Elsevier

Carbohydrate Polymers

Volume 93, Issue 1, 1 March 2013, Pages 207-215
Carbohydrate Polymers

Oxidized cellulose—Survey of the most recent achievements

https://doi.org/10.1016/j.carbpol.2012.03.086Get rights and content

Abstract

The functionalization and particularly the oxidation of cellulose is an intriguing and challenging topic due to the presence of multiple reactive sites, which can undergo specific reactions. The variety of the oxidizing agents used to improve the selectivity and yields of these transformations is illustrated by the steadily growing of the number of publications and patents reported. This paper is focused on the most selective agents for cellulose oxidations, i.e., sodium periodate and stable or non persistent nitroxyl radicals, emphasizing on the most recent developments reported so far.

Highlights

► The recent advances on selective oxidation of cellulose are described. ► TEMPO oxidation of cellulose, occurs mainly at primary OH groups. ► Non persistent nitroxyl radicals are efficient and selective mediators for cellulose oxidation. ► Development of new ecologically friendly protocols for the oxidation of polysaccharides are required.

Introduction

The oxidation of cellulosic materials is a pivotal reaction in cellulose chemistry, used to impart special properties on the different cellulosic sorts. The cellulose's chemical modification through oxidation leads to added value products, being a prime factor to determine macroscopic properties and chemical behavior of cellulosic materials.

Moreover, the preparation of oxidized cellulose containing carboxyl groups is of special interest because it has several useful medical applications. Oxidized cellulose is completely bioresorbable and easily degradable under physiological conditions, being widely used as absorbable hemostatic scaffolding material (Dias et al., 2003, Galgut, 1990), and as a postsurgical adhesion prevention layer (Wiseman, Saferstein, & Wolf, 2002). Other applications of oxidized cellulose as carrier material for agricultural, cosmetic and pharmaceutical applications are reported (Banker and Kumar, 1995, Jin and Wu, 2005). Oxidized cellulose is also used for the treatment of moderate tubal hemorrhage during laparoscopic sterilization of women and for small uterine perforations (Sharma and Malhotra, 2003, Sharma et al., 2003). As blood clotting agents, oxidized cellulose fibers are superior to oxidized regenerated cellulose (Pameijer & Jensen, 2007). Remarkable application on using oxidized cellulose in osseous regeneration have been reported (Dias et al., 2003), making oxidized cellulose an excellent scaffolding material, able to replace the most widely used material today, i.e., collagen. In the field of separation techniques, the oxidized cellulose exerts a powerful activity to purify and fractionate proteins, including enzymes, hemoglobins, hormones and seed proteins. Oxidized cellulose is extensively used as well in the chromatography of peptides, amino acids, alkaloids, nucleic acids, nucleotides and metallic ions (Guthrie, 1971). In the paper industry, it is well known that carbonyl and carboxyl functionalities play a decisive role in the pulping process and therefore in the final paper properties. For example, sheets made from the partially oxidized fibers (below 8% conversion) experienced higher wet and dry tensile index, presumably due to an increased opportunity of electrostatic interactions between anionic pulp and cationic polyamideamine-epichlorohydrin, which was added as a wet-strength agent (Kitaoka, Isogai, & Onabe, 1999). In the last five years the preparation of individualized, surface-carboxylated cellulose nanofibers from abundant and renewable plant celluloses (Saito, Nishiyama, Putaux, Vignon, & Isogai 2006), lead to new patented applications of the cellulose nanofibers, namely oxygen barrier (Mukai et al., 2010), gel (Isogai, Kado, & Goi, 2010a), thickener (Isogai, Kado, & Goi 2010b), papermaking (Suzuki et al., 2009), composite (Kato, Isogai, Saito, Oaki, & Nishimura, 2010), cosmetic (Isogai, Kado, & Goi, 2010c) and flexible display panels, electrical devices (Isogai, Saito, & Fukuzumi, 2011). The main object of the present work is focused on reviewing the most recent papers on cellulose selective oxidation using 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and N-hydroxyphthalimide (NHPI).

Section snippets

Cellulose oxidation

Cellulose, because of its polyhydric alcohol structure, is very sensitive to various oxidizing reagents. The extensive modifications which occur during oxidation, give rise to products whose physico-chemical properties strongly depend upon the factors such as: the nature of the oxidizing reagent used, the acidity or basicity of the oxidation medium, and so on. The chemical structure of cellulose is changed in a way that hydroxyl groups are oxidized into the corresponding carbonyl structure,

Conclusions and future work

There is still much effort to carry in the direction of using oxidizing agents like nitrogen oxides, permanganates, peroxides for cellulose, to find the proper reaction conditions (temperature, pressure, appropriate solvents) in order to diminish the non-selective character of those. The introduction of supercritical carbon dioxide as reaction solvent could be a step forward, especially for biomedical applications where the product purity must be strictly ensured. Sodium periodate is one of the

Acknowledgments

One of the authors (S. Coseri) acknowledges the financial support of European Social Fund – “Cristofor I. Simionescu” Postdoctoral Fellowship Programme (ID POSDRU/89/1.5/S/55216), Sectorial Operational Programme Human Resources Development 2007–2013.

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    Members of European Polysaccharides Network of Excellence (EPNOE).

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