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1.
Biodegradable polymers based on a blend of polycaprolactone (PCL) and aliphatic polyanhydrides with various monomer lengths were prepared to obtain desired polymer blends for use as drug carriers. The physicochemical, mechanical, and drug‐release properties of these blends were investigated by various techniques to evaluate the uniformity degree of the polymer blends to establish their potential applications in drug delivery. The results demonstrated that the heat of fusion (ΔH) of the polyanhydride or the blend is increased in relation to the length of the aliphatic chain. However, the blends had different properties than pure polyanhydride, and the crystallization degree of the blends, as expressed by the ΔH, decreased in relation to the ΔH of the pure polyanhydride. Drug‐release studies from blends of PCL and aliphatic polyanhydrides demonstrated first‐order kinetics of the release rate. Polymer degradation was independent at the polyanhydride monomer length. On the basis of theoretical calculation of the interaction factor, a blend of PCL and poly(dodecanedeoic anhydride) was chosen for further elucidation of its thermal, mechanical, and degradation properties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3781–3787, 2003  相似文献   

2.
Morphology is presented as a powerful tool to control the in vitro degradation and drug release characteristics of novel drug delivery microspheres prepared from homopolymer blends of 1,5‐dioxepan‐2‐one, DXO, and L ‐lactide, L‐LA. Their performance in this respect was compared to analogous P(L‐LA‐co‐DXO) microspheres. Blends formed denser and less porous microspheres with a higher degree of matrix crystallinity than copolymers of corresponding L‐LA:DXO composition. The morphology differences of blends and copolymers, further adjustable by means of component ratio, are shown to have a vital impact on the in vitro performance. Sustained drug delivery was obtained from both copolymers and blends. Molecular weight loss was retarded and diffusion‐mediated release was inhibited in the latter case, further delaying the release process. The effects of storage on the physicochemical properties of these systems were evaluated under desiccated and moist conditions for 5 months. Storage‐induced physicochemical changes, such as matrix crystallization and molecular weight decrease, were accelerated at higher relative humidities. P(L‐LA‐co‐DXO) demonstrated higher moisture sensitivity than a PLLA‐PDXO blend of corresponding composition. The more crystalline and dense morphology of blend microspheres may thus be considered an improvement of the storage stability. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 786–796, 2000  相似文献   

3.
The objective of this review is to organize literature data on the thermodynamic properties of salt‐containing polystyrene/poly(ethylene oxide) (PS/PEO) blends and polystyrene‐b‐poly(ethylene oxide) (SEO) diblock copolymers. These systems are of interest due to their potential to serve as electrolytes in all‐solid rechargeable lithium batteries. Mean‐field theories, developed for pure polymer blends and block copolymers, are used to describe phenomenon seen in salt‐containing systems. An effective Flory–Huggins interaction parameter, χeff , that increases linearly with salt concentration is used to describe the effect of salt addition for both blends and block copolymers. Segregation strength, χeffN , where N is the chain length of the homopolymers or block copolymers, is used to map phase behavior of salty systems as a function of composition. Domain spacing of salt‐containing block copolymers is normalized to account for the effect of copolymer composition using an expression obtained in the weak segregation limit. The phase behavior of salty blends, salty block copolymers, and domain spacings of the latter systems, are presented as a function of chain length, composition and salt concentration on universal plots. While the proposed framework has limitations, the universal plots should serve as a starting point for organizing data from other salt‐containing polymer mixtures. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1177–1187  相似文献   

4.
Amphiphilic block‐graft copolymers mPEG‐b‐P(DTC‐ADTC‐g‐Pal) were synthesized by ring‐opening polymerization of 2,2‐dimethyltrimethylene carbonate (DTC) and 2,2‐bis(azidomethyl)trimethylene carbonate (ADTC) with poly(ethylene glycol) monomethyl ether (mPEG) as an initiator, followed by the click reaction of propargyl palmitate and the pendant azido groups on the polymer chains. Stable micelle solutions of the amphiphilic block‐graft copolymers could be prepared by adding water to a THF solution of the polymer followed by the removal of the organic solvent by dialysis. Dynamic light scattering measurements showed that the micelles had a narrow size distribution. Transmission electron microscopy images displayed that the micelles were in spherical shape. The grafted structure could enhance the interaction of polymer chains with drug molecules and improve the drug‐loading capacity and entrapment efficiency. Further, the amphiphilic block‐graft copolymers mPEG‐b‐P(DTC‐ADTC‐g‐Pal) were low cytotoxic and had more sustained drug release behavior. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

