Self-assembled supermolecular hydrogel based on hydroxyethyl cellulose: Formation, in vitro release and bacteriostasis application
Introduction
Hydrogel is a kind of three-dimensional network which consists of covalently crosslinked hydrophilic polymers, and has been subjected to extensive studies due to its importance and future potential in a wide range of applications (Can, 2005; Maswal, Chat, & Dar, 2015; Mohammed, Grishkewich, Berry, & Tam, 2015), such as cosmetics, biomaterials and drug delivery systems (Shen et al., 2016; Yan, Lin, Zhang, & Huang, 2011; Zhang, Zhang, Zou, & Mcclements, 2016). Recently, the hydrogel system based on polysaccharide, including chitosan, alginate, carrageenan, dextran, hyaluronan, cellulose and so on, has received increasing interest in many practical applications (Coviello, Matricardi, Marianecci, & Alhaique, 2007; Kong, Kim, & Park, 2016; Vieira & Airoldi, 2008), because polysaccharides are extremely advantageous compared to synthetic polymers for the properties of biodegradable, renewable and easily available from commercial sources on an industrial scale (Shulepov, Kozhikhova, Panfilova, Ivantsova, & Mironov, 2016). In these years polysaccharide hydrogel system with self-assemble ability draws more and more attention for its noncovalent interactions with many molecules (Daoud-Mahammed et al., 2007; Fraix, Gref, & Sortino, 2014; Huh et al., 2004, Nakagawa et al., 2012).
As the most abundant polysaccharide available in nature, cellulose is popular with many research groups for its renewability, excellent biocompatibility and biodegradability (Altomare, Cochis, Carletta, Rimondini, & Farè, 2016; Pandey, Ahn, Lee, Mohanty, & Misra, 2010; Pandey, Takagi, Nakagaito, Saini, & Ahn, 2012), and it is a versatile molecule which bears potential for many applications in native or modified forms (Costa et al., 2013; Khan, Huq, Khan, Riedl, & Lacroix, 2014; Peng, Meng, & Li, 2016; Sangeetha, Meenakshi, & Sundaram, 2016; Stepan, Monshizadeh, Hummel, Roselli, & Sixta, 2016; Wu & Farnood, 2015). Cellulose is a linear polysaccharide composed of 1,4-β-d-glucopyranosyl units (Vadodaria and English, 2016; Xu, Chen, Rosswurm, Yao, & Janaswamy, 2016), the chains in it form a tight network which are stabilized through strong inter- and intra-chain hydrogen bonds (Nishiyama, Langan, & Chanzy, 2002; O’Sullivan, 1997). Such structure make cellulose insoluble in water and thus its wholesome utility has been limited.
In that case, cellulose derivative such as HEC is employed in many application areas. HEC is a kind of non-ionic cellulose ether with good water solubility which is easily manufactured by using natural cellulose as raw materials. Hydrophobically modified HEC was synthesized by adding small amounts of hydrophobic groups to the starting material HEC (Wang & Ye, 2013). Since hydrophobically modification of HEC was first investigated by Landoll (1982), it had been extensively studied in many aspects for past two decades, including the solution behavior, rheological property, hydrodynamic and thermodynamic parameters (Gonzalez, Muller, Torres, & Saez, 2005; Laschet, Plog, Clasen, & Kulicke, 2004; Li, Meunier, & Partain, 2014; Maestro, Gonzalez, & Gutierrez, 2002; Vadodaria and English, 2016, Zhao and Chen, 2007). The advantages of hydrophobically modified HEC over HEC can be divided into two aspects. On one hand, the former has remarkable abilities of viscosification property at relatively lower molecular mass compared to the latter as a result of the formation of interacting networks, and the networks are formed due to the intra- and intermolecular aggregation of hydrophobic groups in the hydrophobically modified HEC (Vadodaria & English, 2016). On the other hand, the small amounts of hydrophobic groups on HEC can self-assemble into particles with hydrophobic cores, and the particles can also encapsulate hydrophobic drugs to provide hydrophobically modified HEC with new functions (Tomatsu, Hashidzume, & Harada, 2005). Thus, hydrophobically modified HEC has been of particular interest because of their potential for biomedical applications (Kwon, Park, Chung, Kwon, & Jeong, 2003).
