Photoresponsive cellulose fibers by surface modification with multifunctional cellulose derivatives
Graphical abstract
Introduction
Pulp fibers are intermediate products mainly used in the production of paper and paper boards (Freire, Silvestre, Gandini, & Neto, 2011). However, pulp fibers represent also an attractive substrate for the manufacturing of novel materials owing to their outstanding characteristics. They are relatively cheap, renewable, biodegradable, and can be recycled or converted to energy by combustion at the end of the life cycle of the product. Additionally, the fibers have good mechanical properties and relatively low density (Belgacem and Gandini, 2008, Freire et al., 2011, Ly et al., 2010).
Currently more than 180 million ton per year of pulp fibers (Sixta, 2006) are produced by well-established technologies like mechanical, chemo-mechanical and chemical pulping methods. The properties and the chemical composition (bulk and surface) of pulp fibers from the classical pulping techniques are very well-studied and vary significantly depending on the raw material and the way of the manufacturing. In order to utilize pulp fibers in new value added products, current research is focusing on the modification of their surfaces while keeping bulk properties such as morphology and native fiber wall structure (Grönqvist et al., 2006, Hedenberg and Gatenholm, 1995, Pan and Ragauskas, 2012). Biological (e.g. by enzymes, fungi), chemical (carboxylation, grafting) or plasma treatments and adsorption methods can be applied for this purpose (Gandini and Pasquini, 2012, Utsel, 2012).
From our point of view, the adsorption method appears to be the most promising tool among the techniques mentioned since it is water-based and can be easily combined with existing fiber line stages (Muguet, Pedrazzi, & Colodette, 2011). Traditionally, the research in fiber chemistry and technology has been mainly focusing on the improvement of mechanical, drainage and optical properties of pulp by adsorbing polysaccharides and polysaccharide-based polyelectrolytes for paper manufacture (Köhnke et al., 2010, Schönberg et al., 2001). In this regard, the application of underutilized biomass derived polysaccharides like hemicelluloses recently came into focus (Schwikal et al., 2011, Silva et al., 2011, Vega et al., 2012).
Functional biopolymers with stimuli-responsive capabilities can be used for the modification of pulp in order to generate new fiber-based materials, whose properties could be triggered by an external stimulus. Multifunctional polysaccharide derivatives decorated with cationic and, in particular, light responsive substituents can be applied for this purpose. The light induced alterations, including isomerization, dissociation or crosslinking, of the photoactive substituents were described to cause changes in physical properties of the polymers itself or polymeric solutions (Irie, 1990, Wondraczek et al., 2010, Wondraczek et al., 2011). Consequently, the possibility to control the properties of the interface of the fibers to which they are attached can be expected, and the properties of fiber-based materials and composites might be influenced.
The focus of the studies presented in this paper was to gain information about the interaction of pulp fibers and cellulose derivatives, which were decorated on one hand with cationic (3-carboxypropyl)trimethylammonium chloride ester moieties and on the other with hydrophobic (photoactive) 2-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]acetate substituents (Wondraczek, Pfeifer, & Heinze, 2012). In particular, the influence of the hydrophobic/hydrophilic balance of the derivatives on the adsorption behavior was investigated and a tentative hypothesis of the interaction of pulp fibers and such multifunctional cellulose derivatives was suggested. Moreover, the fiber surface composition and lateral distribution was evaluated by means of ToF-SIMS spectrometry and imaging.
Section snippets
Materials
Eucalyptus air-dried unrefined bleached kraft pulp (bleaching sequence: A-ZD-EOP-D-Z-P brightness: 86% ISO) obtained from Botnia (Kaskö) was disintegrated according ISO 5263:1995(E). The disintegrated pulp was dewatered by centrifugation and the dry matter content according to ISO 638-1978 was determined to be approximately 30%. The total amount of anionic groups in the pulp was determined by the methylene blue sorption method (Fardim, Moreno, & Holmbom, 2005) to be 99 μmol/g. The amount of
Interaction of PCCDs with the pulp fibers
Multifunctional cellulose-based polyelectrolytes decorated with photoactive 2-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]acetate and cationic (3-carboxypropyl)trimethylammonium chloride ester moieties were applied for the modification of eucalyptus unrefined bleached kraft pulp (Fig. 1). The different photoactive cationic cellulose derivatives (PCCDs) possess a degree of substitution of cationic groups (DSN+) of 0.34 and photoactive groups (DSPhoto) of 0.11 (PCCD-1) and 0.37 (PCCD-2), respectively.
Conclusions
Novel multifunctional cellulose derivatives decorated with both cationic and photoactive moieties were adsorbed onto the pulp fiber surfaces. Based on the results from UV–vis spectroscopy and SPR measurements, it was found that the electrostatic interaction was the main driving force of the adsorption of the derivatives onto the fibers. However, hydrophobic interactions between the fibers and the cellulose derivatives as well as between the cellulose derivatives themselves also contributed to
Acknowledgements
Finnish Funding Agency for Technology and Innovation (Tekes) is acknowledged for funding. The authors are grateful to Professor Peter Mattjus from Åbo Akademi University for the access to the SPR instrument and to Josefin Halin for her assistance with the SPR measurements. Annett Pfeifer and Cíntia Salomão Pinto Zarth are acknowledged for providing PCCDs and CCDs.
References (29)
- et al.
Surface modification of cellulose fibers
- et al.
