Poly PNIPAAm

Many kinds of nonbiodegradable vinyl-type hydrophilic polymers were also used in combination with aliphatic polyesters to prepare amphiphilic block copolymers. Two typical examples of the vinyl-polymers used are poly(/V-isopropylacrylamide) (PNIPAAm) [149-152] and poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) [153]. PNIPAAm is well known as a temperature-responsive polymer and has been used in biomedicine to provide smart materials. Temperature-responsive nanoparticles or polymer micelles could be prepared using PNIPAAm-6-PLA block copolymers [149-152]. PMPC is also a well-known biocompatible polymer that suppresses protein adsorption and platelet adhesion, and has been used as the hydrophilic outer shell of polymer micelles consisting of a block copolymer of PMPC -co-PLA [153]. Many other vinyl-type polymers used for PLA-based amphiphilic block copolymers were also introduced in a recent review [16]. 

Methoxy poly(ethyleneglycol) (mPEG) was the most frequently used semitelechelic polymer for over 2 decades. It has been successfully used for the modification of various proteins, biomedical surfaces and hydrophobic anticancer drugs (for reviews see References [3,9,10]. Recently, a number of new semitelechelic (ST) polymers, such as ST-poly(A -isopropylacry-lamide) (ST-PNIPAAM) [11-15], ST-poly(4-acryloylmorpholine) (ST-PAcM) [16], ST-poly(A-vinylpyrrolidone) (ST-PVP) [17], and ST-poly[A-(2-hydroxypropyl)methacrylamide] (ST-PHPMA) [18-21] have been prepared and shown to be effective in the modification of proteins or biomedical surfaces. 

Poly(A-isopropyl acrylamide) (PNIPAAm) is the most extensively studied temperature-sensitive polymer [10-20]. Crosslinked PNIPAAm exhibits drastic swelling transition at its lower critical solution temperature... 

The temperature-sensitive poly(A-isopropyl acrylamide) and pH-sensitive poly(methacrylic acid) were used as the two component networks in the IPN system. Since both A-isopropyl acrylamide (NIPAAm) (Fisher Scientific, Pittsburgh, PA) and methacrylic acid (MAA) (Aldrich, Milwaukee, Wl) react by the same polymerization mechanism, a sequential method was used to avoid the formation of a PNIPAAm/PMAA copolymer. A UV-initiated solution-polymerization technique offered a quick and convenient way to achieve the interpenetration of the networks. Polymer network I was prepared and purified before polymer network II was synthesized in the presence of network I. Figure I shows the typical IPN structure. 

Many recent studies on polymer gels are related to volume phase transition phenomena of poly(acrylamide) PAAm gel [7] and poly(N-isopropyl acrylamide) PNIPAAm gel [8, 9]. The volume phase transition in gels was extensively studied by Tanaka and his coworkers [10, 11]. 

Mi, K. Y., Yong, K. S., Young, M. L., and Chong, S. C. Effect of polymer complex formation on the cloud-point of poly(Al-isopropylacrylamide) (PNIPAAm) in the poly(NIPAAm-co-acrylic acid) polyelectrolyte complex between poly(acrylic acid) and poly(l-lysine). Polymer 39 3703-3708, 1998. 

The effect of reactive plasma and its distance form the PE film surface has also been studied in detail [138]. The surface of polyethylene films was modified with various water-soluble polymers [(poly[2-(methacryloy-loxy)ethyl phosphorylcholine] (PMPC), poly[2-(glucosyloxy)ethyl methacrylate] (PGEMA), poly(N-isopropylacrylamide) (PNIPAAm) and poly[N-(2-hy-droxypropyl) methacrylamide] (PHPMA)] using Ar plasma-post polymerisation technique [139]. Here, the reactive sites were generated on the PE surface under the influence of argon plasma. These reactive sites on the surface were then utilised to covalently anchor the functional monomers as shown in Scheme 11. 

Affinity chromatography of streptavidin was performed on a PET chip. The microchannel was first filled with the dual-modified latex beads (as shown in Figure 6.3). The biotinylated beads were surface-modified with a temperature-sensitive polymer, poly(N-isopropylacrylamide (PNIPAAm, 11 kDa). When the temperature was raised above the lower critical solution temperature (LCST) of PNIPAAm, the beads aggregated and adhered to the channel wall, because of a hydrophilic-to-hydrophobic phase transition. Then streptavidin from a sample solution was captured by these adhered biotinylated beads. Thereafter, when the temperature was reduced below the LCST, the beads dissociated and eluted from the channel wall together with the captured streptavidin [203],... 

During precipitation polymerization, all ingredients are dissolved in a solvent (water) to form a homogeneous mixture in which initiation of polymerization takes place. The formed polymers are transformed into a collapsed state because the reaction temperature is far above VPTT (for example in the case of PNIPAAm) and become crosslinked by crosslinker molecules to form a colloidal polymer network or microgel. This technique has been widely used for the synthesis of thermosensitive PNIPAAm [30-35] and poly(/V-vinyl caprolactam) (PVCL) [36] microgels. 

Lapeyre et al. [99] prepared aqueous microgels consisting of thermorespon-sive PNIPAAm core and thermo- and glucose-responsive poly(NIPAAm-co-acrylamidophenylboronic acid) shell. The radius of the core in the collapsed state (40°C) was 65 nm. By variation of the monomer concentrations added during the second polymerization step from 20 to 80 mM, the shell thickness increased from 15 to 38 nm. 

Li et al. [100] synthesized core-shell microgels with temperature-sensitive PNIPAAm core and pH-sensitive poly(4-vinylpyridine) (P4VP) shell. Narrowly distributed microgel particles with core diameter of 95 nm and shell thickness of approximately 30 nm were obtained. 

Okano and coworkers have patterned poly(N-isopropylacryl-amide) (PNIPAAm), a material similar to BSA and PEG in that it does not adhere to cells at room temperature. In this experiment, a composite solution of PNIPAAm dissolved in propanol (55 wt%) was uniformly coated inside a commercial cell culture dish. The polymer was then patterned, using standard e-beam lithography, onto the surface of a cell culture dish to test the dynamic behavior of cells for potential clinical applications. A metal mask (60 mm o.d. 

Poly(amino acid)s (PAAs) have also been used in drug delivery PEO-(l-aspartic acid) block copolymer nano-associates , formed by dialysis from a dimethyl acetamide solution against water, could be loaded with vasopressin. PLA-(L-lysine) block copolymer microcapsules loaded with fluorescently labelled (FITC) dextran showed release profiles dependent on amino acid content. In a nice study, poly(glutamate(OMe)-sarcosine) block copolymer particles were surface-grafted with poly(A-isopropyl acrylamide) (PNIPAAm) to produce a thermally responsive delivery system FITC-dextran release was faster below the lower critical solution temperature (LCST) than above it. PAAs are prepared by ring-opening polymerisation of A-carboxyanhydride amino acid derivatives, as shown in Scheme 1. 

To mimic the macromolecular-based ECM in biological tissue, the cell adhesion and proliferation properties of hydrogels are critical parameters. However, various hydrogels that originate from natural resources, such as alginate [87], chitosan [88, 89], and hyaluronic acid [90], and that are synthetically created, such as poly (7V-isopropylacrylamide) (PNIPAAm) [91], PEO [92], PVA [93], and poly(ethylene glycol) (PEG) [94], show a poor cellular viability without modification with cell adhesive proteins or peptides, such as collagen, laminin, fibronectin, and the RGD (Arg-Gly-Asp) sequence. 

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