Cellulose: Fascinating Biopolymer and Sustainable Raw Material
TL;DR: The current knowledge in the structure and chemistry of cellulose, and in the development of innovative cellulose esters and ethers for coatings, films, membranes, building materials, drilling techniques, pharmaceuticals, and foodstuffs are assembled.
Abstract: As the most important skeletal component in plants, the polysaccharide cellulose is an almost inexhaustible polymeric raw material with fascinating structure and properties. Formed by the repeated connection of D-glucose building blocks, the highly functionalized, linear stiff-chain homopolymer is characterized by its hydrophilicity, chirality, biodegradability, broad chemical modifying capacity, and its formation of versatile semicrystalline fiber morphologies. In view of the considerable increase in interdisciplinary cellulose research and product development over the past decade worldwide, this paper assembles the current knowledge in the structure and chemistry of cellulose, and in the development of innovative cellulose esters and ethers for coatings, films, membranes, building materials, drilling techniques, pharmaceuticals, and foodstuffs. New frontiers, including environmentally friendly cellulose fiber technologies, bacterial cellulose biomaterials, and in-vitro syntheses of cellulose are highlighted together with future aims, strategies, and perspectives of cellulose research and its applications.
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TL;DR: This critical review provides a processing-structure-property perspective on recent advances in cellulose nanoparticles and composites produced from them, and summarizes cellulOSE nanoparticles in terms of particle morphology, crystal structure, and properties.
Abstract: This critical review provides a processing-structure-property perspective on recent advances in cellulose nanoparticles and composites produced from them. It summarizes cellulose nanoparticles in terms of particle morphology, crystal structure, and properties. Also described are the self-assembly and rheological properties of cellulose nanoparticle suspensions. The methodology of composite processing and resulting properties are fully covered, with an emphasis on neat and high fraction cellulose composites. Additionally, advances in predictive modeling from molecular dynamic simulations of crystalline cellulose to the continuum modeling of composites made with such particles are reviewed (392 references).
4,920 citations
TL;DR: Dr. Youssef Habibi’s research interests include the sustainable production of materials from biomass, development of high performance nanocomposites from lignocellulosic materials, biomass conversion technologies, and the application of novel analytical tools in biomass research.
Abstract: Cellulose constitutes the most abundant renewable polymer resource available today. As a chemical raw material, it is generally well-known that it has been used in the form of fibers or derivatives for nearly 150 years for a wide spectrum of products and materials in daily life. What has not been known until relatively recently is that when cellulose fibers are subjected to acid hydrolysis, the fibers yield defect-free, rod-like crystalline residues. Cellulose nanocrystals (CNs) have garnered in the materials community a tremendous level of attention that does not appear to be relenting. These biopolymeric assemblies warrant such attention not only because of their unsurpassed quintessential physical and chemical properties (as will become evident in the review) but also because of their inherent renewability and sustainability in addition to their abundance. They have been the subject of a wide array of research efforts as reinforcing agents in nanocomposites due to their low cost, availability, renewability, light weight, nanoscale dimension, and unique morphology. Indeed, CNs are the fundamental constitutive polymeric motifs of macroscopic cellulosic-based fibers whose sheer volume dwarfs any known natural or synthetic biomaterial. Biopolymers such as cellulose and lignin and † North Carolina State University. ‡ Helsinki University of Technology. Dr. Youssef Habibi is a research assistant professor at the Department of Forest Biomaterials at North Carolina State University. He received his Ph.D. in 2004 in organic chemistry from Joseph Fourier University (Grenoble, France) jointly with CERMAV (Centre de Recherche sur les Macromolecules Vegetales) and Cadi Ayyad University (Marrakesh, Morocco). During his Ph.D., he worked on the structural characterization of cell wall polysaccharides and also performed surface chemical modification, mainly TEMPO-mediated oxidation, of crystalline polysaccharides, as well as their nanocrystals. Prior to joining NCSU, he worked as assistant professor at the French Engineering School of Paper, Printing and Biomaterials (PAGORA, Grenoble Institute of Technology, France) on the development of biodegradable nanocomposites based on nanocrystalline polysaccharides. He also spent two years as postdoctoral fellow at the French Institute for Agricultural Research, INRA, where he developed new nanostructured thin films based on cellulose nanowiskers. Dr. Habibi’s research interests include the sustainable production of materials from biomass, development of high performance nanocomposites from lignocellulosic materials, biomass conversion technologies, and the application of novel analytical tools in biomass research. Chem. Rev. 2010, 110, 3479–3500 3479
4,664 citations
TL;DR: This Review assembles the current knowledge on the isolation of microfibrillated cellulose from wood and its application in nanocomposites; the preparation of nanocrystalline cellulose and its use as a reinforcing agent; and the biofabrication of bacterial nanocellulose, as well as its evaluation as a biomaterial for medical implants.
