Synthesis and characterization of an amphiphilic hyperbranched poly(amine‐ester)‐co‐D,L‐lactide (HPAE‐co‐PLA) copolymers and their nanoparticles for protein drug delivery

A series of hyperbranched poly(amine‐ester)‐co‐D ,L ‐lactide (HPAE‐co‐PLA) copolymer were synthesized by ring‐opening polymerization of D ,L ‐lactide with Sn(Oct)₂ as catalyst to a fourth generation branched poly(amine‐ester) (HPAE‐OHs4). The chemical structures of copolymers were determined by FTIR, ¹H‐NMR, ¹³C‐NMR, and TGA. Double emulsion (DE) and nanoprecipitation (NP) method were used to fabricate the nanoparticles of these copolymers encapsulating bovine serum albumin (BSA) as a model. DSC thermo‐grams indicated that the nanoparticles with BSA kept stable below 40°C. Different factors which influence on particular size and encapsulation efficiency (EE) were investigated. Their EE to BSA could reach 97.8% at an available condition. In vitro release behavior of NPs showed a continuous release after a burst release. The stability maintenance of BSA in the nanoparticle release in vitro was also measured via circular dichroism and fluorescence spectrometry. The results showed that the copolymer nanoparticles have a promising potential in protein delivery system. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of cyhalothrin‐loaded poly(2‐hydroxyethyl methacrylate)‐co‐polylactide (PHEMA‐co‐PLA) ultrafine particles

Poly(2‐hydroxyethyl methacrylate)‐co‐polylactide (PHEMA‐co‐PLA) and its corresponding cyhalothrin‐loaded ultrafine particles were successfully synthesized and prepared, respectively. The chemical structures of the copolymers have been confirmed by Fourier transform infrared spectroscopy (FTIR), ¹H‐nuclear magnetic resonance (¹H‐NMR), ¹³C‐nuclear magnetic resonance (¹³C‐NMR), and thermogravimetric analysis (TGA). Furthermore, the particle size, the cyhalothrin loading content (LC), and the cyhalothrin release behavior were investigated. PHEMA‐co‐PLA proved to be a good material for the preparation of ultrafine particles for lipophilic pesticide delivery. The developed cyhalothrin‐loaded PHEMA‐co‐PLA ultrafine particles showed good dispersity in water and sustained release behavior. In addition, it is easy to be prepared by both nanoprecipitation method and emulsion/solvent evaporation method. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of amphiphilic pluronic (F68)‐1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphoethanolamine copolymers and their micelles as a drug carrier

A new Pluronic (F68)‐1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphoethanolamine (DPPE) (Pluronic (F68)–DPPE) copolymer was synthesized with Pluronic (F68) and DPPE. The chemical structure and physical properties of copolymers were determined by FTIR, ¹H NMR, ¹³C NMR, ³¹P NMR, and TGA. Environmental scanning electron microscopy, fluorescence spectroscopy, and dynamic light scattering method confirmed the formation of copolymeric micelles of Pluronic (F68)‐DPPE. To estimate the feasibility as novel drug carriers, the copolymer micelles were prepared by the phase separation dialysis method. Amphotericin B as a lipophilic model drug was incorporated into copolymeric micelles and the drug release behavior was investigated. It was found that the chemical composition of the micelle was a key factor in controlling micelles size, drug‐loading content, and drug release behavior. As DPPE segment weight ratio increased, the micelle size and drug‐loading content increased, and the drug release rate decreased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Design of hemocompatible poly(DMAEMA‐co‐PEGMA) hydrogels for controlled release of insulin

This works aims at (i) studying the antiadhesive properties and the hemocompatibility of poly[2‐(dimethylamino)ethyl methacrylate]‐co‐poly[(ethylene glycol)methacrylate] [poly(DMAEMA‐co‐PEGMA)] copolymers and (ii) investigating the insulin delivery kinetics through hydrogels at physiological pH. A series of poly(DMAEMA‐co‐PEGMA) hydrogels have been synthesized, and their controlled composition was confirmed by X‐ray photoelectron spectroscopy. Then, antibiofouling properties of hydrogels—fibrinogen, erythrocytes, and thrombocytes adhesion—are correlated to their molecular compositions through their hydrophilic properties. As DMAEMA/PEGMA ratio of 70/30 (D70) offers the best compromise between pH sensitivity and hemocompatibility, it is selected for investigating the kinetic rate of insulin release at physiological pH, and the diffusion coefficient of insulin in gel is found to be 0.64 × 10^?7 cm² s^?1. Overall, this study unveils that poly(DMAEMA‐co‐PEGMA) copolymers are promising hemocompatible materials for drug delivery systems. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42365.     

