Kinetic model for the hydrolysis of lignocellulosic biomass in the ionic liquid, 1-ethyl-3-methyl-imidazolium chloride†

The kinetics of the acid-catalysed hydrolysis of cellobiose in the ionic liquid 1-ethyl-3-methylimidazolium chloride, [C(2)mim]Cl, was studied as a model for general lignocellulosic biomass hydrolysis in ionic liquid systems. The results show that the rate of the two competing reactions, polysaccharide hydrolysis and sugar decomposition, vary with acid strength, and that for acids with an aqueous pK(a) below approximately zero, the hydrolysis reaction is significantly faster than the degradation of glucose, thus allowing hydrolysis to be performed with a high selectivity in glucose. In tests with soluble cellulose, hemicellulose (xylan), and lignocellulosic biomass (Miscanthus grass), comparable hydrolysis rates were observed with bond scission occurring randomly along the biopolymer chains, in contrast to end-group hydrolysis observed with aqueous acids.

Development and Single-Laboratory Validation of a Pseudofunctional Biosensor Immunoassay for the Detection of the Okadaic Acid Group of Toxins

A rapid analytical optical biosensor-based immunoassay was developed and validated for the detection of okadaic acid (OA) and its structurally related toxins from shellfish matrix. The assay utilizes a monoclonal antibody which binds to the OA group of toxins in order of their toxicities, resulting in a pseudofunctional assay. Single-laboratory validation of the assay for quantitative detection of OA determined that it has an action limit of 120 mu g/kg, a limit of detection of 31 mu g/kg, and a working range of 31-174 mu g/kg. The midpoint on the standard matrix calibration curve is 80 mu g/kg, half the current regulatory limit. Inter- and intra-assay studies of negative mussel samples spiked with various OA concentrations produced average coefficient of variation (CV) and standard deviation (SD) values of 7.9 and 10.1, respectively. The assay was also validated to confirm the ability to accurately codetect and quantify dinophysistoxin-1 (DTX-1), DTX-2, and DTX-3 from shellfish matrix. Alkaline hydrolysis was not required for the detection of DTX-3 from matrix. Excellent correlations with the data generated by the biosensor method and liquid chromatography/tandem mass spectrometry (LC/MS/MS) were obtained using a certified reference material (R-2 = 0.99), laboratory reference material, and naturally contaminated mussel samples (R-2 = 0.97). This new procedure could be used as a rapid screening procedure replacing animal-based tests for DSP toxins.

Comparison of the efficiences of enzymatic and chemical hydrolysis of (nortestosterone and diethylstilboestrol) glucuronides in bovine urine

Residues of 19-nortestosterone (19-NT) and diethylstilboestrol (DES) are excreted in bovine urine, mainly conjugated to glucuronic acid. Prior to quantification, urine must be deconjugated, which is commonly performed by enzymatic or chemical hydrolysis. The efficiencies of two enzymatic and two chemical deconjugation methods were studied. The range of efficiencies obtained for DES were 51.8% (beta -glucuronidase, incubation at 37 degreesC overnight) and 2.7% (methanolic HCl), respectively. Similarly, efficiencies for NT ranged from 43.1% (beta -glucuronidase, incubation at 55 degreesC for 2 h) to 12.7% (methanolic HCl). The results highlight that within control laboratories significant underestimation of drug residue content in samples may occur, due to poor deconjugation. (C) 2001 Elsevier Science B.V. All rights reserved.

Hydrolysis characteristics and kinetics of waste hay biomass as a potential energy crop for fermentable sugars production using autoclave parr reactor system

The use of the organic fraction of municipal solid waste crops has received considerable attention as a sustainable feedstock that can replace fossil fuels for the production of renewable energy. Therefore, municipal bin-waste in the form of hay was investigated as a potential energy crop for fermentable sugars production. Hydrolysis of hay by dilute phosphoric acid was carried out in autoclave parr reactor, where reactor temperature (135-200 degrees c) and acid concentration (2.5-10% (w/w)) were examined. Analysis of the decomposition rate of hemicellulosic biomass was undertaken using HPLC of the reaction products. Xylose production reached a maximum value of 13.5 g/100 g dry mass corresponding to a yield of 67% at the best identified conditions of 2.5 wt% H3PO4, 175 degrees C, 10 min reaction time, and at 5 wt% H3PO4, 150 degrees C, and 5 min reaction time. For glucose, an average yield of 25% was obtained at 5 wt% H3PO4, 175 degrees C and 30 min. Glucose degradation to HMF was achieved at 10 wt% H3PO4 and 200 degrees C. The maximum yield for produced arabinose was an average of 3 g/100 g dry. mass corresponding to 100% of the total possible arabinose. The kinetic study of the acid hydrolysis was also carried out using the Saeman and the Two-fraction models. It was found for both models that the kinetic constants (k) depend on the acid concentration and temperature. For xylose and arabinose it was found that the rate of formation was more favoured than the rate of degradation. By contrast, for glucose it was found that glucose degradation was occurring faster than glucose formation. It can be concluded that dilute phosphoric acid hydrolysis of hay crop is feasible for the production of fermentable sugars which are essential for bioethanol synthesis. 

