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Microsoft Photo Editor NC STATE UNIVERSITY BioResources, a peer-reviewed journal College of Natural Resources devoted to the science of lignocellulosic Department of Wood and Paper Science materials, chemicals, and applications Campus Box 8005 Raleigh, NC 27695-8005 919.515.7707/919.513.3022 919.515.6302 (fax) B i o R e s o u r c e s Contents: Vol. 2, Issue 4, November 2007 Hubbe, M. A., and Lucia, L. A. (2007). "The 'love-hate' relationship present in lignocellulosic materials," BioRes. 2(4), 534-535. Tschirner, J., Barsness, J., and Keeler, T. (2007). "Recycling of chemical pulp from wheat straw and corn stover," BioRes. 2(4), 536-543. Zhu, J. Y., Scott, C. T., Gleisner, R., Mann, D., Dykstra, D. P., Quinn, G. H., and Edwards, L. L. (2007). "Mill demonstration of TMP production from forest thinnings: Pulp quality, refining energy, and handsheet properties," BioRes. 2(4), 544-559. Chauhan, V. S., Singh, S. P., and Bajpai, P. K. (2007). "Fiber loading of hardwood pulp by in-situ precipitation of aluminosilicate," BioRes. 2(4), 560-571. Shulga, G., Betkers, T., Shakels, V., Neiberte, B., Verovkins, A., Brovkina, J., Belous, O., Ambrazaintene, D., and Žukauskaite, A. (2007). "Effect of the modification of lignocellulosic materials with a lignin- polymer complex on their mulching properties," BioRes. 2(4), 572-582. Laka, M., and Chernyavskaya, S. (2007). "Obtaining microcrystalline cellulose from softwood and hardwood pulp," BioRes. 2(4), 583-589. Langer, V., Lundquist, K., and Parkås, J. (2007). "The stereochemistry and conformation of lignin as judged by X-ray crystallographic investigations of lignin model compounds: Arylglycerol beta- guaiacyl ethers," BioRes. 2(4), 590-597. Xie, J., Feng, L., Xu, N., Zhu, G., Yang, J., Xu, X., and Fu, S. (2007). "Studies on the fusion of ligninolytic ezyme cDNAs and their expression," BioRes. 2(4), 598-604. Riedlinger, D. A., Sun, N., and Frazier, C. E. (2007). "Tg as an index of conversion in PMDI-impregnated wood," BioRes. 2(4), 605-615. da Silva, T. A., Mocchiutti, P., Zanuttini, M. A., and Ramos, L. P. (2007). "Chemical characterization of pulp components in unbleached softwood kraft fibers recycled with the assistance of laccase/HBT system," BioRes. 2(4), 616-629. Bianchini, R., Catelani, G., Frino, E., Isaad, J., and Rolla, M. (2007). "Lactose to naturalize textile dyes," BioRes. 2(4), 630-637. Saarimaa, V. J., Pranovich, A. V., Sundberg, A. C., and Holmbom, B. R. (2007). "Isolation of pectic acids from bleached TMP water and aggregation of model and TMP pectic acids by calcium," BioRes. 2(4), 638-651. Lindfors, J., Salmi, J., Laine, J., and Stenius, P. (2007). "AKD and ASA model surfaces: Preparation and characterization," BioRes. 2(4), 652-670. Porankiewicz, B., Bermudez, J. C., and Tanaka, C. (2007). "Cutting forces by peripheral cutting of low density wood species," BioRes. 2(4), 671-681. Yang, Q., Zhan, H., Wang, S., Fu, S., and Li, K. (2007). "Bio-modification of eucalyptus chemithermo- mechanical pulp with different white-rot fungi," BioRes. 2(4), 682-692. Dwivedi, U. K., Ghosh, A., and Chand, N. (2007). "Abrasive wear behaviour of bamboo (dendrocalamus strictus) powder filled polyester composites," BioRes. 2(4), 693-698. Dobele, G., Urbanovich, I., Volpert, A., Kampars, V. and Samulis, E. (2007). "Fast pyrolysis - Effect of wood drying on the yield and properties of bio-oil," BioRes. 2(4), 699-706. Taherzadeh, M. J., and Karimi, K. (2007). "Enzyme-based hydrolysis processes for ethanol from lignocellulosic materials: A review," BioRes. 2(4), 707-738. Hubbe, M. A., Venditti, R. A., and Rojas, O. J. (2007). "What happens to cellulosic fibers during papermaking and recycling? A review," BioRes. 2(4), 739-788. BioResources is a peer-reviewed scholarly journal devoted to the science of lignocellulosic materials, chemicals, and their applications. The journal is a service of North Carolina State University, College of Natural Resources (http://cnr.ncsu.edu). You can download PDF files without charge from http://ncsu.edu/bioresources, where you also can find Author instructions, journal policies, etc. Please direct correspondence to co-editors Martin A. Hubbe ([email protected], 919-513-3022) and Lucian A. Lucia ([email protected], 919-515-7707). EDITORIAL ncsu.edu/bioresources THE “LOVE-HATE” RELATIONSHIP PRESENT IN LIGNOCELLULOSIC MATERIALS Martin A. Hubbe and Lucian A. Lucia The three main types of chemical components in wood are cellulose, hemicellulose, and lignin. These three components have rather different physical and chemical characteristics. In some respects, the three types of materials can be described as “incompatible.” However, most of the biomass existing on the planet depends on their successful interactions. It can be useful to think of wood as being a natural