First report on the kinetics of the uncatalyzed esterification of cellulose under homogeneous reaction conditions: a rationale for the effect of carboxylic acid anhydride chain-length on the degree of biopolymer substitution

The kinetics of the homogeneous acylation of microcrystalline cellulose, MCC, with carboxylic acid anhydrides with different acyl chain-length (Nc; ethanoic to hexanoic) in LiCl/N,N-dimethylacetamide have been studied by conductivity measurements from 65 to 85 A degrees C. We have employed cyclohexylmethanol, CHM, and trans-1,2-cyclohexanediol, CHD, as model compounds for the hydroxyl groups of the anhydroglucose unit of cellulose. The ratios of rate constants of acylation of primary (CHM; Prim-OH) and secondary (CHD; Sec-OH) groups have been employed, after correction, in order to split the overall rate constants of the reaction of MCC into contributions from the discrete OH groups. For the model compounds, we have found that k((Prim-OH))/k((Sec-OH)) > 1, akin to reactions of cellulose under heterogeneous conditions; this ratio increases as a function of increasing Nc. The overall, and partial rate constants of the acylation of MCC decrease from ethanoic- to butanoic-anhydride and then increase for pentanoic- and hexanoic anhydride, due to subtle changes in- and compensations of the enthalpy and entropy of activation.

Use of cellulose fibers from hemp core in fiber-cement production. Effect on flocculation, retention, drainage and product properties

The aim of this paper is to study the feasibility of using cellulose fibers obtained from an agricultural waste, hemp core (Cannabis Sativa L), through different new environmental friendly cooking processes for fiber-cement production. The physical and mechanical properties of the fiber reinforced concrete, which depend on the nature and morphology of the fibers, matrix properties and the interactions between them, must be kept between the limits required for its application. Therefore, the morphology of the fibers and how its use affects the flocculation, retention and drainage processes in the fiber-cement manufacture, and the mechanical and physical properties of the fiber-cement product have been studied. The use of pulp obtained by means of the hemp core cooking in ethanolamine at 60% concentration at 180 degrees C during 90 min resulted in the highest solids retention and the best mechanical properties among the studied hemp core pulps. (C) 2012 Elsevier B.V. All rights reserved.

Effect of amino-terminated substrates onto surface properties of cellulose esters and their interaction with lectins

Films of cellulose acetate butyrate (CAB) and carboxymethylcellulose acetate butyrate (CMCAB) were deposited from ethyl acetate solutions onto bare silicon wafers (Si/SiO2) or amino-terminated surfaces (APS) by means of equilibrium adsorption. All surfaces were characterized by means of ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The presence of amino groups on the support surface favored the adsorption of CAB and CMCAB, inducing the orientation almost polar groups to the surface and the exposition of alkyl group to the air. Such molecular orientation caused increase of the dispersive component of surface energy (gamma(d)(s)) and decrease of the polar component of surface energy (gamma(p)(s)) of cellulose esters in comparison to those values determined for films deposited onto bare Si/SiO2 wafers. Adsorption behavior of jacalin or concanavalin A onto CAB and CMCAB films was also investigated. The adsorbed amounts of lectins were more pronounced on cellulose esters with high (gamma(p)(s)) and total surface energy (gamma(t)(s)) values. (C) 2011 Elsevier B.V. All rights reserved.

Effect of cellulose physical characteristics, especially the water sorption value, on the efficiency of its hydrolysis catalyzed by free or immobilized cellulase

