Chitin and chitosan: Properties and applications

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.

Cellulose: Fascinating Biopolymer and Sustainable Raw Material

Chitin is the most abundant natural amino polysaccharide and is estimated to be produced annually almost as much as cellulose. It has become of great interest not only as an underutilized resource, but also as a new functional material of high potential in various fields, and recent progress in chitin chemistry is quite noteworthy. The purpose of this review is to take a closer look at chitin and chitosan applications. Based on current research and existing products, some new and futuristic approaches in this fascinating area are thoroughly discussed.

A review of chitin and chitosan applications

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

Cellulose nanocrystals: chemistry, self-assembly, and applications.

Poly(ethylene glycol) (PEG) is the most used polymer and also the gold standard for stealth polymers in the emerging field of polymer-based drug delivery. The properties that account for the overwhelming use of PEG in biomedical applications are outlined in this Review. The first approved PEGylated products have already been on the market for 20 years. A vast amount of clinical experience has since been gained with this polymer--not only benefits, but possible side effects and complications have also been found. The areas that might need consideration and more intensive and careful examination can be divided into the following categories: hypersensitivity, unexpected changes in pharmacokinetic behavior, toxic side products, and an antagonism arising from the easy degradation of the polymer under mechanical stress as a result of its ether structure and its non-biodegradability, as well as the resulting possible accumulation in the body. These possible side effects will be discussed in this Review and alternative polymers will be evaluated.

Poly(ethylene glycol) in Drug Delivery: Pros and Cons as Well as Potential Alternatives

Synthesis and solution properties of zwitterionic polymers.

Homopolymers of sodium 4-styrenesulfonate have been synthesized directly in aqueous media by reversible addition−fragmentation chain transfer polymerization (RAFT). The resulting homopolymers have narrow molecular weight distributions, with polydispersity indices in the range 1.12−1.25, as determined by aqueous size exclusion chromatography. Using a dithioester-capped sodium 4-styrenesulfonate homopolymer as a macro chain transfer agent, a block copolymer with sodium 4-vinylbenzoate has been prepared in aqueous media. Additionally, a block copolymer of (ar-vinylbenzyl)trimethylammonium chloride with N,N-dimethylvinylbenzylamine has been synthesized, using the same methodology. We believe these represent the first examples of AB diblock copolymers prepared directly in aqueous media via the RAFT process. Both block copolymers are stimuli-responsive and undergo reversible pH-induced micellization in aqueous solution. Micelles with hydrodynamic diameters in the range 18−38 nm were observed by dynamic light sc...

Water-Soluble Polymers. 81. Direct Synthesis of Hydrophilic Styrenic-Based Homopolymers and Block Copolymers in Aqueous Solution via RAFT

Reversible addition–fragmentation chain transfer (RAFT) radical polymerization and the synthesis of water-soluble (co)polymers under homogeneous conditions in organic and aqueous media

Solution studies of cellulose in lithium chloride and N,N-dimethylacetamide

Reversible addition−fragmentation chain transfer (RAFT) polymerization has been the focus of intensive research over the past few years since this methodology allows the synthetic tailoring of macromolecules with complex architectures including block, graft, comb, and star structures with predetermined molecular weight, terminal functionality, and narrow molecular weight distribution. In this paper we recount significant milestones in achieving controlled free radical homopolymerization and block copolymerization of water-soluble and amphiphilic monomers including nonionic, cationic, anionic, and zwitterionic species. It is shown that under aqueous conditions, control of homopolymerization and further blocking to extend the molecular weight or to produce precisely structured block copolymers require not only careful selection of reagents (initiator, chain transfer agent, and monomer) but also regulation or elimination of hydrolysis of the ω-terminal thiocarbonylthio functionality. The technological potent...

Charles L. McCormick

Papers

Synthesis and solution properties of zwitterionic polymers.

Water-Soluble Polymers. 81. Direct Synthesis of Hydrophilic Styrenic-Based Homopolymers and Block Copolymers in Aqueous Solution via RAFT

Reversible addition–fragmentation chain transfer (RAFT) radical polymerization and the synthesis of water-soluble (co)polymers under homogeneous conditions in organic and aqueous media

Solution studies of cellulose in lithium chloride and N,N-dimethylacetamide

Aqueous RAFT polymerization: recent developments in synthesis of functional water-soluble (co)polymers with controlled structures.