Abstract: Cellulose fibrils with widths in the nanometer range are nature-based materials with unique and potentially useful features. Most importantly, these novel nanocelluloses open up the strongly expanding fields of sustainable materials and nanocomposites, as well as medical and life-science devices, to the natural polymer cellulose. The nanodimensions of the structural elements result in a high surface area and hence the powerful interaction of these celluloses with surrounding species, such as water, organic and polymeric compounds, nanoparticles, and living cells. This Review assembles the current knowledge on the isolation of microfibrillated cellulose from wood and its application in nanocomposites; the preparation of nanocrystalline cellulose and its use as a reinforcing agent; and the biofabrication of bacterial nanocellulose, as well as its evaluation as a biomaterial for medical implants.
3,452 citations
Grenoble Institute of Technology1, National University of Mar del Plata2, Case Western Reserve University3, University of Fribourg4, University of Nottingham5, Virginia Tech6, University of Natural Resources and Life Sciences, Vienna7, University of Leoben8, Kyoto University9, Oregon State University10, Portland State University11, Imperial College London12, Queen Mary University of London13
TL;DR: An overview of recent progress in the area of cellulose nanofibre-based nanocomposites is given in this article, with particular emphasis on applications, such as reinforced adhesives, to make optically transparent paper for electronic displays, to create DNA-hybrid materials, to generate hierarchical composites and for use in foams, aerogels and starch nanocom composites.
Abstract: This paper provides an overview of recent progress made in the area of cellulose nanofibre-based nanocomposites. An introduction into the methods used to isolate cellulose nanofibres (nanowhiskers, nanofibrils) is given, with details of their structure. Following this, the article is split into sections dealing with processing and characterisation of cellulose nanocomposites and new developments in the area, with particular emphasis on applications. The types of cellulose nanofibres covered are those extracted from plants by acid hydrolysis (nanowhiskers), mechanical treatment and those that occur naturally (tunicate nanowhiskers) or under culturing conditions (bacterial cellulose nanofibrils). Research highlighted in the article are the use of cellulose nanowhiskers for shape memory nanocomposites, analysis of the interfacial properties of cellulose nanowhisker and nanofibril-based composites using Raman spectroscopy, switchable interfaces that mimic sea cucumbers, polymerisation from the surface of cellulose nanowhiskers by atom transfer radical polymerisation and ring opening polymerisation, and methods to analyse the dispersion of nanowhiskers. The applications and new advances covered in this review are the use of cellulose nanofibres to reinforce adhesives, to make optically transparent paper for electronic displays, to create DNA-hybrid materials, to generate hierarchical composites and for use in foams, aerogels and starch nanocomposites and the use of all-cellulose nanocomposites for enhanced coupling between matrix and fibre. A comprehensive coverage of the literature is given and some suggestions on where the field is likely to advance in the future are discussed.
2,214 citations
TL;DR: This critical review provides a survey illustrated by recent references of different strategies to achieve a sustainable conversion of biomass to bioproducts to examine critically the green character of conversion processes.
Abstract: This critical review provides a survey illustrated by recent references of different strategies to achieve a sustainable conversion of biomass to bioproducts. Because of the huge number of chemical products that can be potentially manufactured, a selection of starting materials and targeted chemicals has been done. Also, thermochemical conversion processes such as biomass pyrolysis or gasification as well as the synthesis of biofuels were not considered. The synthesis of chemicals by conversion of platform molecules obtained by depolymerisation and fermentation of biopolymers is presently the most widely envisioned approach. Successful catalytic conversion of these building blocks into intermediates, specialties and fine chemicals will be examined. However, the platform molecule value chain is in competition with well-optimised, cost-effective synthesis routes from fossil resources to produce chemicals that have already a market. The literature covering alternative value chains whereby biopolymers are converted in one or few steps to functional materials will be analysed. This approach which does not require the use of isolated, pure chemicals is well adapted to produce high tonnage products, such as paper additives, paints, resins, foams, surfactants, lubricants, and plasticisers. Another objective of the review was to examine critically the green character of conversion processes because using renewables as raw materials does not exempt from abiding by green chemistry principles (368 references).