Cellulase, an enzymatic complex that synergically promotes the degradation of cellulose to glucose and cellobiose, free or adsorbed onto Si/SiO(2) wafers at 60 degrees C has been employed as catalyst in the hydrolysis of microcrystalline cellulose (Avicel), microcrystalline cellulose pre-treated with hot phosphoric acid (CP), cotton cellulose (CC) and eucalyptus cellulose (EC). The physical characteristics such as index of crystallinity (I(C)), degree of polymerization (DP) and water sorption values were determined for all samples. The largest conversion rates of cellulose into the above-mentioned products using free cellulase were observed for samples with the largest water sorption values; conversion rates showed no correlation with either IC or DP of the biopolymer. Cellulose with large water sorption value possesses large pore volumes, hence higher accessibility. The catalytic efficiency of immobilized cellulase could not be correlated with the physical characteristics of cellulose samples. The hydrolysis rates of the same cellulose samples with immobilized cellulase were lower than those by the free enzyme, due to the diffusion barrier (biopolymer chains approaching to the immobilized enzyme) and less effective contact between the enzyme active site and its substrate. Immobilized cellulase, unlike its free counterpart, can be recycled at least six times without loss of catalytic activity, leading to higher overall cellulose conversion. (C) 2011 Elsevier B.V. All rights reserved.

Dilute Acid Hydrolysis of Sugar Cane Bagasse at High Temperatures: A Kinetic Study of Cellulose Saccharification and Glucose Decomposition. Part I: Sulfuric Acid as the Catalyst

The kinetics of sugar cane bagasse cellulose saccharification and the decomposition of glucose under extremely low acid (ELA) conditions, (0.07%), 0.14%, and 0.28% H2SO4, and at high temperatures were investigated using batch reactors. The first-order rate constants were obtained by weight loss, remaining glucose, and fitting glucose concentration profiles determined with HPLC using the Saeman model. The maximum glucose yields reached 67.6% (200 degrees C, 0.07% H2SO4, 30 min), 69.8% (210 degrees C, 0.14% H2SO4, 10 min), and 67.3% (210 degrees C, 0.28% H2SO4, 6 min). ELA conditions produced remarkable glucose yields when applied to bagasse cellulose. The first-order rate constants were used to calculate activation energies and extrathermodynamic parameters to elucidate the reaction mechanism under ELA conditions. The effect of acid concentration on cellulose hydrolysis and glucose decomposition was also investigated. The observed activation energies and reaction orders with respect to hydronium ion for cellulose hydrolysis and glucose decomposition were 184.9 and 124.5 kJ/mol and 1.27 and 0.75, respectively.

Development of cellulose-based bactericidal nanocomposites containing silver nanoparticles and their use as active food packaging

The use of nanomaterials, including metallic as active fillers in polymeric nanocomposites for food packaging has been extensively investigated. Silver nanoparticles (AgNPs), in particular, have been exploited for technological applications as bactericidal agents. In this paper, AgNPs were incorporated into a hydroxypropyl methylcellulose (HPMC) matrix for applications as food packaging materials. The average sizes of the silver nanoparticles were 41 nm and 100 nm, respectively. Mechanical analyses and water vapor barrier properties of the HPMC/AgNPs nanocomposites were analysed. The best results were observed for films containing smaller (41 nm) AgNPs. The antibacterial properties of HPMC/AgNPs thin films were evaluated based on the diameter of inhibition zone in a disk diffusion test against Escherichia coli (E. coil) and Staphylococcus aureus (S. aureus). The disk diffusion studies revealed a greater bactericidal effectiveness for nanocomposites films containing 41 nm Ag nanoparticles. (C) 2011 Elsevier Ltd. All rights reserved.

Effect of sorbitan-based surfactants on glass transition temperature of cellulose esters

Thermal behavior of mixtures composed of cellulose acetate butyrate (CAB), carboxymethylcellulose acetate butyrate (CMCAB), or cellulose acetate phthalate (CAPh), and sorbitan-based surfactants was investigated as a function of mixture composition by means of differential scanning calorimetry (DSC). Surfactants with three different alkyl chain lengths, namely, polyoxyethylenesorbitan monolaurate (Tween 20), polyoxyethylenesorbitan monopalmitate (Tween 40), and polyoxyethylene sorbitan monostearate (Tween 60) were chosen. DSC measurements revealed that Tween 20, 40, and 60 act as plasticizers for CAB, CMCAB, and CAPh (except for Tween 60), leading to a dramatic reduction of glass transition temperature (T-g). The dependence of experimental T-g values on the mixture composition was compared with theoretical predictions using the Fox equation. Plasticization was strongly dependent on mixture composition, surfactant hydrophobic chain length, and type of cellulose ester functional group.