5.
We report on the preparation of reduction‐responsive amphiphilic block copolymers containing pendent p‐nitrobenzyl carbamate (pNBC)‐caged primary amine moieties by reversible addition–fragmentation chain transfer (RAFT) radical polymerization using a poly(ethylene glycol)‐based macro‐RAFT agent. The block copolymers self‐assembled to form micelles or vesicles in water, depending on the length of hydrophobic block. Triggered by a chemical reductant, sodium dithionite, the pNBC moieties decomposed through a cascade 1,6‐elimination and decarboxylation reactions to liberate primary amine groups of the linkages, resulting in the disruption of the assemblies. The reduction sensitivity of assemblies was affected by the length of hydrophobic block and the structure of amino acid‐derived linkers. Using hydrophobic dye Nile red (NR) as a model drug, the polymeric assemblies were used as nanocarriers to evaluate the potential for drug delivery. The NR‐loaded nanoparticles demonstrated a reduction‐triggered release profile. Moreover, the liberation of amine groups converted the reduction‐responsive polymer into a pH‐sensitive polymer with which an accelerated release of NR was observed by simultaneous application of reduction and pH triggers. It is expected that these reduction‐responsive block copolymers can offer a new platform for intracellular drug delivery. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1333–1343  相似文献   

6.
Well‐defined diblock copolymers of linear polyethylene (PE) and poly(dimethylsiloxane) (PDMS) have been synthesized through a facile route combining the thiol‐ene click chemistry of vinyl‐terminated polyethylene (PE‐ene) and the sequential esterification reaction. The resulting diblock copolymers are characterized by 1H NMR, FT‐IR, DSC, TGA, and TEM. In addition, the PE‐b‐PDMS diblock copolymers have been evaluated as compatibilizers in the blends of high‐density polyethylene (HDPE) and silicone oil. The morphological analysis and mechanical properties demonstrate that the compatibilized blends with low loading concentration of PE‐b‐PDMS display significant improvements in modulus of elasticity and elongation at break as compared to the uncompatibilized binary blends. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3205–3212  相似文献   

7.
Thermoresponsive, biodegradable polymeric hydrogel networks are used widely in medicinal applications. Poly(d ,l ‐lactic acid‐co‐glycolic acid)‐b‐poly(ethylene glycol)‐b‐poly(d ,l ‐lactic acid‐co‐glycolic acid) (PLGA‐PEG‐PLGA) triblock copolymers exhibit a sol–gel transition upon heating. The effect of PLGA block and PEG chain molecular weights (MWs) on the gelling temperature of polymer aqueous solution (20% w/w) is described. All polymer solutions convert into a hard gel within 2 °C of the gelling temperature. The release properties of the gels were displayed using paracetamol as a representative drug. A linear relation is described between the gelling temperature and PLGA block MW. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 35–39  相似文献   

8.
9.
Dendron‐like poly(ε‐benzyloxycarbonyl‐L ‐lysine)/linear poly(ethylene oxide) block copolymers (i.e., Dm‐PZLys‐b‐PEO, m = 0 and 3; Dm are the propargyl focal point poly(amido amine) dendrons having 2m primary amine groups) were for the first time synthesized by combining ring‐opening polymerization (ROP) of ε‐benzyloxycarbonyl‐L ‐lysine N‐carboxyanhydride (Z‐Lys‐NCA) and click chemistry, where Dm‐PZLys homopolypeptides were click conjugated with azide‐terminated PEO. Their molecular structures and physical properties were characterized in detail by FTIR, 1H NMR, gel permeation chromatography, differential scanning calorimetry, polarized optical microscopy, and wide angle X‐ray diffraction. Both homopolypeptides and copolymers presented a liquid crystalline phase transition for PZLys block, and the transition was irreversible. Moreover, the degree of crystallinity of PEO block within linear copolymers decreased from 96.2% to 20.4% with increasing PZLys composition, whereas that within dendritic copolymers decreased to zero. The secondary conformation of PZLys progressively changed from β‐sheet to α‐helix with increasing the chain length. These copolymers self‐assembled into spherical nanoparticles in aqueous solution, and the anticancer drug doxorubicin‐loaded nanoparticles gave a similar morphology compared with their blank counterparts. The drug‐loaded nanoparticles showed a triphasic drug‐release profile at aqueous pH 7.4 or 5.5 and 37 °C and sustained a longer drug‐release period for about 2 months. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