Development of chitosan packaging films with carvacrol and grape seed extract as antimicrobial and antioxidant agents

In order to produce packaging films with a broad spectrum of action on microorganisms, the effect of two antimicrobial (AM) to be included in the films, carvacrol and GSE were studied separately on different microorganisms. Carvacrol was more effective against the grampositive bacteria than against the gram-negative bacterium. GSE was not effective against yeast. Subsequently, a search for optimal combinations of carvacrol, GSE and the addition of chitosan (as a third component with film forming properties) was carried out. Response surface analysis showed several synergetic effects and three optimal AM combinations (OAMC) were obtained for each microorganism. The experimental validation confirmed that the optimal solutions found can successfully predict the response for each microorganism. The optimization of mixtures of the three components, but this time, using the same concentration for all microorganisms, was also studied to obtain an OAMC with wide spectrum of activity. The results of the response surface analysis showed several synergistic effects for all microorganisms. Three OAMC, OAMC-1, OAMC-2, OAMC-3, were found to be the optimal mixtures for all microorganisms. The radical scavenging activity (RSA) of the different agents was then compared with a standard antioxidant (AOX) BHT, at different concentrations; as also at the OAMC. The RSA increased in the following order: chitosanof OAMC-3. The physico-mechanical properties of 3 films, film-1 with OAMC-1, film-2 with OAMC-2 and film-3 with OAMC-3 were studied. Film-3 presented the lowest WVP, CO2P and TS values and the highest O2P whereas film-1 presented the highest WVP and the lowest crystallinity, CO2P, TS and luminosity. Being one of the components of GSE, gallic acid (GA) release in water from film-1, film-2 and film-3 was next studied over a 30 day period. The mathematical model for the release of GA based on Fick’s law successfully fitted the experimental data and GA diffusion coefficients, assumed to be Arrhenius temperature dependent were obtained for each film. This work will contribute to the development of environmentally friendly packaging films, resulting in improved food preservation and shelf-life extension.

ORGANOSILICON BIOTECHNOLOGY: A BIO-INSPIRED APPROACH TO THE HYDROLYSIS OF ALKOXYSILANES and THE LIPASE-CATALYZED SYNTHESIS OF SILOXANE-CONTAINING POLYESTERS AND POLYAMIDES

The first part of this thesis studied the capacity of amino acids and enzymes to catalyze the hydrolysis and condensation of tetraethoxysilane and phenyltrimethoxysilane. Selected amino acids were shown to accelerate the hydrolysis and condensation of tetraethoxysilane under ambient temperature, pressure and at neutral pH (pH 7±0.02). The nature of the side chain of the amino acid was important in promoting hydrolysis and condensation. Several proteases were shown to have a capacity to hydrolyze tri- and tet-ra- alkoxysilanes under the same mild reaction conditions. The second part of this thesis employed an immobilized Candida antarctica lipase B (Novozym-435, N435) to produce siloxane-containing polyesters, polyamides, and polyester amides under solvent-free conditions. Enzymatic activity was shown to be temperature dependent, increasing until enzyme denaturation became the dominant pro-cess, which typically occurred between 120-130ᵒC. The residual activity of N435 was, on average, greater than 90%, when used in the synthesis of disiloxane-containing polyesters, regardless of the polymerization temperature except at the very highest temperatures, 140-150ᵒC. A study of the thermal tolerance of N435 determined that, over ten reaction cycles, there was a decrease in the initial rate of polymerization with each consecutive use of the catalyst. No change in the degree of monomer conversion after a 24 hour reaction cycle was found.

