Preparation of polymeric vesicles through ultrasonic treatment of poly(styrene‐block‐2‐vinylpyridine) micelles under alkaline conditions

An approach for the preparation of block copolymer vesicles through ultrasonic treatment of polystyrene‐block‐poly(2‐vinyl pyridine) (PS‐b‐P2VP) micelles under alkaline conditions is reported. PS‐b‐P2VP block copolymers in toluene, a selective solvent for PS, form spherical micelles. If a small amount of NaOH solution is added to the micelles solution during ultrasonic treatment, organic‐inorganic Janus‐like particles composed of the PS‐b‐P2VP block copolymers and NaOH are generated. After removal of NaOH, block copolymer vesicles are obtained. A possible mechanism for the morphological transition from spherical micelles to vesicles or Janus‐like particles is discussed. If the block copolymer micelles contain inorganic precursors, such as FeCl₃, hybrid vesicles are formed, which may be useful as biological and chemical sensors or nanostructured templates. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 953–959     

Self‐assembled complexes of poly(acrylic acid) and poly(styrene)‐block‐poly(4‐vinyl pyridine)

Polymer complexes were prepared from high molecular weight poly(acrylic acid) (PAA) and poly(styrene)‐block‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) in dimethyl formamide (DMF). The hydrogen bonding interactions, phase behavior, and morphology of the complexes were investigated using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In this A‐b‐B/C type block copolymer/homopolymer system, P4VP block of the block copolymer has strong intermolecular interaction with PAA which led to the formation of nanostructured micelles at various PAA concentrations. The pure PS‐b‐P4VP block copolymer showed a cylindrical rodlike morphology. Spherical micelles were observed in the complexes and the size of the micelles increased with increasing PAA concentration. The micelles are composed of hydrogen‐bonded PAA/P4VP core and non‐bonded PS corona. Finally, a model was proposed to explain the microphase morphology of complex based on the experimental results obtained. The selective swelling of the PS‐b‐P4VP block copolymer by PAA resulted in the formation of different micelles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1192–1202, 2009     

Self‐assembly of H‐bonded side‐chain and cross‐linking copolymers containing diblock‐copolymeric donors and single/double H‐bonded light‐emitting acceptors

A series of diblock‐copolymers were synthesized through anionic polymerization of styrene and tert‐butyl methacrylate (tBuA) with different monomer ratios, and analogous block‐copolymeric derivatives (PS‐b‐PAA)s with monofunctional carboxylic acid groups were obtained by further hydrolyzation as hydrogen‐bonded (H‐bonded) proton donors. Via H‐bonded interaction, these diblock‐coplymeric donors (PS‐b‐PAA)s were incorporated with luminescent mono‐pyridyl/bis‐pyridyl acceptors to form single/double H‐bonded supramolecules, that is, H‐bonded side‐chain/cross‐linking copolymers, respectively. The supramolecular architectures formed by donor polymers and light‐emitting acceptors were influenced by the ratio of acid blocks in the diblock copolymeric donors and the type of single/double H‐bonded light‐emitting acceptors. Their thermal and luminescent properties can be adjusted by H‐bonds, and more than 100 nm of red‐shifted photoluminescence (PL) emissions were observed, which depend on the degrees of the H‐bonding interactions. Self‐assembled phenomena of amphiphilic dibolck copolymers and their H‐bonded complexes were confirmed by TEM micrographs, and supramolecular microphase separation of spherical micelle‐like morphology was demonstrated to affect the photophysical properties. Polymer light‐emitting diode (PLED) devices containing H‐bonded complexes showed electroluminescence (EL) emissions of 503–560 nm under turn‐on voltages of 7.5–9.0 V, maximum power efficiencies of 0.23–0.37 cd/A (at 100 mA/cm²), and maximum luminances of 318–519 cd/m² (around 25 V). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4685–4702, 2009     

Synthesis of linear and 4‐arm star block copolymers of poly(methyl acrylate‐b‐solketal acrylate) by SET‐LRP at 25 °C