Effect of humidity and solvent vapor phase on cellulose esters films

In the present study the effect of relative humidity (RH) during spin-coating process on the structural characteristics of cellulose acetate (CA), cellulose acetate phthalate (C-A-P), cellulose acetate butyrate (CAB) and carboxymethyl cellulose acetate butyrate (CMCAB) films was investigated by means of atomic force microscopy (AFM), ellipsometry and contact angle measurements. All polymer solutions were prepared in tetrahydrofuran (THF), which is a good solvent for all cellulose esters, and used for spin-coating at RH of (35 +/- A 5)%, (55 +/- A 5)% or (75 +/- A 5)%. The structural features were correlated with the molecular characteristics of each cellulose ester and with the balance between surface energies of water and THF and interface energy between water and THF. CA, CAB, CMCAB and C-A-P films spin-coated at RH of (55 +/- A 5)% were exposed to THF vapor during 3, 6, 9, 60 and 720 min. The structural changes on the cellulose esters films due to THF vapor exposition were monitored by means of AFM and ellipsometry. THF vapor enabled the mobility of cellulose esters chains, causing considerable changes in the film morphology. In the case of CA films, which are thermodynamically unstable, dewetting was observed after 6 min exposure to THF vapor. On the other hand, porous structures observed for C-A-P, CAB and CMCAB turned smooth and homogeneous after only 3 min exposure to THF vapor.

Characterization of depolymerized residues from extremely low acid hydrolysis (ELA) of sugarcane bagasse cellulose: Effects of degree of polymerization, crystallinity and crystallite size on thermal decomposition

Sugarcane bagasse cellulose was subjected to the extremely low acid (ELA) hydrolysis in 0.07% H2SO4 at 190, 210 and 225 degrees C for various times. The cellulose residues from this process were characterized by TGA, XRD, GPC, FIR and SEM. A kinetic study of thermal decomposition of the residues was also carried out, using the ASTM and Kissinger methods. The thermal studies revealed that residues of cellulose hydrolyzed at 190, 210 and 225 degrees C for 80,40 and 8 min have initial decomposition temperature and activation energy for the main decomposition step similar to those of Avicel PH-101. XRD studies confirmed this finding by showing that these cellulose residues are similar to Avicel in crystallinity index and crystallite size in relation to the 110 and 200 planes. FTIR spectra revealed no significant changes in the cellulose chemical structure and analysis of SEM micrographs demonstrated that the particle size of the cellulose residues hydrolyzed at 190 and 210 degrees C were similar to that of Avicel. (C) 2011 Elsevier B.V. All rights reserved.

Saccharification of Brazilian sisal pulp: evaluating the impact of mercerization on non-hydrolyzed pulp and hydrolysis products

Cultivation of sisal, a plant with a short growth cycle, is highly productive in Brazil. This work is part of extensive research in which sisal is valued. In these studies, sisal fibers are used in the preparation of bio-based composites and in the derivatization of the pulp, including posterior preparation of films. This study aimed to examine the use of sisal pulp in the production of bioethanol, which can potentially be a high efficiency process because of the cellulose content of this fiber. A previous paper addressed the hydrolysis of sisal pulp using sulfuric acid as a catalyst. In the present study, the influence of the mercerization process on the acid hydrolysis of sisal pulp was evaluated. Mercerization was achieved in a 20% wt NaOH solution, and the cellulosic pulp was suspended and vigorously mixed for 1, 2 and 3 h, at 50 A degrees C. The previously characterized mercerized pulps were hydrolyzed (100 A degrees C, 30% H2SO4, v/v), and the results are compared with those obtained for unmercerized pulp (described in a companion paper). The starting sample was characterized by viscometry, alpha-cellulose content, crystallinity index and scanning electron microscopy. During the reactions, aliquots were withdrawn, and the liquor was analyzed by HPLC. The residual pulps (non-hydrolyzed) were also characterized by the techniques described for the initial sample. The results revealed that pretreatment decreases the polyoses content as well as causes a decrease of up to 23% in the crystallinity and up to 21% in the average molar mass of cellulose after 3 h of mercerization. The mercerization process proved to be very important to achieve the final target. Under the same reaction conditions (30% and 100 A degrees C, 6 h), the hydrolysis of mercerized pulp generated yields of up to 50% more glucose. The results of this paper will be compared with the results of subsequent studies obtained using other acids, and enzymes, as catalysts.