Anionic groups on cellulosic fiber surfaces investigated by XPS, FTIR-ATR, and different sorption methods
Journal of Colloid and Interface Science
(2005) - et al.
The impact of cellulose fiber surface modification on some physico-chemical properties of the ensuing papers
Industrial Crops and Products
(2012) - et al.
Understanding the adsorption mechanism of chitosan onto poly(lactide-co-glycolide) particles
European Journal of Pharmaceutics and Biopharmaceutics
(2008) - et al.
Kraft pulp hornification: A closer look at the preventive effect gained by glucuronoxylan adsorption
Carbohydrate Polymers
(2010) - et al.
Surface functionalization of cellulose by grafting oligoether chains
Materials Chemistry and Physics
(2010) - et al.
Preparation of superabsorbent cellulosic hydrogels
Carbohydrate Polymers
(2012) - et al.
Studies on the fiber surfaces modified with xylan polyelectrolytes
Carbohydrate Polymers
(2012) - et al.
Photoactive polysaccharides
Carbohydrate Polymers
(2011) - et al.
Synthetic photocrosslinkable polysaccharide sulfates
European Polymer Journal
(2010)
New materials from cellulose fibers. A contribution to the implementation of the integrated biorefinery concept
O PAPEL
Laccase-catalysed functionalisation of TMP with tyramine
Holzforschung
Conversion of plastic/cellulose waste into composites. I. Model of the interphase
Journal of Applied Polymer Science
Properties and applications of photoresponsive polymers
Pure and Applied Chemistry
Cited by (24)
Isolation of cellulose fibers from wetland reed grass through an integrated subcritical water hydrolysis-pulping-bleaching process
2022, FuelCitation Excerpt :The applications of cellulose fiber are recognized in several industries such as pulp and paper [3], textiles [4], pharmaceuticals [5], biomedical [6], electrical devices [7], electronics [8], biofuels [9], biochemicals [10,11] and biocomposites [12]. Apart from the cellulose fibers, cellulose derivatives such as alkyl cellulose, cellulose acetates, nitrates, sulfates, epoxides and halides are vastly implemented in different fields [13,14]. The popularity and emerging market of natural cellulosic fiber are dependent on its potential to replace synthetic plastic polymers, which cause the environment and pose health hazards to animals and human health [15].
Fundamental aspects of the non-covalent modification of cellulose via polymer adsorption
2021, Advances in Colloid and Interface ScienceCitation Excerpt :In fact, it is almost impossible to vary these parameters independently and thereby determine their separate effects in experimental situations [75]. Grigoray et al. [76] proposed that there should be a hydrophilic-hydrophobic balance in polymers to make adsorption possible, which is actually the balance between χ and χs. This rationale was used by Grigoray et al. to make a water-soluble photo-responsive derivative of CMC that could adsorb on the fibre surfaces and exhibit photo-responsive cross-linking [76].
Natural polymers-based light-induced hydrogels: Promising biomaterials for biomedical applications
2020, Coordination Chemistry ReviewsCitation Excerpt :Although its pure form has been successfully used in a variety of biomedical applications, it is predominantly used as a precursor for ester-based derivatives such as carboxymethyl cellulose, and cellulose nitrate derivatives [161,166]. Alternatively, it can also be used as composite or blend component, serving as a natural constituent of a structure, which improves the mechanical and biological properties of said structure through its versatile and easily manipulatable composition [167,168]. Different physical forms of cellulose with various micro- and macro-morphology can used, which include but are not limited to cellulose nanofibers, cellulose-based hydrogels, and cellulose-based membranes [161].
Fabrication and characterization of cellulose-based green materials
2020, Advanced Green Materials: Fabrication, Characterization and Applications of Biopolymers and BiocompositesPreparation of reactive fibre interfaces using multifunctional cellulose derivatives
2015, Carbohydrate PolymersCitation Excerpt :In the context of the emerging biorefinery concept and due to the limited economic growth in the field of classical pulp- and paper production, an intense search for added-value materials from wood pulp has been reported recently. For example, functional fibres (Grigoray, Wondraczek, Heikkilä, Fardim, & Heinze, 2014; Martínez, Phillips, & Whitesides, 2010; Vega et al., 2013; Zhou, Yang, & Zhou, 2014), cellulose-based nanomaterials (Dufresne, 2012; Filpponen et al., 2012; Junka et al., 2014; Kettunen née Pääkkö, 2013; Klemm et al., 2011; Missoum, Belgacem, & Bras, 2013; Moon, Martini, Nairn, Simonsen, & Youngblood, 2011; Peresin, Habibi, Zoppe, Pawlak, & Rojas, 2010), cellulose beads (Gericke, Trygg, & Fardim, 2013), cellulose-based composites (Khalil, Bhat, Ireana, & Yusra, 2012; Huber et al., 2012; Lange, Touaiti, & Fardim, 2013; Narewska, Lassila, & Fardim, 2014; Satyanarayana, Arizaga, & Wypych, 2009) have been successfully prepared at the laboratory scale. Functional fibres, which possess particular functionalities while preserving the excellent mechanical properties of the traditional pulp fibres, can be obtained by different chemical, enzymatic, or physical treatments (Elegir, Kindl, Sadocco, & Orlandi, 2008; Kim, Zille, Murkovic, Güebitz, & Cavaco-Paulo, 2007; Li, Tabil, & Panigrahi, 2007; Persson, 2004; Qiu & Hu, 2013).