The new SET‐LRP (using Cu(0) powder for organic synthesis) was successfully used to produce well‐defined linear and star homo‐ and diblock‐copolymers of PMA, PSA, and P(MA‐b‐GA)_n (where n = 1 or 4). The kinetic data showed that all SET‐LRP were first order and reached high conversions in a short period of time. The other advantage of using such a system is that the copper can easily be removed through filtration, allowing the production of highly pure polymer. The molecular weight distributions were well controlled with polydispersity indexes below 1.1 and the number‐average molecular weight close to theory, especially upon the addition of Cu(II)Br₂/Me₆‐TREN complex. The linear and star block copolymers were then hydrolyzed to produce the biocompatible amphiphilic P(MA‐b‐GA)_n, where the glycerol side‐groups make the outer block hydrophilic. These blocks were micellized into water and found to have a R_g/R_H equal to 0.8 and 1.59 for the liner and star blocks, respectively. This together with the TEM's supported that the linear blocks formed the classical core‐shell micelles, where as, the star blocks formed vesicles. We found direct support for the vesicle structure from a TEM where one vesicle squashed a second vesicle consistent with a hollow structure. Such vesicle structures have potential applications as delivery nanoscaled devices for drugs and other important biomolecules. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6346–6357, 2008     

Dendritic poly(benzyl ether)‐b‐poly(N‐vinylcaprolactam) block copolymers: Self‐organization in aqueous media,thermoresponsiveness and biocompatibility

Four generations of new amphiphilic thermoresponsive linear‐dendritic block copolymers (LDBCs) with a linear poly(N‐vinylcaprolactam) (PNVCL) block and a dendritic poly(benzyl ether) block are synthesized by atom transfer radical polymerization (ATRP) of N‐vinylcaprolactam (NVCL) using dendritic poly(benzyl ether) chlorides as initiators. The copolymers have been characterized by ¹H NMR, FTIR, and GPC showing controlled molecular weight and narrow molecular weight distribution (PDI ≤ 1.25). Their self‐organization in aqueous media and thermoresponsive property are highly dependent on the generation of dendritic poly(benzyl ether) block. It is observed for the LDBCs that the self‐assembled morphology changes from irregularly spherical micelles, vesicles, rod‐like large compound vesicles (LCVs), to the coexistence of spherical micelles and rod‐like LCVs, as the generation of the dendritic poly(benzyl ether) increases. The results of a cytotoxicity study using an MTT assay method with L929 cells show that the LDBCs are biocompatible. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 300–308     

Design and proof of reversible micelle‐to‐vesicle multistimuli‐responsive morphological regulations

Multistimuli‐responsive precise morphological control over self‐assembled polymers is of great importance for applications in nanoscience as drug delivery system. A novel pH, photoresponsive, and cyclodextrin‐responsive block copolymer were developed to investigate the reversible morphological transition from micelles to vesicles. The azobenzene‐containing block copolymer poly(ethylene oxide)‐b‐poly(2‐(diethylamino)ethyl methacrylate‐co‐6‐(4‐phenylazo phenoxy)hexyl methacrylate) [PEO‐b‐P(DEAEMA‐co‐PPHMA)] was synthesized by atom transfer radical polymerization. This system can self‐assemble into vesicles in aqueous solution at pH 8. On adjusting the solution pH to 3, there was a transition from vesicles to micelles. The same behavior, that is, transition from vesicles to micelles was also realizable on addition of β‐cyclodextrin (β‐CD) to the PEO‐b‐P(DEAEMA‐co‐PPHMA) solution at pH 8. Furthermore, after β‐CD was added, alternating irradiation of the solution with UV and visible light can also induce the reversible micelle‐to‐vesicle transition because of the photoinduced trans‐to‐cis isomerization of azobenzene units. The multistimuli‐responsive precise morphological changes were studied by laser light scattering, transmission electron microscopy, and UV–vis spectra. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Thermo‐ and pH‐induced self‐assembly of P(AA‐b‐NIPAAm‐b‐AA) triblock copolymers synthesized via RAFT polymerization

