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     

Synthesis,characterization, and self‐assembly of comb‐dendronized amphiphilic block copolymers

Novel amphiphilic comb‐dendronized diblock copolymers composed of hydrophobic Percec‐type dendronized polystyrene block and hydrophilic comb‐like poly(ethylene oxide) grafted polymethacrylate P(PEOMA) block were designed and synthesized via two steps of atom transfer radical polymerization (ATRP). The comb‐like P(PEOMA) prepared by ATRP of macromonomers (PEOMA) with two different molecular weights (M_n = 300 and 475) were used to initiate the sequent ATRP of dendritic styrene macromonomer (DS). The molecular weights and compositions of the obtained block copolymers were determined by ¹H NMR analysis. The copolymers with relatively narrow polydispersities (1.27–1.38) were thus obtained. The bulk properties of comb‐dendronized block copolymers were studied by using differential scanning calorimetry, polarized optical microscopy and wide‐angle X‐ray diffraction (WAXD). Similar to dendronized homopolymers, the block copolymers exhibited hexagonal columnar liquid‐crystalline phase structure. By using such amphiphilic comb‐dendronized block copolymers as building blocks, the rich self‐assembly morphologies, such as twisted string, vesicle, and large compound micelle (LCM), were obtained in a mixture of CH₃OH and THF. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4205–4217, 2008     

UV‐induced crosslinking of ring opening metathesis block copolymer micelles

Statistical and amphiphilic block copolymers bearing cinnamoyl groups were prepared by ring opening metathesis polymerization (ROMP). The UV‐induced [2 + 2] cycloaddition reaction of polymer bound cinnamic acid groups was studied in polymer thin films as well as in block copolymer micelles. In both cases, exposure to UV‐light for 10 min led to a crosslinking conversion of about 60%, as determined by FT‐IR spectroscopy and UV–vis absorption measurements. Time based IR‐spectroscopy revealed a maximum conversion of 78% reached after an irradiation time of about 16 min. For micelles obtained from polymers bearing 5 mol % or more cinnamoyl groups, the crosslinking reaction proceeded smoothly, yielding in crosslinked particles which were stable in a non‐selective solvent (CHCl₃). Diameters determined by dynamic light scattering in the selective solvent (MeOH) were similar for both, non‐crosslinked and crosslinked micelles, whereas diameters of crosslinked micelles in the non‐selective solvent (CHCl₃) were significantly larger compared to MeOH samples. This strategy of direct self assembly of block‐copolymers in a selective solvent followed by “clean” crosslinking, without the need for additional crosslinking reagents or crosslinking initiators, provides a straight forward approach toward ROMP‐based polymeric nano‐particles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2402–2413, 2008     

Insights into poly(3‐hexylthiophene)‐b‐poly(ethylene oxide) block copolymer: Synthesis and solvent‐induced structure formation in thin films

We report the synthesis, characterization, and solvent‐induced structure formation in thin films of an amphiphilic rod‐coil conjugated block copolymer, poly(3‐hexylthiophene)‐b‐poly(ethylene oxide). The diblock copolymers were prepared by a facile click reaction and their characterizations as well as thermal, crystalline, optical properties, and self‐assembly behavior have been investigated in detail. A series of morphologies including two‐phase separated nanostructure, nanofibrils, and their mixed morphology could be obtained depending on the selectivity of solvents to different blocks. Structural analyses demonstrate there is a subtle balance between microphase separation of copolymer and the π‐π stacking of the conjugated P3HT and such balance can be controlled by changing the solvents of different selectivity in solution and the length of P3HT block. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Recent advances in the solution self‐assembly of amphiphilic “rod‐coil” copolymers