10.
Symmetric reduction‐responsive amphiphilic comblike copolymers mid‐disulfide‐functionalized comblike copolymers with alternating copolymer comprised of styrenic unit and N‐(2‐hydroxyethyl) maleimide (HEMI) unit (poly(St‐alt‐HEMI)) backbones and alternating PEG and PCL side chains (S‐CP(PEG‐alt‐PCL)) with poly(St‐alt‐HEMI) backbones and alternating poly(ε‐caprolactone) (PCL) and poly(ethylene glycol) (PEG) side chains were synthesized and used as nanocarriers for in vitro release of doxorubicin. The target copolymers with predetermined molecular weight and narrow molecular weight distribution (Mw/Mn = 1.15–1.20) were synthesized by reversible addition‐fragmentation chain transfer (RAFT) copolymerization of vinylbenzyl‐terminated PEG and N‐(2‐hydroxyethyl) maleimide mediated by a disulfide‐functionalized RAFT agent S‐CPDB, and followed by ring‐opening polymerization of ε‐caprolactone. When compared with linear block copolymer comprised of poly(ethylene glycol) (PEG) and poly(?‐caprolactone) (PCL) segments (PEG‐b‐PCL) copolymers, comblike copolymers with similar PCL contents usually exhibited decreased crystallization temperature, melting temperature, and degree of crystallinity, indicating the significant influence of copolymer architecture on physicochemical properties. Dynamic light scattering measurements revealed that comblike copolymers were liable to self‐assemble into aggregates involving vesicles and micelles with average diameter in the range of 56–226 nm and particle size distribution ranging between 0.07 and 0.20. In contrast to linear copolymer aggregates, comblike copolymer aggregates with similar compositions were of improved storage stability and enhanced drug‐loading efficiency. In vitro drug release confirmed the disulfide‐linked comblike copolymer aggregates could rapidly release the encapsulated drug when triggered by 10 mM DL ‐dithiothreitol. These reduction‐sensitive, biocompatible, and biodegradable aggregates have a potential as controlled delivery vehicles. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

11.
We report here a reversible self‐assembly formation system using block copolymers with thermo‐tunable properties. A series of double‐responsive block copolymers, poly(N‐isopropylacrylamide (NIPAAm))‐block‐poly(NIPAAm‐coN‐(isobutoxymethyl)acrylamide (BMAAm)) with two lower critical solution temperatures were synthesized by one‐pot atom transfer radical polymerization via sequential monomer addition. When dissolved in aqueous solution at room temperature, the block copolymers remained unimeric. Upon heating above room temperature, the block copolymers self‐assembled into micellar structures. The micelle formation temperature and the resulting diameter were controlled by varying the BMAAm content. 1H Nuclear Magnetic Resonance, dynamic light scattering, field‐emission scanning electron microscopy, and fluorescence spectra revealed the presence of a monodisperse nanoassembly, and demonstrated the assembly formation/inversion process was fully reversible. Moreover, a model hydrophobic molecule, pyrene, was successfully loaded into the micelle core by including pyrene in the original polymer solution. Further heating resulted in mesoscopic micelle aggregation and precipitation. This dual micelle and aggregation system will find utility in drug delivery applications as a thermal trigger permits both aqueous loading of hydrophobic drugs and their subsequent release. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

12.
Novel, biodegradable poly(?‐caprolactone)‐block‐poly(trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline)‐block‐poly(?‐caprolactone) triblock copolymers were synthesized by ring‐opening polymerization from dihydroxyl‐terminated macroinitiator poly(trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline) (PHpr) and ?‐caprolactone (?‐CL) with stannous octoate as the catalyst. The molecular weights were characterized with gel permeation chromatography and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. With an increase in the contents of ?‐CL incorporated into the copolymers, a decrease in the glass‐transition temperature (Tg) was observed. The Tg values of copoly(4‐phenyl‐?‐caprolactone) and copoly(4‐methyl‐?‐caprolactone) were higher than Tg of copoly(?‐caprolactone). Their micellar characteristics in an aqueous phase were investigated with fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. The block copolymers formed micelles in the aqueous phase with critical micelle concentrations in the range of 1.00–1.36 mg L?1. With higher molecular weights and hydrophobic components in the copolymers, a higher critical micelle concentration was observed. As the feed weight ratio of antitriptyline hydrochloride (AM) to the polymer increased, the drug loading increased. The micelles exhibited a spherical shape, and the average size was less than 250 nm. The in vitro hydrolytic degradation and controlled drug release properties of the triblock copolymers were also investigated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4268–4280, 2006  相似文献   

