from palm kernel oil (FHPKO), palm oil (FHPO), cottonseed oil (FHCO), soybean oil (FHSO), and crambe oil (FHCrO), were considered. Blends of CB/hardfats, at concentrations of 1%, 3%, and 5% (by weight) were produced and the crystallization isotherms, thermal behavior, and polymorphism determined. Hardfats FHPO, FHCO, FHSO, and FHCrO proved to be effective additives to modulate the crystallization characteristics of CB, in respect to crystallization kinetics and thermal behavior. Only the hardfat from crambe oil, FHCrO, presented stabilizing effect on the polymorphism of CB, delaying the transition V → VI. Physical evaluation of biodegradable films of calcium alginate plasticized with polyols Santana, A.A.; Kieckbusch, T.G. Brazilian Journal of Chemical Engineering, 30 (2013), 835-845. ISSN: 0104-6632. Qualis A2. doi:10.1590/S0104-66322013000400015 The influence of different polyols as plasticizers of alginate films on their physical attributes like moisture content, soluble mass in water, water uptake, water vapor permeability, opacity and mechanical properties were determined and the results discussed based on scanning electron microscopy observations and glass transition temperature. The alginate films were obtained by casting, using three different gramatures. Calcium crosslinked and non-reticulated films were considered. The films plasticized with glycerol and xylitol were more hygroscopic than the films with mannitol. The lowest water vapor permeability values were found for films plasticized with mannitol, at all studied thicknesses. The films plasticized with glycerol and xylitol showed very similar functional attributes regarding their application as food wrappings. The Ca2+ crosslinked mannitol films showed the highest tensile strength at rupture (>140 MPa). Reliability of directly-molded polymer surge arresters: degradation by immersion test versus electrical performance Silva, D.A.; Costa, E.C.M.; De Franco, J.L.; Antonionni, M.; Jesus, R.C.; Abreu, S.R.; Lahti, K.; Innocentini Mei, L.H.; Pissolato, J. International Journal of Electrical Power & Energy Systems, 53 (2013), 488-498. ISSN: 0142-0615. FI = 2.247. doi:10.1016/j.ijepes.2013.05.023 This technical report describes an experimental analysis of metal–oxide surge arresters applied to power distribution network. This analysis is performed from periodical measurements of leakage current of the samples and hydrophobicity of the external polymeric housing correlated to the aging/degradation process

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by saline water immersion at 90C for 3 months, in order to simulate 20 years of field application. Based on this evaluation, the useful life and time degradation of polymer arresters are analyzed from the progressive variation of their electrical characteristics as a function of the immersion time. PLA and organoclays nanocomposites: degradation process and evaluation of ecotoxicity using Allium cepa as test organism Souza, P.M.S.; Corroqué, N.A.; Morales, A.R.; Marin-Morales, M.A.; Innocentini Mei, L.H. Journal of Polymers and the Environment, 21 (2013), 1052-1063. ISSN: 1566-2543. FI = 1.349. Qualis A1. doi:10.1007/s10924-013-0604-0 In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by Transmission Electron Microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products.

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Teses e Dissertações Outubro - Dezembro 2013