Thermosensitive polymeric micelles based on the triblock copolymer poly(d,l‐lactide)‐b‐poly(N‐isopropyl acrylamide)‐b‐poly(d,l‐lactide) for controllable drug delivery

A thermosensitive amphiphilic triblock copolymer, poly(d,l ‐lactide) (PLA)‐b‐poly(N‐isopropyl acrylamide) (PNIPAAM)‐b‐PLA, was synthesized by the ring‐opening polymerization of d,l ‐lactide; the reaction was initiated from a dihydroxy‐terminated poly(N‐isopropyl acrylamide) homopolymer (HO‐PNIPAAM‐OH) created by radical polymerization. The molecular structure, thermosensitive characteristics, and micellization behavior of the obtained triblock copolymer were characterized with Fourier transform infrared spectroscopy, ¹H‐NMR, gel permeation chromatography, dynamic light scattering, and transmission electron microscopy. The obtained results indicate that the composition of PLA‐b‐PNIPAAM‐b‐PLA was in good agreement with what was preconceived. This copolymer could self‐assemble into spherical core–shell micelles (ca. 75–80 nm) in aqueous solution and exhibited a phase‐transition temperature around 26 °C. Furthermore, the drug‐delivery properties of the PLA‐b‐PNIPAAM‐b‐PLA micelles were investigated. The drug‐release test indicated that the synthesized PLA‐b‐PNIPAAM‐b‐PLA micelles could be used as nanocarriers of the anticancer drug adriamycin (ADR) to effectively control the release of the drug. The drug‐delivery properties of PLA‐b‐PNIPAAM‐b‐PLA showed obvious thermosensitive characteristics, and the release time of ADR could be extended to 50 h. This represents a significant improvement from previous PNIPAAM‐based drug‐delivery systems. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45304.     

Bioinspired photo-degradable amphiphilic hyperbranched poly(amino ester)s: Facile synthesis and intracellular drug delivery

A novel amphiphilic photo-degradable hyperbranched polymer was reported at the first time. The hyperbranched o-nitrobenzyl containing poly(amino ester)s (HPAE) were prepared by one-pot Michael addition polymerization. The photo-induced degradation of hyperbranched poly(amino ester)s was confirmed by gel permeation chromatography (GPC) and UV-vis spectra. Bioinspired phosphorylcholine grafted HPAE (HPAE-PC) was synthesized via thiol-ene click chemistry. HPAE-PC can self-assemble to micelles and the micelles could be disassembled under UV irradiation because of the photo-degradation of HPAE. HPAE-PC micelles were used to load anticancer drug Doxorubicin (DOX). In vitro drug release studies showed that the release of DOX was much faster in the presence of UV irradiation than that without UV irradiation. The fluorescence microscope results indicated that DOX-loaded micelles exhibited faster drug release in A549 cells after UV irradiation. Moreover, the DOX-loaded HPAE-PC micelles under UV irradiation exhibited better anticancer activity against A549 cells than that of the nonirradiated ones. The novel amphiphilic photo-degradable hyperbranched polymers can be used to construct spatiotemporal on-demand drug delivery system for cancer therapy.     

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) graft copolymers and their application as carriers for drug delivery system

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) [P(NIPAM‐co‐HEMA)] copolymer was synthesized by controlled radical polymerization from respective N‐isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) monomers with a predetermined ratio. To prepare the thermosensitive and biodegradable nanoparticles, new thermosensitive graft copolymer, poly(L ‐lactide)‐graft‐poly(N‐isoporylacrylamide‐co‐hydroxyethyl methacrylate) [PLLA‐g‐P(NIPAM‐co‐HEMA)], with the lower critical solution temperature (LCST) near the normal body temperature, was synthesized by ring opening polymerization of L ‐lactide in the presence of P(NIPAM‐co‐HEMA). The amphiphilic property of the graft copolymers was formed by the grafting of the PLLA hydrophobic chains onto the PNIPAM based hydrophilic backbone. Therefore, the graft copolymers can self‐assemble into uniformly spherical micelles ò about 150–240 nm in diameter as observed by the field emission scanning electron microscope and dynamic light scattering. Dexamethasone can be loaded into these nanostructures during dialysis with a relative high loading capacity and its in vitro release depends on temperature. Above the LCST, most of the drugs were released from the drug‐loaded micelles, whereas a large amount of drugs still remains in the micelles after 48 h below the LCST. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fabrication and drug release properties of poly(5‐benzyloxy‐trimethylene‐co‐glycolide) microspheres