Cyclodextrins (CDs), which are composed of hydrophilic outer surfaces and hydrophobic inner cavities, are non-reducing cyclic maltooligosaccharides produced from starch by cyclodextrin glycosyltransferase (Bibby, Davies, & Tucker, 2000; Uitdehaag, Van, Dijkhuizen, Elber, & Dijkstra, 2001; Wibaux & Paesen, 2010). They are one of the most widely used host molecules due to their noncovalent interactions with various guest moieties and hydrophobic side chains (Fu et al., 2016, Li et al., 2015; Liu, Fan, Hu, & Tang, 2004; Quaglia et al., 2001, Shen et al., 2016). Thereafter, CD-based polysaccharide hydrogels become one of the most widely studied hydrogels in the field of self-assembly (Tan, Katharina, Fu, Blencowe, & Qiao, 2014; Tan et al., 2015). Furthermore, the encapsulation ability of CDs makes CD-based hydrogels with various functions, which has widened the applications of self-assembled hydrogel, especially in the fields of biomedical and pharmaceutical (Li, Ni, & Leong, 2003; Liu and Fan, 2005, Liu, Fan, Hu et al., 2004; Liu, Fan, Kang, & Sun, 2004; Quaglia et al., 2001, Sreenivasan, 1997). Water soluble β-CD polymers, which can be obtained by the reaction of β-CD with epichorohydrin (EPI) in an alkaline medium, have been widely studied and applied for many years (Gref et al., 2006, Koopmans and Ritter, 2008, Oliveira et al., 2015; Renard, Deratani, Volet, & Sebille, 1997). To our knowledge, no reports have been performed on the formation of self-assembled supermolecular hydrogel between hydrophobically modified HEC and β-CDP.
In the field of self-assembled hydrogel, cyclodextrin is used the most for the easily obtaining of the binding site, however, few reports about self-assembled hydrogel have been focused on cellulose. Herein, we prepared a cyclodextrin-based hydrogel containing HEC, which was based on the host-guest interaction between hydrophobic modified HEC and cyclodextrin polymer. The purpose of this study is focus on the preparation of a self-assembled bacteriostatic hydrogel based on HEC. As an important biopolymer, HEC was used here instead of synthetic polymers, taking the advantages of cellulose resources, including renewable ability, biocompatibility and biodegradability. Meanwhile, self-assembly is an effective method for synthesizing functional materials, owing to its simplicity and free of organic reagents in preparation. Firstly, HEC was grafted by hydrophobic lauryl side chains. Then, β-cyclodextrin polymer was controlled synthesized by crosslinking of β-CD with EPI under certain reaction conditions (Koopmans & Ritter, 2008), which could improve the water solubility of β-CD and enhanced the strength of the formation self-assembled supermolecular hydrogel. According to the CD inclusion chemistry, a cellulose-based gel-(β)CDP-HEC could be obtained just in aqueous solution due to the self-assembly process. Furthermore, functional molecules of EG were also loaded into parts of the inner cavities of β-CDP in gel-(β)CDP-HEC through the host-guest interaction (Gong et al., 2016), which could be extracted from clove oil, cinnamon, nutmeg and basil and had been widely used as preservatives in food, active pharmaceutical ingredient as well as cosmetics (Phunpee et al., 2015, Pramod et al., 2016). Besides, the release characteristics, thermal stability and bacteriostasis application of the gel-(β)CDP-HEC containing EG were also evaluated in this paper.
Section snippets
Materials
HEC (720 000 g mol−1, Molar degree of substitution = 1.0 ∼ 1.2) was purchased from Sigma-Aldrich Co., Ltd. (St. Louis, MO, USA) and used without further purification. 1-Chlorododecane (C12, AR), EG (AR), EPI (AR), phenolphthalein (AR) and β-CD (1135 g mol−1, purity >98%) were obtained from Aladdin Industrial Co., Ltd. (Shanghai, China). N,N-dimethylacetamide (DMAc, AR), lithium chloride (LiCl, AR) and pyridine (AR) were supplied by Kermel Chemical Reagent Co., Ltd. (Tianjin, China). Escherichia coli
Characterization of HECC12
The hydrophobic C12 side chains are grafted onto HEC by Williamson etherification reaction. After etherification, the cavities of β-CDP can provide hydrophobic binding sites with C12 side chains during the formation of gel-(β)CDP-HEC. The grafting of C12 side chains on HEC are characterized by FTIR, SEM and 1H NMR, respectively.
Fig. 1a and b are the FTIR spectra of HEC and HECC12, respectively. Compared to Fig. 1a, the strong bands at 2924 and 2874 cm−1 in Fig. 1b, which are attributed to the
Conclusions
A new self-assembled, cellulose-based hydrogel system: gel-(β)CDP-HEC is synthesized through the host-guest interaction. The critical concentrations of HECC12 and β-CDP are both fixed at 30 mg mL−1 according to the detection results of dynamic viscosity, rheological property and swelling ratio. Furthermore, in the self-assembled process, the hydrophobic cavities of β-CDP not only provided binding sites for associating with HECC12, but also have 21.89 wt% of active residual cavities which can load
Acknowledgments
This study is supported by the National Natural Science Fund of China (NSFC, 51403030), Fundamental Research Funds for the Central Universities of China (2572017CB23), China Postdoctoral Science Foundation (2012M520696) and Heilongjiang Postdoctoral Grant (LBH-Z12009) are also gratefully acknowledged for support.
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