Effect of pH and temperature on the global compactness, structure, and activity of cellobiohydrolase Cel7A from Trichoderma harzianum

Due to its elevated cellulolytic activity, the filamentous fungus Trichoderma harzianum (T. harzianum) has considerable potential in biomass hydrolysis application. Cellulases from Trichoderma reesei have been widely used in studies of cellulose breakdown. However, cellulases from T. harzianum are less-studied enzymes that have not been characterized biophysically and biochemically as yet. Here, we examined the effects of pH and temperature on the secondary and tertiary structures, compactness, and enzymatic activity of cellobiohydrolase Cel7A from T. harzianum (Th Cel7A) using a number of biophysical and biochemical techniques. Our results show that pH and temperature perturbations affect Th Cel7A stability by two different mechanisms. Variations in pH modify protonation of the enzyme residues, directly affecting its activity, while leading to structural destabilization only at extreme pH limits. Temperature, on the other hand, has direct influence on mobility, fold, and compactness of the enzyme, causing unfolding of Th Cel7A just above the optimum temperature limit. Finally, we demonstrated that incubation with cellobiose, the product of the reaction and a competitive inhibitor, significantly increased the thermal stability of Th Cel7A. Our studies might provide insights into understanding, at a molecular level, the interplay between structure and activity of Th Cel7A at different pH and temperature conditions.

Edible films from alginate-acerola puree reinforced with cellulose whiskers

Fruit purees, combined or not with polysaccharides, have been used in some studies to elaborate edible films. The present study was conducted to evaluate tensile properties and water vapor barrier of alginate-acerola puree films plasticized with corn syrup, and to study the influence of cellulose whiskers from different origins (cotton fiber or coconut husk fiber, the latter submitted to one- or multi-stage bleaching) on the film properties. The whiskers improved the overall tensile properties (except by elongation) and the water vapor barrier of the films. The films with coconut whiskers, even those submitted only to a one-stage bleaching, presented similar properties to those of films with cotton whiskers, despite the low compatibility between the matrix and the remaining lignin in coconut whiskers. This was probably ascribed to a counterbalancing effect of the higher aspect ratios of the coconut whiskers. (C) 2011 Elsevier Ltd. All rights reserved.

Alkaline sulfite/anthraquinone pretreatment followed by disk refining of Pinus radiata and Pinus caribaea wood chips for biochemical ethanol production

BACKGROUND: Alkaline sulfite/anthraquinone (ASA) cooking of Pinus radiata and Pinus caribaea wood chips followed by disk refining was used as a pretreatment for the production of low lignified and high fibrillated pulps. The pulps produced with different delignification degrees and refined at different energy inputs (250, 750 and 1600 Wh) were saccharified with cellulases and fermented to ethanol with Saccharomyces cerevisiae using separated hydrolysis and fermentation (SHF) or semi-simultaneous saccharification and fermentation (SSSF) processes. RESULTS: Delignification of ASA pulps was between 25% and 50%, with low glucans losses. Pulp yield was from 70 to 78% for pulps of P. radiata and 60% for the pulp of P. caribaea. Pulps obtained after refining were evaluated in assays of enzymatic hydrolysis. Glucans-to-glucose conversion varied from 20 to 70%, depending on the degree of delignification and fibrillation of the pulps. The best ASA pulp of P. radiata was used in SHF and SSSF experiments of ethanol production. Such experiments produced maximum ethanol concentration of 20 g L-1, which represented roughly90% of glucose conversion and an estimated amount of 260 L ethanol ton(-1) wood. P. caribaea pulp also presented good performance in the enzymatic hydrolysis and fermentation but, due to the low amount of cellulose present, only 140 L ethanol would be obtained from each ton of wood. CONCLUSION: ASA cooking followed by disk refining was shown to be an efficient pretreatment process, which generated a low lignified and high-fibrillated substrate that allowed the production of ethanol from the softwoods with high conversion yields. (C) 2012 Society of Chemical Industry