composite structure. Concepts related to composites also are useful as we envision possible new and improved uses of wood-derived materials. Keywords: Cellulose, Hemicellulose, Lignin, Hydrophilic, Hydrophobic, Compatibility Contact information: Department of Forest Biomaterials Science and Engineering, North Carolina State University, Campus Box 8005, Raleigh, NC 27695-8005 USA; E-mail: [email protected], [email protected] A RELATIONSHIP MEANT TO LAST? Most of the world’s biomass consists primarily of three somewhat incompatible types of biopolymers – cellulose, hemicellulose, and lignin. Together, these are the most abundant natural organic polymers. Our very existence depends on the successful interactions and structures involving an intimate relationship among these three. Let us examine each of these biopolymers piecemeal. Cellulose is a regular, linear polymer, having a high tendency to form crystalline regions. Though it has a very strong hydrogen bonding tendency, many of the hydrogen bonding sites of cellulose become tied up in the intra-chain and inter-chain associations inherent in the crystalline nature of this macromolecule. From a materials standpoint, cellulose is quite rigid, having a high dimensional stability in the direction of the macromolecular chains. It also has a tendency to swell – especially in the amorphous regions – in dimensions perpen- dicular to the primary orientation of the macromolecules and fibrils. Despite their similar name, hemicelluloses are quite different from cellulose. The macromolecules are irregular, having side groups or substituent groups, as well as different sugar units along the chains. Hemicellulose materials, by themselves, do not have sufficient moduli of elasticity to hold promise as a structural material. Rather, hemicellulose acts like a semi-soluble polyelectrolyte and bonding agent. Finally, lignin’s characteristics from a constructionist’s point of view can cause even greater doubts regarding whether the relationship among these three types of chemicals is destined to last. Lignin is a highly randomized condensed polymer, full of aromatic groups, as well as chemically resistant cross-links of various types. Lignin is much more hydrophobic than cellulose, let alone hemicellulose. Based on solubility principles alone, the three components would be classed as “incompatible” Hubbe and Lucia (2007). “Love, hate, and biomaterials,” BioResources 2(4), 534-535. 1 EDITORIAL ncsu.edu/bioresources A NATURAL COMPOSITE As in any composite, the physical properties of wood seldom equal what would be predicted from a linear sum of properties of its main constituents. Manufacturers of counter-top laminates take advantage of this principle when they impregnate highly porous “saturating kraft” paper with phenolic or melamine resins. The combination of the cellulosic fiber matrix, together with solidified resin filling the void spaces, achieves a dimensional stability far in excess of what can be achieved by either component. The success of a final paper product often depends on the relative abundance of hemicelluloses. Paper’s tear strength is directly related to the levels of hemicelluloses, but pulping operations tend to remove it easily by virtue of its relatively labile nature. Clever scientists are pursuing the concept of VPP (Value Prior to Pulping) to take advantage of this materials loss. The idea is to collect the hemicelluloses and then use them in standard fermentation reactions to make bioethanol. To further extend the idea of a “natural composite” (perhaps dangerously so), one can regard hemicellulose as an adhesive between the rigid semi-crystalline cellulose and the tough “inclusions” of lignin within the wood structure. A need to explain the coupling between the cellulosic and lignin-rich phases lends credibility to some recent results supporting the existence of covalent bonds between hemicelluloses and lignin. Hemicellulose and lignin also help wood resist microbial attack. Whereas it can take as few as three enzymes to efficiently degrade cellulose, it takes a wide assortment of enzymes, working together, to degrade all of the different types of chemical structures present in hemicellulose and lignin. These same factors help to explain why it has been such a challenge to bring lignocellulosic ethanol into widespread commercial success. NEW USES AND NEW OPPORTUNITIES Manufacturers of kraft pulp for papermaking work hard to remove lignin, retaining just the polysaccharide materials to make paper structures having high strength or high brightness. The lignin portion is mainly incinerated to recover its heat value, providing power and steam for the pulping and papermaking processes, as well as recovering the pulping chemicals. Opportunities to make fuller use of byproducts
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