13.
Small‐angle neutron scattering (SANS) was used to examine the melt phase behavior of a heavily branched comb PEE polymer blended separately with two linear PEE copolymers. In this case, PEE refers to poly(ethylene‐r‐ethylethylene) with 10% ethylene units; therefore, the molecular architecture was the only difference between the two components of the blends. The molecular weights of the two linear random copolymers were 60 and 220 kg/mol, respectively. The comb polymer contained an average of 54 long branches, with a molecular weight of 13.7 kg/mol, attached to a backbone with a molecular weight of 10 kg/mol. Three different volume compositions (25/75, 50/50, and 75/25) were investigated for both types of blends. SANS results indicate that all the blends containing the lower molecular weight linear polymer formed single‐phase mixtures, whereas all the blends containing the high molecular weight linear polymer phase‐separated. These results are discussed in the context of current theories for polymer blend miscibility. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2965–2975, 2000  相似文献   

14.
Medicated‐fibers have been obtained through electrospinning after rifampin was dissolved in poly (lactic acid)/chloroform solution. The relationship between polymer variables [such as concentration, molecular weight (Mw), and introducing hydrophilic block] and drug release from the electrospun fibers is disclosed. The results show that polymeric concentration and Mw are crucial for producing the medicated fibers, which influence not only the morphology of the medicated‐fiber but also drug release rate from fiber. At the same Mw, the drug release rate decreases with the increase of spinning concentration. At two different Mw blends, drug release behaviors change. When the low Mw content is in a dominant position, drug release rate depends largely on mixing ratio of two Mw contents; on the other hand, drug release rate is also dependent on concentration of spinning fluid. In addition, the block copolymer [poly‐L ‐lactic acid (PLLA)‐polyethylene glycol‐PLLA] shows faster release rate as compared to homopolymer (PLLA). © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011  相似文献   

15.
In attempt to improve the properties of polyanhydrides based on aliphatic anhydrides, we synthesized novel polyanhydrides containing amide groups in the main chains. In this work, N,N′‐bis(L ‐alanine)‐sebacoylamide (BSAM) was prepared from natural amino acid and sebacic acid (SA) and characterized by IR and 1H NMR. In addition, polymers of PBSAM, P[1,6‐bis(P‐carboxyphenoxy) hexane (CPH)‐BSAM], and P(CPH‐SA), blends of P(CPH‐SA)/polylactide (PLA), P(CPH‐BSAM)/PLA were also prepared and characterized by IR, gel permeation chromatography, and differential scanning calorimetry. The hydrolytic degradation of polyanhydrides and their blends with PLA (number‐average molecular weight = 2.90 × 105) was evaluated in 0.1 M phosphate buffer pH 7.4 at 37 °C. The results indicate that the existence of amide, aromatic, and ester bonds in the main chain of polymers slows down the degradation rate, and the tendency becomes clearer with the increasing amount of them, and the copolymers and their blends with PLA possess excellent physical and mechanical properties. These can make them more widely used in drug delivery and nerve regeneration. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4311–4317, 2004  相似文献   

16.
Novel and well‐defined amphiphilic dendrimer‐star copolymer poly(ε‐caprolactone)‐block‐(poly(2‐(2‐methoxyethoxy)ethylmethacrylate‐co‐oligo(ethylene glycol) methacrylate))2 with Y‐shaped arms were synthesized by the combination of ring‐opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The investigation of thermal properties and the analysis of crystalline morphology indicate that the high‐branched structure of dendrimer‐star copolymers with Y‐shaped arms and the presence of amorphous P(MEO2MA‐co‐OEGMA) segments together led to the complete destruction of crystallinity of the PCL segments in the dendrimer‐star copolymer. In addition, the hydrophilicity–hydrophobicity transition of the dendrimer‐star copolymer film can be achieved by altering the external temperatures. The amphiphilic copolymers can self‐assemble into spherical nanomicelles in water. Because the lower critical solution temperature of the copolymers can be adjusted by varying the ratio of MEO2MA and OEGMA, the tunable thermosensitive properties can be observed by transmittance, dynamic laser light scattering, and transmission electron microscopy (TEM). The release rate of model drug chlorambucil from the micelles can be effectively controlled by changing the external temperatures, which indicates that these unique high‐branched amphiphilic copolymers have the potential applications in biomedical field. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