Solution self‐assembly of amphiphilic “rod‐coil” copolymers, especially linear block copolymers and graft copolymers (also referred to as polymer brushes), has attracted considerable interest, as replacing one of the blocks of a coil‐coil copolymer with a rigid segment results in distinct self‐assembly features compared with those of the coil‐coil copolymer. The unique interplay between microphase separation of the rod and coil blocks with great geometric disparities can lead to the formation of unusual morphologies that are distinctly different from those known for coil‐coil copolymers. This review presents the recent achievements in the controlled self‐assembly of rod‐coil linear block copolymers and graft copolymers in solution, focusing on copolymer systems containing conjugated polymers, liquid crystalline polymers, polypeptides, and polyisocyanates as the rod segments. The discussions concentrate on the principle of controlling over the morphology of rod‐coil copolymer assemblies, as well as their distinctive optical and optoelectronic properties or biocompatibility and stimuli‐responsiveness, which afford the assemblies great potential as functional materials particularly for optical, optoelectronic and biological applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1459–1477     

Synthesis and self assembly of eosin functionalized amphiphilic block‐random copolymers prepared by ring opening metathesis polymerization

Self assembly of block copolymers has gained considerable attention because of its potential use in various areas such as medical and biomedical applications, nanotechnology, and electronics. Herein, we present the synthesis and characterization of amphiphilic block‐random copolymers with a covalently incorporated pH‐sensitive dye, namely eosin. Ring opening metathesis polymerization was chosen for the preparation of well defined block copolymers and block‐random copolymers using a modified “2nd Generation Grubbs” initiator. The self assembly behavior of the block‐random copolymers in solution was studied by dynamic light scattering and small angle X‐ray scattering (SAXS). The influence of dye incorporation on the result of the self assembly process in methanol and ethanol was investigated and a subtle interplay of the nature of the selective solvent, the chain‐length of the block copolymer and the position of the dye within the polymer chain was established. Structural investigations using SAXS revealed a spherical shape and a core‐shell structure of exemplary block and block‐random copolymer micelles. UV–vis absorption and photoluminescence measurements revealed similar optical properties for polymer micelles in methanol compared to polymer solutions in THF. The pH‐sensitive behavior of the eosin dye was preserved within the micelles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 401–413, 2008     

Biofunctionalized block copolymer nanoparticles based on ring‐opening metathesis polymerization

We present an approach to the synthesis of biofunctionalized block copolymer nanoparticles based on ring‐opening metathesis polymerization; these nanoparticles may serve as novel scaffolds for the multivalent display of ligands. The nanoparticles are formed by the self‐assembly of diblock copolymers composed of a hydrophobic block and a hydrophilic activated block that can be functionalized with thiolated ligands in aqueous media. The activated block enables control over the orientation of the displayed ligands, which may be sugars, peptides, or proteins engineered to contain cysteine residues at suitable locations. The nanoparticle diameter can be varied over a wide range through changes in the composition of the block copolymer, and biofunctionalization of the nanoparticles has been demonstrated by the attachment of a peptide previously shown to inhibit the assembly of anthrax toxin. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 928–939, 2006     

Synthesis of new amphiphilic diblock copolymers containing poly(ethylene oxide) and poly(α‐olefin)

This article discusses an effective route to prepare amphiphilic diblock copolymers containing a poly(ethylene oxide) block and a polyolefin block that includes semicrystalline thermoplastics, such as polyethylene and syndiotactic polystyrene (s‐PS), and elastomers, such as poly(ethylene‐co‐1‐octene) and poly(ethylene‐co‐styrene) random copolymers. The broad choice of polyolefin blocks provides the amphiphilic copolymers with a wide range of thermal properties from high melting temperature ～270 °C to low glass‐transition temperature ～?60 °C. The chemistry involves two reaction steps, including the preparation of a borane group‐terminated polyolefin by the combination of a metallocene catalyst and a borane chain‐transfer agent as well as the interconversion of a borane terminal group to an anionic (? O^?K⁺) terminal group for the subsequent ring‐opening polymerization of ethylene oxide. The overall reaction process resembles a transformation from the metallocene polymerization of α‐olefins to the ring‐opening polymerization of ethylene oxide. The well‐defined reaction mechanisms in both steps provide the diblock copolymer with controlled molecular structure in terms of composition, molecular weight, moderate molecular weight distribution (M_w/M_n < 2.5), and absence of homopolymer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3416–3425, 2002     

