Influence of gelation time on the morphological and physico-chemical properties of the sol-gel entrapped lipase

Different gelation times (4, 18, 24 and 48 h) were used for the preparation of silica sol-gel supports and encapsulated Candida rugosa lipase using tetraethoxysilane (TEOS) as precursor. The hydrophobic matrices and immobilized lipases produced were characterized with regard to pore volume and size by nitrogen adsorption (BJH method), weight loss upon heating (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), chemical composition (FTIR) and percentage of hydrolysis (POH%) of olive oil. These structural parameters were found to change with the gelation time, but no direct relation was found between the percentage of oil hydrolysis (POH%) and the gelation time. The best combination of high thermal stability and high POH% (99.5%) occurred for encapsulated lipase produced with 24 h gelation time. (C) 2007 Elsevier B.V. All rights reserved.

Clarification of a wheat straw-derived medium with ion-exchange resins for xylitol crystallization

BACKGROUND: Xylitol bioproduction from lignocellulosic residues comprises hydrolysis of the hemicellulose, detoxification of the hydrolysate, bioconversion of the xylose, and recovery of xylitol from the fermented hydrolysate. There are relatively few reports on xylitol recovery from fermented media. In the present study, ion-exchange resins were used to clarify a fermented wheat straw hemicellulosic hydrolysate, which was then vacuum-concentrated and submitted to cooling in the presence of ethanol for xylitol crystallization. RESULTS: Sequential adsorption into two anion-exchange resins (A-860S and A-500PS) promoted considerable reductions in the content of soluble by-products (up to 97.5%) and in medium coloration (99.5%). Vacuum concentration led to a dark-colored viscous solution that inhibited xylitol crystallization. This inhibition could be overcome by mixing the concentrated medium with a commercial xylitol solution. Such a strategy led to xylitol crystals with up to 95.9% purity. The crystallization yield (43.5%) was close to that observed when using commercial xylitol solution (51.4%). CONCLUSION: The experimental data demonstrate the feasibility of using ion-exchange resins followed by cooling in the presence of ethanol as a strategy to promote the fast recovery and purification of xylitol from hemicellulose-derived fermentation media. (c) 2008 Society of Chemical Industry.

Use of activated charcoal and ion-exchange resin to cleaN up and concentrate enzymes in extracts from biodegraded wood.

Use of activated charcoal and ion-exchange resin to cleaN up and concentrate enzymes in extracts from biodegraded wood. Ceriporiopsis subvermispora was used for the biodegradation of Eucalyptus grandis chips in the presence or absence of co-substrates (glucose and corn steep liquor) during 7, 14 and 28 days. Afterwards, the biodegraded chips were extracted with 50 mM sodium acetate buffer (pH 5.5) supplemented with 0.01% Tween 60. High activities of manganese peroxidases (MnPs) were observed in all the extracts, both in the absence (430, 765 and 896 UI kg(-1) respectively) and in the presence of co-substrates (1,013; 2,066 and 2,323 UI kg(-1) respectively). The extracts presented a high ratio between absorbances at 280 and 405 nm, indicating a strong abundance of aromatic compounds derived from lignin over heme-peroxidases. Adsorption into activated charcoal showed to be an adequate strategy to reduce the absorbance at 280 urn in all the extracts. Moreover, it allowed to maximize the capacity of an anion exchange resin bed (DEAE-Sepharose) used to concentrate the MnPs present in the extracts. It was concluded that the use of activated charcoal followed by adsorption into DEAE Sepharose is a strategy that can be used to concentrate MnPs in extracts obtained during the biodegradation of E. grandis by C. subvermispora.

Ethanol Production from Sugarcane Bagasse Hydrolysate Using Pichia stipitis

The objective of this study was to evaluate the ethanol production from the sugars contained in the sugarcane bagasse hemicellulosic hydrolysate with the yeast Pichia stipitis DSM 3651. The fermentations were carried out in 250-mL Erlenmeyers with 100 mL of medium incubated at 200 rpm and 30 A degrees C for 120 h. The medium was composed by raw (non-detoxified) hydrolysate or by hydrolysates detoxified by pH alteration followed by active charcoal adsorption or by adsorption into ion-exchange resins, all of them supplemented with yeast extract (3 g/L), malt extract (3 g/L), and peptone (5 g/L). The initial concentration of cells was 3 g/L. According to the results, the detoxification procedures removed inhibitory compounds from the hemicellulosic hydrolysate and, thus, improved the bioconversion of the sugars into ethanol. The fermentation using the non-detoxified hydrolysate led to 4.9 g/L ethanol in 120 h, with a yield of 0.20 g/g and a productivity of 0.04 g L(-1) h(-1). The detoxification by pH alteration and active charcoal adsorption led to 6.1 g/L ethanol in 48 h, with a yield of 0.30 g/g and a productivity of 0.13 g L(-1) h(-1). The detoxification by adsorption into ion-exchange resins, in turn, provided 7.5 g/L ethanol in 48 h, with a yield of 0.30 g/g and a productivity of 0.16 g L(-1) h(-1).

