Novel ABA type amphiphilic copolymers (PCL-APS-PCL) consisting of polycaprolactone (PCL) (A) as hydrophobic block and N,N′-bis (2-hydroxyethyl) methylamine ammonium propane sulfonate (APS) (B) as hydrophilic segment, self-assembled into nanoparticles (NPs) with solvent evaporation method. The sizes and size distributions of NPs were characterized by dynamic light scattering. The morphology of NPs was observed by scanning electron microscopy (SEM). The critical micelle concentration (CMC) was determined by fluorescent probe. The drug loading content (DLC) and the drug release amount were characterized by UV–visible spectrophotometer. The cytotoxicity of the NPs was measured by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenylte-trazoliumbromide (MTT) assay. It was found that the NPs were spherical in shape with sizes around 100 nm. The CMCs of the copolymers were quite low (×10⁻⁴ mg/mL). The DLC decreased with lengthening of hydrophobic PCL block. In vitro drug release experiment demonstrated that the release rate of paclitaxel sped with the decrease of PCL length. MTT results showed that NPs were nontoxic to osteoblast and human epithelial carcinoma (hela) cells. After drug loading, NPs could restrain the growth of hela or even kill hela cells. Therefore, these preliminary studies suggest that the novel PCL-APS-PCL NPs have a great potential application as anticancer drug-delivery carriers. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2012.

Amphiphilic star shape poly(ε-caprolactone)-b-hyperbranched polyglycidol (sPCL-HPG) were synthesized and used to investigate micell formation and to encapsulate hydrophobic drugs. The synthesis of sPCL-HPG copolymers was carried out by using sPCL as macroinitiator for the ensuing of hypergrafting reaction with glycidols. ¹H-NMR and FTIR were used to characterize sPCL-b-HPG structures. The self-assembled structure of the sPCL-HPG was characterized by scanning electronic microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The size and size dispersities of micelles were measured by dynamic light scattering DLS. Critical micelle concentration (CMC) was determined using pyrene as fluorescent probe. Hydrophobic methyl red was encapsulated in sPCL-HPG micelles to illustrate hydrophobic drug loading. The copolymer micelles were used to enhance paclitaxel solubility. The results showed that hydrophobic drugs could be encapsulated in the sPCL-HPG micelles. The paclitaxel solubility in the micelles of 5 wt% of sPCL23-HPG170 got to 168 µg/ml. sPCL-HPG, which have biodegrability and hydrophobicity at PCL part and smaller size of HPG fragments while maintaining the total repeating units of glycidols, provide an alternative choice of carriers for poorly soluble drugs. Copyright © 2011 John Wiley & Sons, Ltd.

Phosphorylcholine-containing poly(L-lactide) (PLLA-PC) was synthesized by ring-opening polymerization of L-lactide in the presence of glycerophosphorylcholine originated from egg lecithin. Self-assembling micelles were then obtained by film hydration, ultrasonication and stirring. Transmission electron microscopy and confocal laser scanning microscopy confirmed the micellar structure with hydrophobic core and hydrophilic shell. The critical micellar concentration (CMC) value of PLLA-PC was only 1/50 that of naturally occurring PC, in agreement with a better surfactant property of the former. Dynamic light scattering showed that the size and size distribution of micelles varied with dilution, but the CMC was independent of the concentration of NaCl solution within 0.9 wt%, indicating that the micelles could be stable upon intravenous injection. In addition, the micelle solution could be stored at 4 °C over 30 days without any noticeable changes, whereas at 37 °C, the size, size distribution and the number of micelles decreased over time due to degradation. The solubility of clofazimine, a highly hydrophobic drug, was found to be 11.9 µg/ml in the PLLA-PC micellar solution, which was 40 times that in pure water. This preliminary study suggests that PLLA-PC micelles present a great potential as delivery system for hydrophobic drugs. Copyright © 2011 John Wiley & Sons, Ltd.

Novel biodegradable polycaprolactone containing N,N′-bis (2-hydroxyethyl) methylamine ammonium propane sulfonate (PCL-APS) was synthesized by ring-opening polymerization. The resulting polymers were characterized by nuclear magnetic resonance spectrum (NMR), Fourier transform infrared (FTIR) spectroscopy, gel permeation chromatograph (GPC), differential scanning calorimetry (DSC), and water contact angle (WCA). These measurements showed that the APS unit was introduced into polymers. The hydrolysis of PCL-APS was evaluated by soaking the polymer membranes in a pH = 3.20 acid solution. The rate of weight loss was increased with the content of APS increasing in polymer. The compatibility of polymers were evaluated by platelet adhesion, hemolytic test, and activated partial thromboplastic time (APTT) and prothrombin time (PT) experiments. Results showed that adhered platelets deceased after introducing sulfobetaine as compared to the control PCL, little hemolysis took place on PCL-APS, and APTT of PCL-APS polymers was prolonged than that of control PCL. Therefore, polycaprolactone containing sulfobetaine is a promising biodegradable polymer with good blood compatibility. © 2011 Wiley Periodicals, Inc. J Biomed Mater Res Part A:, 2011.

A series of bioresorbable polymers were prepared by ring-opening polymerization of L-lactide (LLA), DL-lactide (DLLA), ϵ-caprolactone (CL) and 1,3-trimethylene carbonate (TMC), using low toxic zinc lactate as catalyst. The various PLLA, PTMC, PCL homopolymers, and PLLA-TMC, PDLLA-TMC, PCL-TMC copolymers with 50/50 molar ratios were characterized by using analytical techniques such as proton nuclear magnetic resonance, gel permeation chromatography, tensiometer, and differential scanning calorimetry. The haemo- and cyto-compatibility were investigated in order to evaluate the potential of the polymers as coating material in drug eluting stents. Haemolysis tests show that all the homo- and copolymers present very low haemolytic ratios, indicating good haemolytic properties. Adhesion and activation of platelets were observed on the surface of PLLA, PCL, PLLA-TMC, and PDLLA-TMC films, while less platelets and lower activation were found on PTMC. The most interesting results were obtained with PCL-TMC which exhibited the lowest degree of activation with few adhered platelets, in agreement with its outstanding anticoagulant properties. Both indirect and direct cytocompatibility studies were performed on the polymers. The relative growth ratio data obtained from the liquid extracts during the 6-day cell culture period indicate that all the polymers present very low cytotoxicity. Microscopic observations demonstrate adhesion, spreading and proliferation of human umbilical vein endothelial cells ECV304. Therefore, it is concluded that these bioresorbable polymers, in particular PCL-TMC, are promising candidate materials as drug loading coating material in drug eluting stents. © 2010 Wiley Periodicals, Inc. J Biomed Mater Res 2010