Thomas Elder

Cell-wall structural changes in wheat straw pretreated for bioethanol production.

BackgroundPretreatment is an essential step in the enzymatic hydrolysis of biomass and subsequent production of bioethanol. Recent results indicate that only a mild pretreatment is necessary in an industrial, economically feasible system. The Integrated Biomass Utilisation System hydrothermal pretreatment process has previously been shown to be effective in preparing wheat straw for these processes without the application of additional chemicals. In the current work, the effect of the pretreatment on the straw cell-wall matrix and its components are characterised microscopically (atomic force microscopy and scanning electron microscopy) and spectroscopically (attenuated total reflectance Fourier transform infrared spectroscopy) in order to understand this increase in digestibility.ResultsThe hydrothermal pretreatment does not degrade the fibrillar structure of cellulose but causes profound lignin re-localisation. Results from the current work indicate that wax has been removed and hemicellulose has been partially removed. Similar changes were found in wheat straw pretreated by steam explosion.ConclusionResults indicate that hydrothermal pretreatment increases the digestibility by increasing the accessibility of the cellulose through a re-localisation of lignin and a partial removal of hemicellulose, rather than by disruption of the cell wall.

Nanoreinforced xylan–cellulose composite foams by freeze-casting

Structured biofoams have been prepared from the readily available renewable biopolymer xylan by employing an ice-templating technique, where the pore morphology of the material can be controlled by the solidification conditions and the molecular structure of the polysaccharide. Furthermore, reinforcement of these biodegradable foams using cellulose nanocrystals shows potential for strongly improved mechanical properties.

Investigations into laccase-mediator delignification of kraft pulps

Summary The structure activity effects of 1-hydroxy benzotriazole and phthalimide derivatives as mediators for laccase were studied. Using a softwood kraft pulp it was shown that the N-hydroxy unit is a key component of 1-hydroxybenzotriazole for efficient laccase mediator delignification to occur. It was also found that the 1-hydroxybenzotriazole structure was very sensitive to substituent effects with respect to laccase-mediator delignification. Computational results from PM3 indicate that the bond dissociation energy, and electronic factors of the radical may contribute to the efficiency of the mediator for LMS delignification.

High oxygen nanocomposite barrier films based on xylan and nanocrystalline cellulose

The goal of this work is to produce nanocomposite film with low oxygen permeability by casting an aqueous solution containing xylan, sorbitol and nanocrystalline cellulose. The morphology of the resulting nanocomposite films was examined by scanning electron microscopy and atomic force microscopy which showed that control films containing xylan and sorbitol had a more open structure as compared to xylan-sorbitol films containing sulfonated nanocrystalline cellulose. The average pore diameter, bulk density, porosity and tortuosity factor measurements of control xylan films and nanocomposite xylan films were examined by mercury intrusion porosimetry techniques. Xylan films reinforced with nanocrystalline cellulose were denser and exhibited higher tortuosity factor than the control xylan films. Control xylan films had average pore diameter, bulk density, porosity and tortuosity factor of 0.1730 µm, 0.6165 g/ml, 53.0161% and 1.258, respectively as compared to xylan films reinforced with 50% nanocrystalline cellulose with average pore diameter of 0.0581 µm, bulk density of 1.1513 g/ml, porosity of 22.8906% and tortuosity factor of 2.005. Oxygen transmission rate tests demonstrated that films prepared with xylan, sorbitol and 5%, 10%, 25% and 50% sulfonated nanocrystalline cellulose exhibited a significantly reduced oxygen permeability of 1.1387, 1.0933, 0.8986 and 0.1799 cm3·µm/m2·d·kPa respectively with respect to films prepared solely from xylan and sorbitol with a oxygen permeability of 189.1665 cm3·µm/m2·d·kPa. These properties suggested these nanocomposite films have promising barrier properties.

Ice templated and cross-linked xylan/nanocrystalline cellulose hydrogels

Structured xylan-based hydrogels, reinforced with cellulose nanocrystals (CNCs), have successfully been prepared from water suspensions by cross-linking during freeze-casting. In order to induce cross-linking during the solidification/sublimation operation, xylan was first oxidized using sodium periodate to introduce dialdehydes. The oxidized xylan was then mixed with CNCs after which the suspension was frozen unidirectionally in order to control the ice crystal formation and by that the pore morphology of the material. Finally the ice crystal templates were removed by freeze-drying. During the freeze-casting process hemiacetal bonds are formed between the aldehyde groups and hydroxyl groups, either on other xylan molecules or on CNCs, which cross-links the system. The proposed cross-linking reaction was confirmed by using cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) spectroscopy. The pore morphology of the obtained materials was analyzed by scanning electron microscopy (SEM). The materials were also tested for compressive strength properties, both in dry and water swollen state. All together this study describes a novel combined freeze-casting/cross-linking process which enables fabrication of nanoreinforced biopolymer-based hydrogels with controlled porosity and 3-D architecture.