Miscibility studies of the blends of chitosan with some cellulose ethers

The polymeric films have been prepared based on blends of chitosan with two cellulose ethers-hydroxypropylmethylcellulose and methylcellulose by casting from acetic acid solutions. The films were transparent and brittle in a dry state but an immersion of the samples in deionized water for over 24 h leads to their disintegration or partial dissolution. The miscibility of the polymers in the blends has been assessed by infrared spectroscopy, wide-angle X-ray diffraction, scanning electron microscopy and thermal gravimetric analysis. It was shown that although weak hydrogen bonding exists between the polymer functional groups the blends are not fully miscible in a dry state. (c) 2005 Elsevier Ltd. All rights reserved.

Synthesis of chitosan/hydroxyapatite membranes coated with hydroxycarbonate apatite for guided tissue regeneration purposes

Chitosan, which is a non-toxic, biodegradable and biocompatible biopolymer, has been widely researched for several applications in the field of biomaterials. Calcium phosphate ceramics stand out among the so-called bioceramics for their absence of local or systemic toxicity, their non-response to foreign bodies or inflammations, and their apparent ability to bond to the host tissue. Hydroxyapatite (HA) is one of the most important bioceramics because it is the main component of the mineral phase of bone. The aim of this work was to produce chitosan membranes coated with hydroxyapatite using the modified biomimetic method. Membranes were synthesized from a solution containing 2% of chitosan in acetic acid (weight/volume) via the solvent evaporation method. Specimens were immersed in a sodium silicate solution and then in a 1.5 SBF (simulated body fluid) solution. The crystallinity of the HA formed over the membranes was correlated to the use of the nucleation agent (the sodium silicate solution itself). Coated membranes were characterized by means of scanning electron microscopy - SEM, X-ray diffraction - XRD, and Fourier transform infrared spectroscopy - FTIR. The results indicate a homogeneous coating covering the entire surface of the membrane and the production of a semi-crystalline hydroxyapatite layer similar to the mineral phase of human bone. (C) 2010 Elsevier B.V. All rights reserved.

Heterodinuclear Fe(III)Zn(II)-Bioinspired Complex Supported on 3-Aminopropyl Silica. Efficient Hydrolysis of Phosphate Diester Bonds

Presented herein is the synthesis and characterization of a new Fe(III)Zn(II) complex containing a Fe(III)-bound phenolate with a carbonyl functional group, which was anchored to 3-aminopropylfunctionalized silica as the solid support. The catalytic efficiency of the immobilized catalyst in the hydrolysis of 2,4-bis (dinitrophenyl) phosphate is comparable to the homogeneous reaction, and the supported catalyst can be reused for subsequent diester hydrolysis reactions.

Approximate solution of the autocatalytic hydrolysis of cellulose

Depolymerization of cellulose in homogeneous acidic medium is analyzed on the basis of autocatalytic model of hydrolysis with a positive feedback of acid production from the degraded biopolymer. The normalized number of scissions per cellulose chain, S(t)/nA degrees A = 1 - C(t)/C(0), follows a sigmoid behavior with reaction time t, and the cellulose concentration C(t) decreases exponentially with a linear and cubic time dependence, C(t) = C(0)exp[-at - bt (3)], where a and b are model parameters easier determined from data analysis.

Post consumer pet depolymerization by acid hydrolysis

The reaction of post-consumer poly(ethylene terephthalate) with aqueous solutions of sulfuric acid 7.5M was investigated in terms of temperature, time and particle size. The reaction extent reached 80% in four days at 100 degrees C and 90% in 5 hours at 135 degrees C. TPA obtained was purified and considered in the same level of quality of the commercial one after tests of elemental analysis, particle size and color. It was concluded that the hydrolysis occurred preferentially at the chain ends and superficially, having as controller mechanism the acid diffusion into the polymer structure. The shrinking-core model can explain the reaction kinetics.

Evaluation of the Genotoxicity of Chitosan Nanoparticles for Use in Food Packaging Films

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

Small-angle X-ray scattering from wet gels prepared from co-hydrolysis of tetraethoxysilane and vinyltriethoxysilane

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

Synthesis of chitosan/hydroxyapatite membranes coated with hydroxycarbonate apatite for guided tissue regeneration purposes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Spectrophotometric Determination of Paracetamol in Pharmaceuticals Using Microwave-Assisted Hydrolysis and a Micellar Medium

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