Production, characterization and application of activated carbon from brewer`s spent grain lignin

Different types of activated carbon were prepared by chemical activation of brewer`s spent grain (BSG) lignin using H(3)PO(4) at various acid/lignin ratios (1, 2, or 3 g/g) and carbonization temperatures (300, 450, or 600 degrees C), according to a 2(2) full-factorial design. The resulting materials were characterized with regard to their surface area, pore volume, and pore size distribution, and used for detoxification of BSG hemicellulosic hydrolysate (a mixture of sugars, phenolic compounds, metallic ions, among other compounds). BSG carbons presented BET surface areas between 33 and 692 m(2)/g, and micro- and mesopores with volumes between 0.058 and 0.453 cm(3)/g. The carbons showed high capacity for adsorption of metallic ions, mainly nickel, iron, chromium, and silicon. The concentration of phenolic compounds and color were also reduced by these sorbents. These results suggest that activated carbons with characteristics similar to those commercially found and high adsorption capacity can be produced from BSG lignin. (C) 2009 Elsevier Ltd. All rights reserved.

Multipoint covalent immobilization of lipase on chitosan hybrid hydrogels: influence of the polyelectrolyte complex type and chemical modification on the catalytic properties of the biocatalysts

This work aimed at the production of stabilized derivatives of Thermomyces lanuginosus lipase (TLL) by multipoint covalent immobilization of the enzyme on chitosan-based matrices. The resulting biocatalysts were tested for synthesis of biodiesel by ethanolysis of palm oil. Different hydrogels were prepared: chitosan alone and in polyelectrolyte complexes (PEC) with kappa-carrageenan, gelatin, alginate, and polyvinyl alcohol (PVA). The obtained supports were chemically modified with 2,4,6-trinitrobenzene sulfonic acid (TNBS) to increase support hydrophobicity, followed by activation with different agents such as glycidol (GLY), epichlorohydrin (EPI), and glutaraldehyde (GLU). The chitosan-alginate hydrogel, chemically modified with TNBS, provided derivatives with higher apparent hydrolytic activity (HA(app)) and thermal stability, being up to 45-fold more stable than soluble lipase. The maximum load of immobilized enzyme was 17.5 mg g(-1) of gel for GLU, 7.76 mg g(-1) of gel for GLY, and 7.65 mg g(-1) of gel for EPI derivatives, the latter presenting the maximum apparent hydrolytic activity (364.8 IU g(-1) of gel). The three derivatives catalyzed conversion of palm oil to biodiesel, but chitosan-alginate-TNBS activated via GLY and EPI led to higher recovered activities of the enzyme. Thus, this is a more attractive option for both hydrolysis and transesterification of vegetable oils using immobilized TLL, although industrial application of this biocatalyst still demands further improvements in its half-life to make the enzymatic process economically attractive.

Sensor arrays to detect humic substances and Cu(II) in waters

The interaction between poly(o-ethoxyaniline) (POEA) adsorbed onto solid substrates and humic substances (HS) and Cu(2+) ions has been investigated using UV-vis spectroscopy and atomic force microscopy (AFM). Both HS and Cu(2+) are able to dope POEA and change film morphology. This interaction was exploited in a sensor array made with nanostructured films of POEA, sulfonated lignin and HS, which could detect small concentrations of HS and Cu(2+) in water. (C) 2009 Elsevier B.V. All rights reserved.

Use of sugarcane bagasse as biomaterial for cell immobilization for xylitol production

This study provides a preliminary contribution to the development of a bioprocess for the contintious production of xylitol from hemicellulosic hydrolyzate utilizing Candida guilliermondii cells immobilized onto natural sugarcane bagasse fibers. To this purpose, cells of this yeast were submitted to batch tests of ""in situ"" adsorption onto crushed and powdered sugarcane bagasse after treatment with 0.5 M NaOH. The results obtained on a xylose-based semi-synthetic medium were evaluated in terms of immobilization efficiency, cell retention and specific growth rates of suspended, immobilized and total cells. The first two parameters were shown to increase along the immobilization process, reached maximum values of 50.5% and 0.31 g immobilized cells/g bagasse after 21 h and then sharply decreased. The specific growth rate of suspended cells continuously increased during the immobilization tests, while that of the immobilized ones, after an initial growth, exhibited decreasing values. Under the conditions selected for cell immobilization, fermentation also took place with promising results. The yields of xylitol and biomass on consumed xylose were 0.65 and 0.18 g/g, respectively, xylitol and biomass productivities 0.66 and 0.13 g L-1 h(-1), and the efficiency of xylose-to-xylitol bioconversion was 70.8%. (C) 2007 Elsevier Ltd. All rights reserved.

