The preparation of a new polysiloxane copolymer with glucosylthioureylene groups on the side chains
Introduction
Synthetic polymers with pendent sugar residues are of great interest, not only as simplified model of biopolymers bearing oligosaccharides but also artificial glycoconjugates in biochemistry and medicine. They can be used as texture-enhancing food additives and biologically active polymers [1], [2], [3]. Some of them that are biocompatible and, or biodegradable are increasing used in tissue engineering and controlled drug release and delivery systems. They also can be used in affinity matrixes or gel electrophoresis for bimolecular and chiral components purification [4]. There are various type of synthetic polymers bearing sugar residues: linear polymer––sugar unite as part of main chain, comb polymers––sugar unite as side groups, dendrimers and cross-link hydro gels. Compared with other types, the comb one is the easiest one from the chemical synthesis view. This type of glycopolymers are prepared by a vinyl-type free-radical polymerization of well-defined saccharide-based monomers. Theses monomers were prepared by coupling an unsaturated component to a protected or an unprotected carbohydrate derivative through an ether, ester or amido linkage. Some of published protected and unprotected vinyl saccharide monomers were shown below (Fig. 1).
These polymers had shown some useful properties as cell-specifically culture substrates, and artificial antigens etc. However, all of these reported-glycopolymers were carbon–carbon chain polymer, and most of them were homopolymers. In the same time, most studies shew that the activity of these polymers strongly depended on the structure of the polymers. Therefore, it is not enough for the study of the relationship between the structure and effect based on these carbon-chain glycopolymers. Furthermore, there are also no reports on polyorganosiloxane (POS) with pendent saccharide units. The POS have been well known to show the particular characteristics, such as flexibility of main chains, low glass transition temperature and physiological inertness, etc, and it is easy to prepare copolymers through equalization reaction. Because of the properties of POS, we can expect the POS with sugar units on the side chain should be different from those carbon-chain glycopolymers.
From these point, the present article describes preparation of a new comb glycopolymer––the copolymer of polydimethylsiloxane––poly(glucosylthioureylenetrimethylenemethylsiloxane). The copolymers were prepared by a two-step method: the first was the preparation of the copolysiloxane with suitable hooks––amino groups; the second, the polysiloxanes with amino groups on the side chain reacted with acetylglucosyl isothiocyanate, then through the deprotected reaction, the polyorganosiloxane with free sugar units were given. By this way, the glucosyl was avoided suffering from strict reaction condition, and it was good for keeping the optical activity of the polymer. The target polymers have not only high potentials as biomedical and biotechnological materials, but also important as a model of amphiphilic polymers. Syntheses of the title polymers are summarized in Fig. 2.
Section snippets
Materials
All reagents were either commercially available or prepared according to the cited reference, and were used after purified using suitable method.
Measurements
1H-NMR, 1H–1H-COSY, 13C-NMR, DEPT spectra were recorded on Bruker AC-300 spectrometer and d1-Chloroform or d6-Acetone as solvent, using 5 mm OD tubes at 303 K, no internal reference.
IR spectrum was obtained on Nicolet FT-IR 20SX spectrometer (Japan).
Molecular weight were determined on a Waters 515 Gel Permeation Chromatography (GPC) using mono-disperse
The hydrosilylation reaction of D4H with allylamine
The key step for the preparation of copolysiloxane with pendant sugar units was the preparation of aminotrimethylene copolysiloxane. Hydrosilation addition is an important and easy reaction for preparation of functionalized polysiloxane [18]. However there was no efficient catalyst for the addition of D4H with allyl amine, because of the poison of amino group to the platinum catalyst. We had tried to use Speier catalyst and Karstedt catalyst to prepare the copolymers of
Conclusions
A new carbohydrate-containing copolymer, polysiloxane with pendent sugar units, was prepared by a new two-step method: the preparation of the copolymer with amino groups on the side chain and then the copolysiloxane reacted with glucosyl isothiocyanate; after deprotected reaction the target comb glycoylpolysiloxane was given. In the same time, Platinum oxide was found to be a versatile and powerful hydrosilylation catalyst in the hydrosilylation reaction of aminotrimethylenepolysiloxanes with
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