2,077 citations
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01 Jan 1981
TL;DR: In this article, the most useful groups for the hydroxyl, amino, carboxyl, carbonyl, and sulfhydryl groups are discussed and the chemistry of the classes of these groups, as well as that of individual groups within the class using structures, equations and references.
Abstract: Provides comprehensive information on the most useful protective groups for the hydroxyl, amino, carboxyl, carbonyl, and sulfhydryl groups. Discusses the chemistry of the classes of protective groups, as well as that of the individual protective groups within the class using structures, equations and references. Reactivity Charts for each class of protective group serve as an aid in their appropriate choice and provide estimates of their relative reactivities toward 108 prototype reagents.
14,841 citations
TL;DR: In this article, the crystal and molecular structure of cellulose Iβ were determined using synchrotron and neutron diffraction data recorded from oriented fibrous samples prepared by aligning cellulose microcrystals from tunicin.
Abstract: The crystal and molecular structure together with the hydrogen-bonding system in cellulose Iβ has been determined using synchrotron and neutron diffraction data recorded from oriented fibrous samples prepared by aligning cellulose microcrystals from tunicin. These samples diffracted both synchrotron X-rays and neutrons to better than 1 A resolution (>300 unique reflections; P21). The X-ray data were used to determine the C and O atom positions. The resulting structure consisted of two parallel chains having slightly different conformations and organized in sheets packed in a “parallel-up” fashion, with all hydroxymethyl groups adopting the tg conformation. The positions of hydrogen atoms involved in hydrogen-bonding were determined from a Fourier-difference analysis using neutron diffraction data collected from hydrogenated and deuterated samples. The hydrogen atoms involved in the intramolecular O3···O5 hydrogen bonds have well-defined positions, whereas those corresponding to O2 and O6 covered a wider v...
2,583 citations
TL;DR: A review of the information gathered on cellulose structure over the last few decades can be found in this paper, where the authors attempt to bring together basic and complex information which has been gathered on the structure of native cellulose.
Abstract: This article attempts to bring together basic and complex information which has been gathered on cellulose structure, principally that of native cellulose, over the last few decades. Even though advances have been made in the field of crystallography, powder crystallography cannot yield a definitive cellulose structure and single crystal diffraction is not possible due to the lack of suitable crystals. Knowledge obtained on the biosynthesis of native cellulose and on the polymorphy of cellulose and its derivatives help our understanding of ultrastructure. Many inconsistencies between early crystallographic studies of native cellulose have been clarified by the discovery that two polymorphs (α and β) of cellulose I exist. Models of the possible ultrastructural arrangements within native cellulose have been put forward over the decades; with advancement in technology, computer simulations of small and large systems are being created to test the viability of these ultrastructural models. It is hoped that this review will aid in the understanding of the complexity and uncertainties that still exist in this subject
1,460 citations
TL;DR: High mechanical strength in wet state, enormous water retention values, low roughness of the inner surface, and a complete ‘vitalization’ of BASYC ® — microvessel-interpositions in rat experiments demonstrate the high potential of BasyC ® as an artificial blood vessel in microsurgery.
1,178 citations
TL;DR: Multiplicities in the resonances of chemically equivalent carbons, which appear in the solid-state carbon-13 nuclear magnetic resonance spectra of native celluloses, have been examined at high resolution and are consistent with the existence of two distinct crystalline forms.
Abstract: Multiplicities in the resonances of chemically equivalent carbons, which appear in the solid-state carbon-13 nuclear magnetic resonance spectra of native celluloses, have been examined at high resolution. The patterns of variation are consistent with the existence of two distinct crystalline forms. One form is dominant in bacterial and algal celluloses, whereas the other is dominant in celluloses from higher plants.
1,092 citations