Pentachlorophenol (PCP) dechlorination in horizontal-flow anaerobic immobilized biomass (HAIB) reactors

This study verifies the potential applicability of horizontal-flow anaerobic immobilized biomass (HAIB) reactors to pentachlorophenol (PCP) dechlorination. Two bench-scale HAIB reactors (R1 and R2) were filled with cubic polyurethane foam matrices containing immobilized anaerobic sludge. The reactors were then continuously fed with synthetic wastewater consisting of PCP, glucose, acetic acid, and formic acid as co-substrates for PCP anaerobic degradation. Before being immobilized in polyurethane foam matrices, the biomass was exposed to wastewater containing PCP in reactors fed at a semi-continuous rate of 2.0 mu g PCP g(-1) VS. The applied PCP loading rate was increased from 0.05 to 2.59 mg PCP l(-1) day(-1) for RI, and from 0.06 to 4.15 mg PCP l(-1) day(-1) for R2. The organic loading rates (OLR) were 1.1 and 1.7 kg COD m(-3) day(-1) at hydraulic retention times (HRT) of 24 h for R1 and 18 In for R2. Under such conditions, chemical oxygen demand (COD) removal efficiencies of up to 98% were achieved in the HAIB reactors. Both reactors exhibited the ability to remove 97% of the loaded PCP. Dichlorophenol (DCP) was the primary chlorophenol detected in the effluent. The adsorption of PCP and metabolites formed during PCP degradation in the packed bed was negligible for PCP removal efficiency. (C) 2009 Elsevier Ltd. All rights reserved.

Influence of support material on the immobilization of biomass for the degradation of linear alkylbenzene sulfonate in anaerobic reactors

Two horizontal-flow anaerobic immobilized biomass reactors (HAIB) were used to study the degradation of the LAS surfactant: one filled with charcoal (HAIB1) and the other with a mixed bed of expanded clay and polyurethane foam (HAIB2). The reactors were fed with synthetic substrate supplemented with 14 mg l(-1) of LAS, kept at 30 +/- 2 degrees C and operated with a hydraulic retention time (HRT) of 12 h. The surfactant was quantified by HPLC. Spatial variation analyses were done to quantify organic matter and LAS consumption along the reactor length. The presence of the surfactant in the load did not affect the removal of organic matter (COD), which was close to 90% in both reactors for an influent COD of 550 ring l(-1). The results of a mass balance indicated that 28% of all LAS added to HAIB1 was removed by degradation. HAIB2 presented 27% degradation. Molecular biology techniques revealed microorgan isms belonging the uncultured Holophaga sp., uncultured delta Proteobacterium, uncultured Verrucomicrobium sp., Bacteroides sp. and uncultured gamma Proteobacterium sp. The reactor with biomass immobilized on charcoal presented lower adsorption and a higher kinetic degradation coefficient. So, it was the most suitable support for LAS anaerobic treatment. (c) 2008 Elsevier Ltd. All rights reserved.

Evaluation of the microbial diversity in a horizontal-flow anaerobic immobilized biomass reactor treating linear alkylbenzene sulfonate

The purpose of this work was to assess the degradation of linear alkylbenzene sulfonate (LAS) in a horizontal-flow anaerobic immobilized biomass (HAIB) reactor. The reactor was filled with polyurethane foam where the sludge from a sanitary sewage treatment was immobilized. The hydraulic detention time (HDT) used in the experiments was of 12 h. The reactor was fed with synthetic substrate (410 mg l(-1) of meat extract, 115 mg l(-1) of starch, 80 mg l(-1) of saccharose, 320 mg l(-1) of sodium bicarbonate and 5 ml l(-1)of salt solution) in the following stages of operation: SI-synthetic substrate, SII-synthetic substrate with 7 mg l(-1) of LAS, SIII-synthetic substrate with 14 mg l(-1) of LAS and SIV-synthetic substrate containing yeast extract (substituting meat extract) and 14 mg l(-1) of LAS, without starch. At the end of the experiment (313 days) a degradation of similar to 35% of LAS was achieved. The higher the concentration of LAS, the greater the amount of foam for its adsorption. This is necessary because the isotherm of LAS adsorption in the foam is linear for the studied concentrations (2 to 50 mg l(-1)). Microscopic analyses of the biofilm revealed diverse microbial morphologies, while Denaturing Gradient Gel Eletrophoresis (DGGE) profiling showed variations in the population of total bacteria and sulphate-reducing bacteria (SRB). The 16S rRNA gene sequencing and phylogenetic analyses revealed that the members of the order Clostridiales were the major components of the bacterial community in the last reactor operation step.