17.
Disulfide‐centered star‐shaped poly(ε‐benzyloxycarbonyl‐l ‐lysine)‐b‐poly(ethylene oxide) block copolymers (i.e., A2B4 type Cy‐PZlys‐b‐PEO) were synthesized by the combination of ring‐opening polymerization and thiol‐yne chemistry. Their molecular structures and physical properties were characterized in detail by FTIR, 1H NMR, gel permeation chromatography, differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscope. Despite mainly exhibiting an α‐helix conformation, the inner PZlys blocks within copolymers greatly prohibited the crystallinity of the outer PEO blocks and presented a liquid crystal phase transition behavior in solid state. These block copolymers Cy‐PZlys‐b‐PEO self‐assembled into nearly spherical micelles in aqueous solution, which had a hydrophobic disulfide‐centered PZlys core surrounded by a hydrophilic PEO corona. As monitored by means of DLS and TEM, these micelles were progressively reduced to smaller micelles in 10 mM 1,4‐dithiothreitol at 37 °C and finally became ones with a half size, demonstrating a reduction‐sensitivity. Despite a good drug‐loading property, the DOX‐loaded micelles of Cy‐PZlys‐b‐PEO exhibited a reduction‐triggered drug release profile with an improved burst‐release behavior compared with the linear counterpart. Importantly, this work provides a versatile strategy for the synthesis of the disulfide‐centered star‐shaped polypeptide block copolymers potential for intracellular glutathione‐triggered drug delivery systems. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2000–2010  相似文献   

18.
A facile approach to synthesis of ABCDE‐type H‐shaped quintopolymer comprising polystyrene (PSt, C) main chain and poly(ethylene glycol) (PEG, A), poly(ε‐caprolactone) (PCL, B), poly(L ‐lactide) (PLLA, D), and poly(acrylic acid) (PAA, E) side chains was described, and physicochemical properties and potential applications as drug carriers of copolymers obtained were investigated. Azide‐alkyne cycloaddition reaction and hydrolysis were used to synthesize well‐defined H‐shaped quintopolymer. Cytotoxicity studies revealed H‐shaped copolymer aggregates were nontoxic and biocompatible, and drug loading and release properties were affected by macromolecular architecture, chemical composition, and pH value. The release rate of doxorubicin from copolymer aggregates at pH 7.4 was decreased in the order PAA‐b‐PLLA > H‐shaped copolymer > PEG‐PCL‐PSt star, and the release kinetics at lower pH was faster. The H‐shaped copolymer aggregates have a potential as controlled delivery vehicles due to their excellent storage stability, satisfactory drug loading capacity, and pH‐sensitive release rate of doxorubicin. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

19.
A new conjugated polymer PBDTT‐ID based on N‐alkylated isoindigo (ID) and bis(2,3‐dialkylthienyl)‐substituted benzo[1,2‐b:4,5‐b′]dithiophene (BDTT) as repeating units was synthesized. It had an optical bandgap of 1.56 eV and a highest occupied molecular orbital (HOMO) energy level of ?5.71 eV. The optical, electrochemical, and photovoltaic properties of new polymer were compared with previous reported polymer PBDT‐ID , which was based on bis(alkoxy)‐substituted benzo[1,2‐b:4,5‐b′]dithiophene. The new polymer displayed lower HOMO energy level and better absorption properties than polymer PBDT‐ID . The solar cells fabricated with PBDTT‐ID /PC61BM (1:2, w/w) blends as active layers exhibited photoresponse in the range of 300–800 nm. A power conversion efficiency of 4.02% and an open circuit voltage (Voc) of 0.94 V were achieved in polymer solar cell device based on the new polymer. This was the highest Voc realized among the isoindigo‐based polymers. The relatively high performances of new polymer in solar cell devices were interpreted in terms of material properties and morphologies of polymer/PCBM blends. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013  相似文献   

20.
The synthesis and self‐assembly properties in aqueous solutions of novel amphiphilic block copolymers composed of one hydrophobic poly (lauryl methacrylate), (PLMA) block and one hydrophilic poly (oligo ethylene glycol methacrylate) (POEGMA) block are reported. The block copolymers were prepared by RAFT polymerization and were molecularly characterized by size exclusion chromatography, NMR and FT‐IR spectroscopy, and DSC. The PLMA‐b‐POEGMA amphiphilic block copolymers self‐assemble in nanosized complex nanostructures resembling compound micelles when inserted in aqueous media, as supported by light scattering and TEM measurements. The encapsulation and release of the model, hydrophobic, nonsteroidal anti‐inflammatory drug indomethacin in the polymeric micelles is also investigated. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 155–163  相似文献   

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