Poly(5‐benzyloxy‐trimethylene carbonate‐co‐glycolide) random copolymers were synthesized through the ring‐opening polymerization of 5‐benzyloxy‐trimethylene carbonate and glycolide (GA). The copolymers with different compositions, PBG‐1 with 17% GA units and PBG‐2 with 45% GA units, were obtained. Using these copolymers, microsphere drug delivery systems with submicron sizes were fabricated using an “ultrasonic assisted precipitation method.” The in‐vitro drug release from these microspheres was investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Drug release from electrospun fibers of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) grafted with poly(N‐vinylpyrrolidone)

Poly(N‐vinylpyrrolidone) (PVP) groups were grafted onto poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) backbone to modify the properties of PHBV and synthesize a new novel biocompatible graft copolymer. Based on these graft copolymers, electrospun fiber mats and commonly cast films were explored as drug delivery vehicles using tetracycline hydrochloride as a model drug. Toward that end, the fibers were electrospun and the films were cast from chloroform solutions containing a small amount of methanol to solubilize the drug. The Brookfield viscosities of the solution were determined to achieve the optimal electrospinning conditions. The vitro release of the tetracycline hydrochloride from these new drug delivery systems was followed by UV–vis spectroscopy. To probe into the factors affected on the release behavior of these drug delivery systems, their water absorbing abilities in phosphate buffer solution were investigated, together with their surface hydrophilicity, porosity and crystallization properties were characterized by water contact angles, capillary flow porometer, DSC, and WAXD, respectively. The morphological changes of these drug delivery vehicles before and after release were also observed with SEM. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Biodegradable amphiphiles of grafted poly(lactide) onto 2‐hydroxyethyl methacrylate‐co‐N‐vinylpyrrolidone copolymers as drug carriers

This article describes the synthesis and characterization of 2‐hydroxylethyl methacrylate‐co‐N‐vinylpyrrolidone copolymers, (HEMA‐co‐NVP), via free radical polymerization followed by grafting of poly(lactide) onto (HEMA‐co‐NVP) copolymers, via ring opening polymerization using tin octoate as a catalyst. The copolymers and the grafted copolymers (i.e., amphiphiles) were subjected to sustained release studies using salicylic acid, as a model drug. Characterization of the formed copolymers was performed using ¹H‐NMR, ¹³C‐NMR, FTIR, TGA, DSC, and SEM techniques. Derivative of TGA thermogram was used to determine %hydrophilicity and %hydrophobicity in the grafted and ungrafted copolymers. The SEM morphology revealed porous layers with crispy structure that were most likely due to the presence of poly(lactide) chains. At lower content of poly(lactide) moiety, grafted copolymers showed non‐Fickian diffusion release rate, whereas Fickian diffusion release rate at higher content of poly(lactide) was observed. The increase of poly(lactide) content (i.e., larger %hydrophobicity) in the copolymer increased the drug‐sustainability, due to the consistent but porous amphiphilic degradable structures that allow controllable release of drug in time interval. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dual pH‐ and thermal‐responsive nanocomposite hydrogels for controllable delivery of hydrophobic drug baicalein