Mestrado: 1047. Talita Katiuska Takizawa Dias Stefanelli. “Remoção de corante de poli(tereftalato de etileno) (PET) através de recristalização e sua posterior despolimerização em meio ácido”. Orientador: Profa. Dra. Maria Regina Wolf Maciel e Dra. Glaucia Maria Ferreira Pinto (FEQ/UNICAMP). Data: 18/10/2013. 1048. Rodolpho Rodrigues Fonseca. “Desenvolvimento de um controlador fuzzy e split-range aplicado em um reator batelada para a produção de biodiesel”. Orientador: Prof. Dr. Flavio Vasconcelos da Silva. Data: 23/10/2013. 1049. Marcel Mafei Serracchiani. “Estratégia de purificação por IMAC de fragmento fab de IgG humana adicionado a extrato proteico de soja”. Orientador: Profa. Dra. Sonia Maria Alves Bueno. Data: 25/10/2013. 1050. Érika Marques Reis. “Transesterificação via etanólise do óleo de levedura para a produção de biodiesel”. Orientadores: Profa. Dra. Telma Teixeira Franco e Prof. Dr. Gustavo Paim Valença. Data: 30/10/2013. 1051. Bruna Torres da Silva. “Produção de ácido propiônico usando láctico fermentado dos açúcares da cana de açúcar”. Orientador: Profa. Dra. Maria Regina Wolf Maciel. Data: 31/10/2013. 1052. Vanessa Soraia Cortez de Oliveira Radke. “Pré-purificação cromatográfica de DNA plasmidial por cromatografia de pseudoafinidade e tiofílica aromática”. Orientadora: Profa. Dra. Sonia Maria Alves Bueno. Data: 21/11/2013. 1053. Kurts Campos. “Utilização de SO2 recuperado a partir do fosfogesso em plantas de ácido sulfúrico”. Orientador: Prof. Dr. Gustavo Paim Valença. Data: 03/12/2013. 1054. Eriksen Koji Miyasaki. “Avaliação da adição de emulsificantes do tipo lecitinas modificadas na cristalização de manteiga de cacau e de chocolate amargo”. Orientadores: Prof. Dr. Theo Guenter Kieckbusch e Dr. Valdecir Luccas (ITAL). Data: 06/12/2013. 1055. Karine Zanella. “Extração da pectina da casca da laranja-pêra (Citrus sinensis L. Osbeck) com solução diluída”. Orientador: Prof. Dr. Osvaldir Pereira Taranto. Data: 06/12/2013. 1056. Roniérick Pioli Vieira. “Modelagem matemática para a otimização e scale up da polimerização radicalar controlada do estireno”. Orientadora: Profa. Dra. Liliane Maria Ferrareso Lona. Data: 10/12/2013. 1057. Giovana Maria Genevro. “Obtenção e caracterização de hidrogéis de glucomanana para aplicação como biomaterial”. Orientador: Profa. Dra. Marisa Masumi Beppu. Data: 10/12/2013. 1058. Daniele Longo Machado. “Estudo da adsorção das enzimas do complexo celulolítico em bagaço de cana-de-açúcar submetido a diferentes pré-tratamentos e Avicel”. Orientadores: Profa. Dra. Aline Carvalho da Costa e Dr. José Geraldo da Cruz Pradella (CTBE). Data: 11/12/2013. Doutorado: 547. Jorge Marcos Rosa. “Efluentes no beneficiamento têxtil: reutilização do efluente tratado via fotocatálise homogênea UV/H2O2 no tingimento de tecidos 100% algodão”. Orientadores: Prof. Dr. Elias Basile Tambourgi e Prof. Dr. José Carlos Curvelo Santana (UNINOVE). Data: 30/10/2013.

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548. Leandro Lodi. “Estudo do processo de desasfaltação em condições normais e supercríticas utilizando diferentes solventes de extração”. Orientadores: Prof. Dra. Maria Regina Wolf Maciel e Dr. Viktor Oswaldo Cardenas Concha (FEQ/UNICAMP). Data: 29/12/2013. 549. Vadson Bastos do Carmo. “Avaliação da eficiência energética renovável de biomassas alternativas para geração de eletricidade”. Orientadora: Profa. Dra. Katia Tannous. Data: 09/12/2013. 550. Gisele Atsuko Medeiros Hirata. “Determinação de diagramas de fases e do segundo coeficiente virial osmótico B22 na cristalização de proteínas com sal volátil carbamato de amônio”. Orientador: Prof. Dr. Everson Alves Miranda e Prof. Dr. Pedro de Alcântara Pessôa Filho (EPUSP). Data: 09/12/2013.

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Notas curtas

A Editora Campus Elsevier lançou o livro “Shelf Life para a Indústria Química”, de autoria de Luciana Oriqui, Milton Mori e Pedro Wongtschwoski. O livro, voltado para profissionais da indu stria quimica e estudantes de graduacao e pos das areas de Farmacia e Bioquimica, Qui mica, Engenharia Quimica, Engenharia de Alimentos e Saude Pu blica, tem como proposta padronizar a metodologia para definicao da validade de produtos e oferecer ainda uma nova possibilidade para revalidacao do prazo, antes do vencimento, condicionando a uma ana lise caso a caso, e nao lote a lote. A obra, dividida em seis capítulos que abordam a industria quimica, estudos de estabilidade e quimiometria, é produto da tese de doutorado em Engenharia Química de Luciana Oriqui, orientada pelo Prof. Milton Mori, do Departamento de Engenharia de Processos (DEPro) e pelo Dr. Pedro Wongtschwoski, diretor do Grupo Ultra. O lançamento do livro aconteceu na sede da ABIQUIM – Associação Brasileira de Indústrias Químicas, São Paulo, no dia 10 de dezembro de 2013.