Mass balance of pilot-scale pretreatment of sugarcane bagasse by steam explosion followed by alkaline delignification

Five pilot-scale steam explosion pretreatments of sugarcane bagasse followed by alkaline delignification were explored. The solubilised lignin was precipitated with 98% sulphuric acid. Most of the pentosan (82.6%), and the acetyl group fractions were solubilised during pretreatment, while 90.2% of cellulose and 87.0% lignin were recovered in the solid fraction. Approximately 91% of the lignin and 72.5% of the pentosans contained in the steam-exploded solids were solubilised by delignification, resulting in a pulp with almost 90% of cellulose. The acidification of the black liquors allowed recovery of 48.3% of the lignin contained in the raw material. Around 14% of lignin, 22% of cellulose and 26% of pentosans were lost during the process. In order to increase material recovery, major changes, such as introduction of efficient condensers and the reduction in the number of washing steps, should be done in the process setup. (C) 2012 Elsevier Ltd. All rights reserved.

Chemical composition and enzymatic digestibility of sugarcane clones selected for varied lignin content

Abstract Background The recalcitrance of lignocellulosic materials is a major limitation for their conversion into fermentable sugars. Lignin depletion in new cultivars or transgenic plants has been identified as a way to diminish this recalcitrance. In this study, we assessed the success of a sugarcane breeding program in selecting sugarcane plants with low lignin content, and report the chemical composition and agronomic characteristics of eleven experimental hybrids and two reference samples. The enzymatic digestion of untreated and chemically delignified samples was evaluated to advance the performance of the sugarcane residue (bagasse) in cellulosic-ethanol production processes. Results The ranges for the percentages of glucan, hemicellulose, lignin, and extractive (based on oven-dry biomass) of the experimental hybrids and reference samples were 38% to 43%, 25% to 32%, 17% to 24%, and 1.6% to 7.5%, respectively. The samples with the smallest amounts of lignin did not produce the largest amounts of total polysaccharides. Instead, a variable increase in the mass of a number of components, including extractives, seemed to compensate for the reduction in lignin content. Hydroxycinnamic acids accounted for a significant part of the aromatic compounds in the samples, with p-coumaric acid predominating, whereas ferulic acid was present only in low amounts. Hydroxycinnamic acids with ester linkage to the hemicelluloses varied from 2.3% to 3.6%. The percentage of total hydroxycinnamic acids (including the fraction linked to lignin through ether linkages) varied from 5.0% to 9.2%, and correlated to some extent with the lignin content. These clones released up to 31% of glucose after 72 hours of digestion with commercial cellulases, whereas chemically delignified samples led to cellulose conversion values of more than 80%. However, plants with lower lignin content required less delignification to reach higher efficiencies of cellulose conversion during the enzymatic treatment. Conclusion Some of the experimental sugarcane hybrids did have the combined characteristics of high biomass and high sucrose production with low lignin content. Conversion of glucan to glucose by commercial cellulases was increased in the samples with low lignin content. Chemical delignification further increased the cellulose conversion to values of more than 80%. Thus, plants with lower lignin content required less delignification to reach higher efficiencies of cellulose conversion during the enzymatic treatment.