Hydrogels have been widely used as mild biomaterials due to their bio‐affinity, high drug loading capability and controllable release profiles. However, hydrogel‐based carriers are greatly limited for the delivery of hydrophobic payloads due to the lack of hydrophobic binding sites. Herein, nano‐liposome micelles were embedded in semi‐interpenetrating poly[(N‐isopropylacrylamide)‐co‐chitosan] (PNIPAAm‐co‐CS) and poly[(N‐isopropylacrylamide)‐co‐(sodium alginate)] (PNIPAAm‐co‐SA) hydrogels which were responsive to both temperature and pH, thereby establishing tunable nanocomposite hydrogel delivery systems. Nano‐micelles formed via the self‐assembly of phospholipid could serve as the link between hydrophobic drug and hydrophilic hydrogel due to their special amphiphilic structure. The results of transmission and scanning electron microscopies and infrared spectroscopy showed that the porous hydrogels were successfully fabricated and the liposomes encapsulated with baicalein could be well contained in the network. In addition, the experimental results of response release in vitro revealed that the smart hydrogels showed different degree of sensitiveness under different pH and temperature stimuli. The results of the study demonstrate that combining PNIPAAm‐co‐SA and PNIPAAm‐co‐CS hydrogels with liposomes encapsulated with hydrophobic drugs is a feasible method for hydrophobic drug delivery and have potential application prospects in the medical field. © 2018 Society of Chemical Industry     

Application of the biodegradable diblock copolymer poly(L‐lactide)‐block‐poly(L‐cysteine): Drug delivery and protein conjugation

A novel approach to self‐assembled and shell‐crosslinked (SCL) micelles from the diblock copolymer poly(L ‐lactide)‐block‐poly(L ‐cysteine) to be used as drug and protein delivery carriers is described. Rifampicin was used as a model drug. The drug‐loaded SCL micelles were obtained by self‐assembly of the copolymer in the presence of the drug in aqueous media. Their morphology and size were studied with dynamic light scattering and field emission scanning electron microscopy. The rifampicin loading capacity and encapsulation efficiency were studied with ultraviolet–visible spectrophotometry. The drug‐release rate in vitro depended on the oxidizing and reducing environment. Moreover, a straightforward approach to the conjugation of the copolymer with bovine serum albumin (BSA) was developed, and a gel electrophoresis test demonstrated that this conjugated BSA could be reversibly released from the copolymer substrate under reducing conditions. In conclusion, this L ‐cysteine copolymer can be used in drug delivery and in protein fixation and recovery. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Lamotrigine‐loaded polyacrylate nanoparticles synthesized through emulsion polymerization

A series of copolymeric nanoparticles of the partially water‐soluble monomer ethyl methacrylate and the water‐soluble monomer 2‐hydroxyl ethyl methacrylate were synthesized from emulsions containing sodium dodecyl sulfate via free‐radical polymerization. Lamotrigine, as a model drug, was loaded in nanoparticles during in situ polymerization. A stable and transparent poly(ethyl methacrylate‐co‐hydroxyl ethyl methacrylate) nanolatex was produced for all compositions and characterized for particle size by dynamic light scattering and transmission electron microscopy. Particles were found to be smaller than 50 nm in size. Structural characterization of copolymers was done by infrared spectrometry, gel permeation chromatography, and NMR spectroscopy. Drug encapsulation efficiency was determined by ultraviolet (UV)–visible spectrometry and was found to be 26–62% for copolymers with different compositions. UV data suggest molecular‐level dispersion of the drug in the nanoparticles. In vitro drug‐release studies showed the controlled release of lamotrigine. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and in vitro drug‐release behavior of 5‐fluorouracil‐loaded poly(hydroxybutyrate‐co‐hydroxyhexanoate) nanoparticles and microparticles

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBHHx) copolymeric microparticles (MPs) and nanoparticles (NPs) were prepared by the double‐emulsion solvent‐evaporation technique. 5‐Fluorouracil (5‐Fu), an anticancer drug, was entrapped in PHBHHx NPs and MPs. A variety of parameters, including the species and concentration of different surfactants, power and time of ultrasonication for particle dispersion, and organic/aqueous solution ratio, that affected the production of the 5‐Fu‐loaded PHBHHx NP and MP particles and the release of 5‐Fu were studied. The results show that the prepared NPs and MPs were spherical in shape and about 160 nm and 3 μm in size, respectively, when cetyltrimethyl ammonium bromide was used as the emulsifier. The drug‐loading content (DLC) varied from 3.53 to 8.03% for 5‐Fu‐loaded NPs and from 4.83 to 18.87% for 5‐Fu‐loaded MPs and depended on the different initial feeding amounts of 5‐Fu. The encapsulation efficiency decreased with increasing DLC. The in vitro drug‐release characteristics appeared to have two phases with an initial burst effect occurring within the first 8 h; this was more obvious for the particles with low DLCs. The NPs with high DLC (8.03%) had the slowest release rate, 49.6% of 5‐Fu within 24 h. Therefore, PHBHHx copolymeric NPs and MPs can possibly be applied as drug‐delivery carrier materials in the future. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel hyperbranched poly (amine-ester)-poly (lactide-co-glycolide) polymeric micelles as amphotericin B carriers