A editora Springer lançou o livro “Platelet-Rich Plasma: Regenerative Medicine: Sports Medicine, Orthopedic, and Recovery of Musculoskeletal Injuries” (ISBN 978-3-642-40117-6), que conta com a participação da professora Maria Helena Andrade Santana, do Departamento de Engenharia de Materiais e Bioprocessos (DEMBio) como editora, junto com os pesquisadores José Fábio Santos Duarte Lana, William Dias Belangero e Ângela Cristina Malheiros Luzo. O plasma rico em plaquetas (PRP) ganhou popularidade nos últimos anos como opção de tratamento em ortopedia, odontologia, medicina esportiva, otorrinolaringologia, neurocirurgia, oftalmologia, urologia, cirurgia vascular e medicina veterinária, entre outras especialidades médicas. O livro proporciona ao leitor uma visão geral do estado da arte da técnica, seguida por estudos aprofundados sobre a estrutura, o metabolismo celular e as aplicações do plasma rico em plaquetas. Além do trabalho como editora, a professora Maria Helena ainda é co-autora de três capítulos: Platelet Rich Plasma and Its Growth Factors: The State of the Art; Challenges and a Feasible Strategy for Studies and Standardization of Platelet-Rich Plasma; e Platelet-Rich Plasma and Tissue Engineering. FEQ inaugura Laboratório de Caracterização de Biomassa (Texto original: Manuel Alves Filho; foto: Antonio Scarpinetti) O Jornal da UNICAMP, na sua edição 585, destacou a inauguração do Laboratório de Caracterização de Biomassa, que foi construído e parcialmente equipado com recursos da Shell Brasil Petróleo Ltda. Ao todo, a companhia investiu R$ 7,9 milhões. A unidade abrigará também o Laboratório de Recursos Analíticos e de Calibração (LRAC), que funcionava anteriormente nas dependências da FEQ. O novo laboratório prestará serviços de análises para

docentes e pesquisadores da universidade e para clientes externos. “Vamos oferecer uma infraestrutura única de pesquisa”, afirmou a professora Maria Aparecida Silva, uma das idealizadoras do espaço. Emocionada, a docente lembrou o longo caminho percorrido até a inauguração do laboratório, que tem 1.300 m2 de área construída. As conversações com a Shell tiveram início em 2007, e em 2008 o projeto foi apresentado à Agência Nacional de Petróleo e Gás Natural (ANP), a quem cabe fiscalizar esse tipo de proposta. Em setembro do mesmo ano o convênio para a construção do laboratório foi finalmente assinado pelas duas partes. As obras

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físicas tiveram início em abril de 2010. “Este laboratório dará um valioso suporte às pesquisas da FEQ e de outras unidades, principalmente na área de caracterização de sólidos”, acrescentou Maria Aparecida.

A professora Maria Aparecida Silva mostra equipamento ao reitor José Tadeu Jorge

De acordo com o reitor José Tadeu Jorge, o esforço da FEQ para a construção do Laboratório de Caracterização de Biomassa é representativo do envolvimento de docentes, estudantes e funcionários no projeto que levou a UNICAMP a ser o que ela é atualmente, uma das melhores escolas de nível superior do mundo. Ele destacou a importância do estreitamento das relações da universidade com a sociedade, inclusive o setor produtivo. “Essa parceria com a Shell é um exemplo importante dos frutos que essa aproximação com a sociedade pode proporcionar. Este laboratório certamente trará impactos positivos para a qualificação das nossas pesquisas e também para a formação de recursos humanos, que é a nossa principal missão”. O diretor de produção e exploração da Shell, Carlos Montagna, destacou igualmente a importância da parceria com a UNICAMP, lembrando que é uma decisão estratégica da empresa investir em pesquisa e desenvolvimento no Brasil, país que está na linha de frente quando o assunto é biocombustível. “A UNICAMP já é uma instituição de excelência. Tenho certeza de que as pesquisas desenvolvidas neste laboratório contribuirão para que o país continue exercendo a liderança na área de biocombustíveis”, previu. Também participaram da inauguração a diretora da FEQ, professora Liliane Maria Ferrareso Lona, e a especialista em regulação da ANP, Luciana Mesquita.

Embora o laboratório tenha uma vocação natural para dar suporte à pesquisa sobre a biomassa e biocombustíveis, principalmente etanol de segunda geração, ele pode servir a pesquisadores de diversas áreas, como biologia, química e engenharia de alimentos, para ficar em somente três exemplos. A construção da unidade compõe um orçamento anual de mais de US$ 1 bilhão investido pela Shell em pesquisa e desenvolvimento ao redor do mundo, o que coloca a empresa em uma posição de liderança entre as companhias internacionais de energia.