Effect of HMEC on the consolidation of cement pastes: Isothermal calorimetry versus oscillatory rheometry

Chemical admixtures increase the theological complexity of cement pastes owing to their chemical and physical interactions with particles, which affects cement hydration and agglomeration kinetics. Using oscillatory rheometry and isothermal calorimetry, this article shows that the cellulose ether HMEC (hydroxymethyl ethylcellulose), widely used as a viscosity modifying agent in self-compacting concretes and dry-set mortars, displayed a steric dispersant barrier effect during the first 2 h of hydration associated to a cement retarding nature, consequently reducing the setting speed. However, despite this stabilization effect, the polymer increased the cohesion strength when comparing cement particles with the same hydration degree. (C) 2009 Elsevier Ltd. All rights reserved.

Quantification of MgO surface excess on the SnO(2) nanoparticles and relationship with nanostability and growth

In this work, we experimentally showed that the spontaneous segregation of MgO as surface excess in MgO doped SnO(2) nanoparticles plays an important role in the system`s energetics and stability. Using Xray fluorescence in specially treated samples, we quantitatively determined the fraction of MgO forming surface excess when doping SnO(2) with several different concentrations and established a relationship between this amount and the surface energy of the nanoparticles using the Gibbs approach. We concluded that the amount of Mg ions on the surface was directly related to the nanoparticles total free energy, in a sense that the dopant will always spontaneously distribute itself to minimize it if enough diffusion is provided. Because we were dealing with nanosized particles, the effect of MgO on the surface was particularly important and has a direct effect on the equilibrium particle size (nanoparticle stability), such that the lower the surface energy is, the smaller the particle sizes are, evidencing and quantifying the thermodynamic basis of using additives to control SnO(2) nanoparticles stability. (C) 2010 Elsevier B.V. All rights reserved.

Interface Energy Measurement of MgO and ZnO: Understanding the Thermodynamic Stability of Nanoparticles

Nanomaterials have triggered excitement in both fundamental science and technological applications in several fields However, the same characteristic high interface area that is responsible for their unique properties causes unconventional instability, often leading to local collapsing during application Thermodynamically, this can be attributed to an increased contribution of the interface to the free energy, activating phenomena such as sintering and grain growth The lack of reliable interface energy data has restricted the development of conceptual models to allow the control of nanoparticle stability on a thermodynamic basis. Here we introduce a novel and accessible methodology to measure interface energy of nanoparticles exploiting the heat released during sintering to establish a quantitative relation between the solid solid and solid vapor interface energies. We exploited this method in MgO and ZnO nanoparticles and determined that the ratio between the solid solid and solid vapor interface energy is 11 for MgO and 0.7 for ZnO. We then discuss that this ratio is responsible for a thermodynamic metastable state that may prevent collapsing of nanoparticles and, therefore, may be used as a tool to design long-term stable nanoparticles.

Colloidal Processing of Glass-Ceramics for Laminated Object Manufacturing

Green tapes of Li(2)O-ZrO(2)-SiO(2)-Al(2)O(3) (LZSA) parent glass were produced by aqueous tape casting as the starting material for the laminated object manufacturing (LOM) process. The rheological behavior of the powder suspensions in aqueous media, as well as the mechanical properties of the cast tapes, was evaluated. According to xi potential measurements, the LZSA glass powder particles showed acid surface characteristics and an IEP of around 4 when in aqueous media. The critical volume fraction of solids was about 72 wt% (27 vol%), which hindered the processability of more concentrated slurries. The glass particles also showed an anisometric profile, which contributed to an increase in the interactions between particles during flow. Therefore, the suspensions could not be processed at high solids loadings. Aqueous-based glass suspensions were also characterized by shear thickening after the addition of dispersants. Three slurry compositions were formulated, suitable green tapes were cast, and tapes were successfully laminated by LOM to a gear wheel geometry. A higher tensile strength of the green tapes corresponded to a higher tensile strength of the laminates. Thermal treatment was then applied to the laminates: pyrolysis at 525 degrees C, sintering at 700 degrees C for 1 h, and crystallization at 850 degrees C for 30 min. A 20% volumetric shrinkage was observed, but no surface flaws or inhomogeneous areas were detected. The sintered part maintained the curved edges and internal profile after heat treatment.