A series of amphiphilic hyperbranched poly (amine-ester)-poly (lactide-co-glycolide) (HPAE-co-PLGA) copolymers were synthesized by ring-opening polymerization of dl-lactide, glycolide and a fourth generation hyperbranched poly (amine-ester) (HPAE-OHs4) with Sn(Oct)₂ as catalyst. The chemical structure of copolymers was characterized by Fourier transform infrared (FT-IR), nuclear magnetic resonance (¹H-NMR, ¹³C-NMR), thermo gravimetric analysis apparatus (TGA), and different scanning calorimetry (DSC). Formation and characteristics of polymeric micelles of the amphiphilic copolymer were studied by environmental scanning electron microscopy (ESEM), fluorescence spectroscopy, and dynamic light scattering (DLS). In order to estimate the feasibility as novel drug carriers, a lipophilic model drug amphotericin B was incorporated into polymeric micelles and the drug release behavior was investigated. The micelle size and drug-loading content were found increased, and the drug-release rate decreased with the increase of molar ratio of dl-lactide/glycolide to HPAE.     

Synthesis,crystallinity and degradation properties of biodegradable poly[(sebacic anhydride)‐co‐caprolactone] triblock copolymers

BACKGROUND: A series of novel biodegradable poly[(sebacic anhydride)‐co‐caprolactone] (PSA‐co‐PCL) triblock copolymers were prepared by melt condensation of acylated PSA and monofunctional hydroxyl‐terminated PCL prepolymers. These copolymers could be used as novel drug delivery carriers with expected good drug permeability due to the PCL component. The degradation rate and mode can be modulated by varying the ratio of monomers in the copolymer. RESULTS: The homopolymers and copolymers were characterized using ¹H NMR, gel permeation chromatography and differential scanning calorimetry (DSC). ¹H NMR confirmed the formation of triblock copolymers that comprise a middle PSA block and two side PCL blocks. DSC revealed that the melting temperature and degree of crystallinity for both sebacic anhydride (SA) and caprolactone (CL) components are strongly composition dependent, implying the hindrance effect of the two components on the crystallinity. In vitro degradation experiments showed that the mass loss is significantly accelerated for samples in base buffer solution and more rapid for the copolymers with a higher SA content. Scanning electron microscopy revealed that for SA‐rich copolymer, PSA(80 wt%)‐co‐PCL, surface erosion dominated the degradation mode of the sample. In contrast, for CL‐rich copolymer, PSA(20 wt%)‐co‐PCL, a micropore structure developed at a degradation time of 155 h along the edges of the sample, owing to the hydrolysis of SA. CONCLUSION: It is concluded that the rate and mode of degradation of these copolymers can be tuned by varying the composition of the copolymers. Copyright © 2007 Society of Chemical Industry     

Poly(acrylic acid‐co‐acrylamide‐co‐2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)‐grafted nanocellulose/poly(vinyl alcohol) composite for the in vitro gastrointestinal release of amoxicillin

Superabsorbent polymer composites (SAPCs) are very promising and versatile materials for biomedical applications. This study concentrates on the development of novel cellulose‐based SAPC, Poly(acrylic acid‐co‐acrylamide‐co?2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)‐grafted nanocellulose/poly(vinyl alcohol) composite, P(AA‐co‐AAm‐co‐AMPS)‐g‐NC/PVA, as a potential drug delivery vehicle. Amoxicillin was selected as a model drug, which is used for the treatment of Helicobacter pylori induced peptic and duodenal ulcers. P(AA‐co‐AAm‐co‐AMPS)‐g‐NC/PVA was synthesized by graft copolymerization reaction, and FTIR, XRD, SEM, and DLS analyses were performed for its characterization. Equilibrium swelling studies were conducted to evaluate the stimuli‐response behavior of the SAPC and found that equilibrium swelling was dependent on pH, contact time, temperature, ionic strength, concentration of crosslinker and PVA. Maximum drug encapsulation efficiency was found out by using different concentrations of amoxicillin. Drug release studies were carried out at simulated gastric and intestinal fluids and the release % was observed as maximum in intestinal fluids within 4 h. The drug release kinetics was investigated using Peppas' potential equation and follows non‐Fickian mechanism at pH 7.4. Thus, the drug release experiments indicate that P(AA‐co‐AAm‐co‐AMPS)‐g‐NC/PVA would be a fascinating vehicle for the in vitro administration of amoxicillin into the gastrointestinal tract. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40699.     