A series of environmentally sensitive ABA triblock copolymers with different block lengths were prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization from acrylic acid (AA) and N‐isopropylacrylamide (NIPAAm). The GPC and ¹H NMR analyses demonstrated the narrow molecular weight distribution and precise chemical structure of the prepared P(AA‐b‐NIPAAm‐b‐AA) triblock copolymers owing to the controlled/living characteristics of RAFT polymerization. The lower critical solution temperature (LCST) of the triblock copolymers could be tailored by adjusting the length of PAA block and controlled by the pH value. Under heating, the triblock copolymers underwent self‐assemble in dilute aqueous solution and formed nanoparticles revealed via TEM images. Physically crosslinked nanogels induced by inter‐/intra‐hydrogen bonding or core‐shell micelle particles thus could be obtained by changing environmental conditions. With a well‐defined structure and stimuli‐responsive properties, the P(AA‐b‐NIPAAm‐b‐AA) copolymer is expected to be employed as a nanocarrier for biomedical applications in controlled‐drug delivery and targeting therapy. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1109–1118     

Formation of Core‐Shell‐Corona Micellar Complexes through Adsorption of Double Hydrophilic Diblock Copolymers into Core‐Shell Micelles

Summary: The complexation between polystyrene‐block‐poly(acrylic acid) (PS‐b‐PAA) micelles and poly(ethylene glycol)‐block‐poly(4‐vinyl pyridine) (PEG‐b‐P4VP) is studied, and a facile strategy is proposed to prepare core‐shell‐corona micellar complexes. Micellization of PS‐b‐PAA in ethanol forms spherical core‐shell micelles with PS block as core and PAA block as shell. When PEG‐b‐P4VP is added into the core‐shell micellar solution, the P4VP block is absorbed into the core‐shell micelles to form spherical core‐shell‐corona micellar complexes with the PS block as core, the combined PAA/P4VP blocks as shell and the PEG block as corona. A model is suggested to characterize the core‐shell‐corona micellar complexes.

Schematic formation of core‐shell‐corona (CSC) micellar complexes by adsorption of PEG‐b‐P4VP into core‐shell PS‐b‐PAA micelles.     

α‐Chymotrypsin‐Catalyzed Reaction Confined in Block‐Copolymer Vesicles

Herein the reactivity of the enzyme α‐chymotrypsin in the confinement of polystyrene‐block‐poly(acrylic acid) (PS‐b‐PAA) vesicles was investigated. Enzyme and substrate molecules were encapsulated in PS‐b‐PAA vesicles with internal diameters ranging from 26 nm to 165 nm during the formation of the vesicles. While the loading efficiencies of enzyme and substrate molecules were practically identical for vesicles of identical size, they were found to increase with decreasing vesicle size. The kinetics of the α‐chymotrypsin catalyzed hydrolysis of N‐succinyl‐Ala‐Ala‐Phe‐7‐amido‐4‐methylcoumarin (AMC) was evaluated following the increase of the absorption of the product 7‐amino‐4‐methylcoumarin by UV/Vis spectroscopy. The values of the catalytic turnover number obtained for reactions inside vesicles with different sizes showed an increase of up to fourteen times compared to the bulk value with decreasing vesicle volume, while the values of the Michaelis–Menten constant decreased, respectively. This increase in reactivity of α‐chymotrypsin is attributed to the effect of vesicle–wall interactions in the finite encapsulated space, where the reagents could diffuse, leading to enhanced collision frequencies.     

Micellar structure and mechanical properties of block copolymer‐modified epoxies

Amphiphilic block copolymers provide a unique means for toughening epoxy resins because they can self‐assemble into different inclusion shapes before epoxy curing. The two examples reported here are spherical micelles and vesicles, which form in blends containing epoxy and symmetric or asymmetric poly(ethylene oxide)–poly(ethylene‐alt‐propylene) (PEO–PEP) block copolymer with PEO volume fractions of 0.5 and 0.26, respectively. The vesicles and spherical micelles were characterized by transmission electron microscopy and small‐angle X‐ray scattering (SAXS), respectively. SAXS data from the spherical micelles were fit to the Percus–Yevick model for a liquid‐like packing of spheres with hard‐core interactions. Mechanical properties of spherical‐micelle‐modified and vesicle‐modified epoxies in the dilute limit are compared. The glass‐transition temperature and Young's (storage) modulus were tested with dynamic mechanical spectroscopy, and compact‐tension experiments were performed to determine the critical plane‐strain energy release rate for fracture. Vesicles were most effective in improving the epoxy fracture resistance. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2996–3010, 2001     