MECHANISMS OF OXIDATIVE DEGRADATION OF CARBOHYDRATES DURING OXYGEN DELIGNIFICATION. II. REACTION OF PHOTOCHEMICALLY GENERATED HYDROXYL RADICALS WITH METHYL β-CELLOBIOSIDE

Reactions involving methyl β-cellobioside and several oxygen species were used to investigate cleavage of glycosidic linkages in cellulose by reaction with photochemical hydroxyl radicals. The intent is not to reproduce delignification conditions, but rather to study the specific behavior of carbohydrate models toward hydroxyl radical. Experiments show that hydroxyl radicals are responsible for the degradation of glycosidic linkages in methyl β-cellobioside by substitution reactions displacing cellobiose, D-glucose, methyl β-D-glucoside, and methanol. Once the glycosidic linkages are broken, the reducing carbohydrates undergo a series of reactions forming aldonic acids and lower order aldoses in the same manner as described previously.[1]

Impact of Steam Explosion on the Wheat Straw Lignin Structure Studied by Solution-State Nuclear Magnetic Resonance and Density Functional Methods

Chemical changes of lignin induced by the steam explosion (SE) process were elucidated. Wheat straw was studied as the raw material, and lignins were isolated by the enzymatic mild acidolysis lignin (EMAL) procedure before and after the SE treatment for analyses mainly by two-dimensional (2D) [heteronuclear single-quantum coherence (HSQC) and heteronuclear multiple-bond correlation (HMBC)] and (31)P nuclear magnetic resonance (NMR). The β-O-4 structures were found to be homolytically cleaved, followed by recoupling to β-5 linkages. The homolytic cleavage/recoupling reactions were also studied by computational methods, which verified their thermodynamic feasibility. The presence of the tricin bound to wheat straw lignin was confirmed, and it was shown to participate in lignin reactions during the SE treatment. The preferred homolytic β-O-4 cleavage reaction was calculated to follow bond dissociation energies: G-O-G (guaiacyl) (69.7 kcal/mol) > G-O-S (syringyl) (68.4 kcal/mol) > G-O-T (tricin) (67.0 kcal/mol).

Integrating Separation and Conversion—Conversion of Biorefinery Process Streams to Biobased Chemicals and Fuels

The concept of the integrated biorefinery is critical to developing a robust biorefining industry in the USA. Within this model, the biorefinery will produce fuel as a high-volume output addressing domestic energy needs and biobased chemical products (high-value organics) as an output providing necessary economic support for fuel production. This paper will overview recent developments within two aspects of the integrated biorefinery—the fractionation of biomass into individual process streams and the subsequent conversion of lignin into chemical products. Solvent-based separation of switchgrass, poplar, and mixed feedstocks is being developed as a biorefinery “front end” and will be described as a function of fractionation conditions. Control over the properties and structure of the individual biomass components (carbohydrates and lignin) can be observed by adjusting the fractionation process. Subsequent conversion of the lignin isolated from this fractionation leads to low molecular weight aromatics from selective chemical oxidation. Together, processes such as these provide examples of foundational technology that will contribute to a robust domestic biorefining industry.

Carboxymethylated-, hydroxypropylsulfonated- and quaternized xylan derivative films.

Under alkaline/water conditions carboxymethyl, 2-hydroxypropylsulfonate and trimethylammonium-2-hydroxypropyl groups were introduced into xylan in one step with the goal to prepare film specimens. The materials were characterized by NMR, SEC-MALS, TG/DTG/DTA, AFM and mechanical testing. The properties of triple, double and mono-substituted materials were compared. The numerical molar masses of the specimens were from 12.3 to 17.6 kg/mol with Mw/Mn from 1.27 to 1.34. The elastic modulus values are decreasing in order: xylan (X; 7354 MPa)>carboxymethyl xylan (CX; 6090MPa)>2-hydroxypropylsulfonate xylan (SX; 6000 MPa)>carboxymethyl/2-hydroxypropylsulfonate xylan (CSX; 4490 MPa)>quaternized xylan (QX; 3600 MPa)>carboxymethyl/quaternary/2-hydroxypropylsulfonate xylan (CQSX; 3380 MPa)>carboxymethyl/quaternary xylan (CQX; 2805 MPa). The onset temperatures of SX (214°C), CQSX (212°C), QSX (211°C) and CQX (207°C) were higher than for X (205°C). The roughness values of the film surfaces (3.634-18.667 nm) are higher on top than on the bottom of the specimen.

Alkaline peroxide treatment of ECF bleached softwood kraft pulps. Part 1. characterizing the effect of alkaline peroxide treatment on carboxyl groups of fibers

Abstract The influence of alkaline peroxide treatment has been characterized on elementally chlorine-free (ECF) bleached softwood (SW) kraft pulp. The results indicate that fiber charge increased with an increase in peroxide charge: a maximum fiber charge increment of 16.6% was obtained with 8.0% more peroxide charge on oven-dried (o.d.) pulp at 60.0°C. Two primary bleaching temperatures of 60.0°C and 90.0°C were investigated during peroxide treatment. Copper number decreased for peroxide charges of 0.5% and 1.0% at 60.0°C and 90.0°C, respectively, then increased with increasing peroxide charge. Both fiber charge and copper number approached constant values when 4.0% or higher peroxide charge was applied. Peroxide treatment on a bleached kraft pulp at 90.0°C resulted in lower fiber charge and lower intrinsic viscosity compared to treatment at 60.0°C. Sodium borohydride (NaBH4) pretreatment was able to protect the fibers from being degraded during peroxide bleaching. Fiber charge and copper number were compared after peroxide treatment of ECF bleached kraft pulp to NaBH4-reduced ECF bleached kraft pulp. The results indicate that the carbonyl group content of fibers is favorable for improving fiber charge after peroxide treatment.