Cytotoxicity and cellular uptake evaluation of mitoxantrone‐loaded poly(lactic acid‐co‐lysine) arginine–glycine–aspartic acid nanoparticles

The purpose of this study was to evaluate the in vitro characteristics of poly(lactic acid‐co‐lysine) arginine–glycine–aspartic acid (PLA–PLL–RGD) nanoparticles (NPs) loaded with mitoxantrone. PLA–PLL–RGD NPs with a particle size of 200 nm were prepared with a modified emulsification solvent‐diffusion method. The encapsulation efficiency of the mitoxantrone‐loaded NPs was 85%. In vitro release experiments showed that the release of the drug was prolonged and sustained, and approximately 60.2% of the mitoxantrone was released in the first week. The released drug was integrated to achieve desired drug‐release profiles and still possessed bioactivity according to a 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐2h‐tetrazolium bromide assay, which indicated that mitoxantrone‐loaded NPs were more cytotoxic against Michigan Cancer Foundation 7 (MCF‐7) breast cancer cells than mitoxantrone. Furthermore, the association processes of NPs with MCF‐7 cells, including binding and effective internalization, were investigated in vitro. The cellular uptake of the NPs was qualitatively studied with confocal laser scanning microscopy and was confirmed with flow cytometry analysis. These experimental results indicated that PLA–PLL–RGD NPs could be used as drug carriers for mitoxantrone. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of polycarbonate copolymers of trimethylene carbonate and 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate

The polycarbonate copolymers poly[trimethylene carbonate‐co‐2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate] [P(TMC‐co‐PTC)] were synthesized by the ring‐opening polymerization of trimethylene carbonate (TMC) and 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate (PTC) with tin(II) 2‐ethylhexanoate and aluminum isopropoxide as the catalysts. These copolymers were further reduced by a palladium/carbonate (Pd/C; 10%) catalyst to produce partly deprotected copolymers. These two types of copolymers were characterized by ¹H‐NMR, Fourier transform infrared spectroscopy, UV spectroscopy, gel permeation chromatography, differential scanning calorimetry, and an automatic contact angle meter. The influences of the feed molar ratio of the monomers, the catalyst concentration, the reaction time, and the reaction temperature on the copolymerization process were also studied. The copolymerization of the TMC and PTC monomers was a nonideal copolymerization, and the copolymerization reactivity ratio of TMC was higher than that of PTC. In vitro degradation tests indicated that the partly deprotected copolymers possessed faster degradation rates and more hydrophilicity than the corresponding unreduced copolymers. Moreover, the degradation of these two type copolymers increased when the pH value of the buffer solutions decreased. In vitro drug‐release experiments showed that these two types of copolymers had steady drug‐release rates and good controlled release properties. Moreover, the partly deprotected copolymers had faster drug‐release rates than the corresponding unreduced copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Self‐assembly and degradation of poly[(2‐methacryloyloxyethyl phosphorylcholine)‐block‐(D,L‐lactide)] diblock copolymers: large compound micelles to vesicles

Biodegradable poly[(2‐methacryloyloxyethyl phosphorylcholine)‐block‐(D ,L ‐lactide)] (PMPC‐b‐PLA) diblock copolymers with various hydrophilic PMPC weight fractions (f_PC) will spontaneously self‐assemble into well‐defined vesicles and large compound micelles (LCMs) in water. Transmission electron microscopy, scanning electron microscopy, dynamic light scattering and fluorescence microscopy were used to observe their aggregate morphologies. The degradation of the LCMs was investigated and the loss of molecular weight of PLA blocks was confirmed using ¹H NMR analysis. The hydrolysis of PLA increases f_PC and consequently shifts the preferred morphology from LCMs to vesicles. Such degradation‐induced morphological transitions mean that the biocompatible and biodegradable LCMs have great application potential in drug delivery. Copyright © 2010 Society of Chemical Industry