Self‐assembly of thermo‐ and pH‐responsive poly(acrylic acid)‐b‐poly(N‐isopropylacrylamide) micelles for drug delivery

Self‐assembled thermo‐ and pH‐responsive poly(acrylic acid)‐b‐poly(N‐isopropylacrylamide) (PAA‐b‐PNIPAM) micelles for entrapment and release of doxorubicin (DOX) was described. Block copolymer PAA‐b‐PNIPAM associated into core‐shell micelles in aqueous solution with collapsed PNIPAM block or protonated PAA block as the core on changing temperature or pH. Complexation of DOX with PAA‐b‐PNIPAM triggered by the electrostatic interaction and release of DOX from the complexes due to the changing of pH or temperature were studied. Complex micelles incorporated with DOX exhibited pH‐responsive and thermoresponsive drug release profile. The release of DOX from micelles was suppressed at pH 7.2 and accelerated at pH 4.0 due to the protonation of carboxyl groups. Furthermore, the cumulative release of DOX from complex micelles was enhanced around LCST ascribed to the structure deformation of the micelles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5028–5035, 2008     

4‐hydroxythiophenol grafted PS‐b‐PAA block copolymers: Preparation and formation of porous and bowl‐shaped assemblies

4‐Hydroxythiophenol (HTP) grafted poly(styrene‐b‐acrylic acid) (PS‐b‐PAA) block copolymers (BCPs) (PS‐b‐PAA‐g‐HTP) was synthesized using the esterification reaction between the carboxyl groups and hydroxyl groups. Self‐assembly behavior of the graft copolymer in 1,4‐dioxane/water was investigated. Assemblies of different morphologies, porous, and bowl‐shaped structures, could be easily prepared. A possible mechanism for the formation of the porous and bowl‐shaped structures was discussed. The present study showed a facile method for the preparation of functionalized PS‐b‐PAA BCPs, which could easily self‐assembly into novel structures in aqueous solution. These assemblies may be used to generate new functional materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1551–1557     

Effect of binary block‐selective solvents on self‐assembly of ABA triblock copolymer in dilute solution

We have studied the self‐assembly of the ABA triblock copolymer (P4VP‐b‐PS‐b‐P4VP) in dilute solution by using binary block‐selective solvents, that is, water and methanol. The triblock copolymer was first dissolved in dioxane to form a homogeneous solution. Subsequently, a given volume of selective solvent was added slowly to the solution to induce self‐assembly of the copolymer. It was found that the copolymer (P4VP₄₃‐b‐PS₃₆₆‐b‐P4VP₄₃) tended to form spherical aggregate or bilayer structure when we used methanol or water as the single selective solvent, respectively. However, the aggregates with various nanostructures were obtained by using mixtures of water and methanol as the block‐selective solvents. The aggregate structure changed from sphere to rod, vesicle, and then to bilayer by changing water content in the block‐selective solvent from 0 to 100%. Moreover, it was found that the vesicle size could be well controlled by changing the copolymer content in the solution. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1536–1545, 2008     

Synthesis and self‐assembly of amphiphilic macrocyclic block copolymer topologies

We demonstrated the synthesis of miktoarm star block copolymers of AB, AB₂, and A₂B, in which block A consisted of linear poly(tert‐butyl acrylate) (P^tBA) and block B consisted of cyclic polystyrene. These structures were produced using the atom transfer radical polymerization to make telechelic polymers that, after modification, were further coupled together by copper‐catalyzed “click” reactions with high coupling efficiency. Deprotection of P^tBA to poly(acrylic acid) (PAA) afforded amphiphilic miktoarm structures that when micellized in water gave vesicle morphologies when the block length of PAA was 21 units. Increasing the PAA block length to 46 units produced spherical core‐shell micelles. AB₂ miktoarm stars packed more densely into the core compared to its linear counterpart (i.e., a four times greater aggregation number with approximately the same hydrodynamic diameter), resulting in the PAA arms being more compressed in the corona and extending into the water phase beyond its normal Gaussian chain conformation. These results show that the cyclic structure attached to an amphiphilic block has a significant influence on increasing the aggregation number through a greater packing density. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

A roadmap for poly(ethylene oxide)‐block‐poly‐ε‐caprolactone self‐assembly in water: Prediction,synthesis, and characterization

Numerical self‐consistent field (SCF) lattice computations allow a priori determination of the equilibrium morphology and size of supramolecular structures originating from the self‐assembly of neutral block copolymers in selective solvents. The self‐assembly behavior of poly(ethylene oxide)‐block‐poly‐ε‐caprolactone (PEO‐PCL) block copolymers in water was studied as a function of the block composition, resulting in equilibrium structure and size diagrams. Guided by the theoretical SCF predictions, PEO‐PCL block copolymers of various compositions have been synthesized and assembled in water. The size and morphology of the resulting structures have been characterized by small‐angle X‐ray scattering, cryogenic transmission electron microscopy, and multiangle dynamic light scattering. The experimental results are consistent with the SCF computations. These findings show that SCF is applicable to build up roadmaps for amphiphilic polymers in solution, where control over size and shape are required, which is relevant, for instance, when designing spherical micelles for drug delivery systems © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 330–339     

Branched poly(styrene‐b‐tert‐butyl acrylate) and poly(styrene‐b‐acrylic acid) by ATRP from a dendritic poly(propylene imine)(NH2)64 core

With the aim of creating highly branched amphiphilic block copolymers, the primary amine end groups of the poly(propylene imine) dendrimers DAB‐dendr‐(NH₂)₈ and DAB‐dendr‐(NH₂)₆₄ were converted to 2‐bromoisobutyramide groups. Poly (styrene‐b‐tert‐butyl methacrylate) (PS‐b‐PtBMA) was synthesized by ATRP from the eight end group initiator, and poly(styrene‐b‐tert‐butyl acrylate) (PS‐b‐PtBA) was synthesized from the 64 end group initiator. The tert‐butyl groups were removed to produce poly(styrene‐b‐methacrylic acid) (PS‐b‐PMAA) and poly(styrene‐b‐acrylic acid) (PS‐b‐PAA). Comparison of size exclusion chromatography (SEC) absolute molecular weight analyses of the polystyrenes with calculated molecular weights showed that the eight end group initiator produced a polystyrene with about eight branches, and that the 64 end group initiator produced polystyrene with many fewer than 64 branches. The PS‐b‐PtBA materials also have many fewer than 64 branches. The PS‐b‐PAA samples dissolved molecularly in DMF but formed aggregates in water even at pH 10. AFM images of the PS‐b‐PtBAs spin coated from THF and DMF onto mica showed aggregates. AFM images of the PS‐b‐PAAs spin coated from various mixtures of DMF and water at pH 10 showed flat disks and worm‐like images similar to those observed with linear PS‐b‐PAAs. Use of a PS‐b‐PAA and a PS‐b‐PMAA as templates for emulsion polymerization of styrene produced latexes 100–200 nm in diameter. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4623–4634, 2007     

Synthesis,self‐assembly and recognition properties of biomimetic star‐shaped poly(ε‐caprolactone)‐b‐glycopolymer block copolymers

Biomimetic star‐shaped poly(ε‐caprolactone)‐b‐poly(gluconamidoethyl methacrylate) block copolymers (SPCL‐PGAMA) were synthesized from the atom transfer radical polymerization (ATRP) of unprotected GAMA glycomonomer using a tetra(2‐bromo‐2‐methylpropionyl)‐terminated star‐shaped poly(ε‐caprolactone) (SPCL‐Br) as a macroinitiator in NMP solution at room temperature. The block length of PGAMA glycopolymer within as‐synthesized SPCL‐PGAMA copolymers could be adjusted linearly by controlling the molar ratio of GAMA glycomonomer to SPCL‐Br macroinitiator, and the molecular weight distribution was reasonably narrow. The degree of crystallization of PCL block within copolymers decreased with the increasing block length ratio of outer PGAMA to inner PCL. Moreover, the self‐assembly properties of the SPCL‐PGAMA copolymers were investigated by NMR, UV‐vis, DLS, and TEM, respectively. The self‐assembled glucose‐installed aggregates changed from spherical micelles to worm‐like aggregates, then to vesicles with the decreasing weight fraction of hydrophilic PGAMA block. Furthermore, the biomolecular binding of SPCL‐PGAMA with Concanavalin A (Con A) was studied by means of UV‐vis, fluorescence spectroscopy, and DLS, which demonstrated that these SPCL‐PGAMA copolymers had specific recognition with Con A. Consequently, this will not only provide biomimetic star‐shaped SPCL‐PGAMA block copolymers for targeted drug delivery, but also improve the compatibility and drug release properties of PCL‐based biomaterials for hydrophilic peptide drugs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 817–829, 2008     

Self‐assembly of di‐ and triblock PEG‐pentavaline amphiphiles

Nanoparticles formed from amphiphilic block copolymers can be used as drug delivery vehicles for hydrophilic therapeutics. Poly(ethylene glycol) (PEG)‐peptide copolymers were investigated for their self‐assembling properties and as consequent potential delivery systems. Mono‐ and dihydroxy PEGs were functionalized with a pentavaline sequence bearing Fmoc end groups. The molecular weight of the PEG component was varied to evaluate copolymer size and block number. These di‐ and tri‐block copolymers readily self‐assemble in aqueous solution with critical aggregation concentrations (CACs) of 0.46–16.29 μM. At concentrations above the CAC, copolymer solutions form spherical assemblies. Dynamic light scattering studies indicate these aggregates have a broad size distribution, with average diameters between 33 and 127 nm. The copolymers are comprised β‐conformations that are stable up to 80 °C, as observed by circular dichroism. This peptide secondary structure is retained in solutions up to 50% MeOH as well. The triblock copolymers proved to be the most stable, with copolymers synthesized from 10 kDa PEG having the most stable particles. Loading of carboxyfluorescein at 2–5 mol % shows that these copolymers have the potential to encapsulate hydrophilic drugs for delivery applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Self‐assembling amphiphilic block copolymer from renewable δ‐decalactone and δ‐dodecalactone

Aliphatic polyesters have many applications in the biomedical field due to their properties and facile degradation. They are commonly synthesized via ring opening polymerization (ROP) with metal‐based catalysts, but as high temperatures are needed and the products contain metal, organocatalysts are now widely adopted to polymerize them at room temperature while also ensuring short reaction times. Here, 1,7,7‐triazabicyclo[4.4.0]‐dec‐5‐ene is used to polymerize less reactive but renewably‐derived lactones, namely δ‐decalactone and δ‐dodecalactone. These monomers were chosen in the attempt of creating renewable and highly lipophilic materials for drug delivery applications as alternatives to the more traditional, but non‐renewable δ‐valerolactone and ?‐caprolactone. A combination of ROP and living radical polymerization Reversible Addition‐Fragmentation Chain Transfer is proposed here to synthesize grafted block copolymers. They are able to self‐assemble in water, forming micelles where the lipophilic polyester core is able to entrap a lipophilic drug, thus making the system a good candidate for drug delivery. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3788–3797     

Synthesis and self‐assembly of helical polypeptide‐random coil amphiphilic diblock copolymer

Three amphiphilic rod‐coil diblock copolymers, poly(2‐ethyl‐2‐oxazoline‐b‐γ‐benzyl‐L ‐glutamate) (PEOz‐b‐PBLG), incorporating the same‐length PEOz block length and various lengths of their PBLG blocks, were synthesized through a combining of living cationic and N‐carboxyanhydride (NCA) ring‐opening polymerizations. In the bulk, these block copolymers display thermotropic liquid crystalline behavior. The self‐assembled aggregates that formed from these diblock copolymers in aqueous solution exhibited morphologies that differed from those obtained in α‐helicogenic solvents, that is, solvents in which the PBLG blocks adopt rigid α‐helix conformations. In aqueous solution, the block copolymers self‐assembled into spherical micelles and vesicular aggregates because of their amphiphilic structures. In helicogenic solvents (in this case, toluene and benzyl alcohol), the PEOz‐b‐PBLG copolymers exhibited rod‐coil chain properties, which result in a diverse array of aggregate morphologies (spheres, vesicles, ribbons, and tube nanostructures) and thermoreversible gelation behavior. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3108–3119, 2008