ABA triblock copolymers with a ring‐opening metathesis polymerization/macromolecular chain‐transfer agent approach

Block copolymers containing polystyrene and polycyclooctene were synthesized with a ring‐opening metathesis polymerization/chain‐transfer approach. Polystyrene, containing appropriately placed olefins, was prepared by anionic polymerization and served as a macromolecular chain‐transfer agent for the ring‐opening metathesis polymerization of cyclooctene. These unsaturated polymers were subsequently converted to the corresponding saturated triblock copolymers with a simple heterogeneous catalytic hydrogenation step. The molecular and morphological characterization of the block copolymers was consistent with the absence of significant branching in the central polycyclooctene and polyethylene blocks [high melting temperatures (114–127 °C) and levels of crystallinity (17–42%)]. A dramatic improvement in both the long‐range order and the mechanical properties of a microphase‐separated, symmetric polystyrene–polycyclooctene–polystyrene block copolymer sample was observed after fractionation. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 361–373, 2007     

Block copolymer nanoparticles of controlled sizes via ring‐opening metathesis polymerization

This article describes the formation and characterization of self‐assembled nanoparticles of controlled sizes based on amphiphilic block copolymers synthesized by ring‐opening metathesis polymerization. We synthesized a novel hydrophobic derivative of norbornene; this monomer could be polymerized using Grubbs' catalyst [Cl₂Ru(CHPh)(PCy₃)₂] forming polymers of controlled molecular weight. We synthesized amphiphilic block copolymers of controlled composition and showed that they assemble into nanoparticles of controlled size. The nanoparticles were characterized using dynamic light scattering and transmission electron microscopy. Tuning the composition of the block copolymer enables the tuning of the diameters of the nanoparticles in the 30‐ to 80‐nm range. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3352–3359, 2004     

Synthesis and characterization of polycholesteryl methacrylate–polyhydroxyethyl methyacrylate block copolymers

We report the synthesis and characterization of a series of novel diblock copolymers, poly(cholesteryl methacrylate‐b‐2‐hydroxyethyl methacrylate) (PCMA‐b‐PHEMA). Monomers, cholesteryl methacrylate (CMA) and 2‐(trimethylsiloxy)ethyl methacrylate (HEMA‐TMS), were prepared from methyacryloyl chloride and 2‐hydroxyethyl methacrylate, respectively. Homopolymers of CMA, PCMA, with well‐defined molecular weights and polydispersity indices (PDI), were prepared by reversible addition fragmentation and chain transfer (RAFT) method. Precursor diblock copolymers, PCMA‐b‐P(HEMA‐TMS), were synthesized using PCMA as macromolecular chain transfer agent and monomer, HEMA‐TMS. Product diblock copolymers, PCMA‐b‐PHEMA, were prepared by deprotecting trimethylsilyl units in the precursor diblock copolymers using acid catalysts. Detailed molecular characterization of the precursor diblock copolymers, PCMA‐b‐P(HEMA‐TMS), and the product diblock copolymers, PCMA‐b‐PHEMA, confirmed the composition and structure of these polymers. This versatile synthetic strategy can be used to prepare new amphiphilic block copolymers with cholesterol in one block and hydrogen‐bonding moieties in the second block. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6801–6809, 2008     

Synthesis of chiral amphiphilic diblock copolymers via consecutive RAFT polymerizations and their aggregation behavior in aqueous solution

Two chiral amphiphilic diblock copolymers with different relative lengths of the hydrophobic and hydrophilic blocks, poly(6‐O‐p‐vinylbenzyl‐1,2:3,4‐Di‐O‐isopropylidene‐D ‐galactopyranose)‐b‐poly(N‐isopropylacrylamide) or poly(VBCPG)‐b‐poly(NIPAAM) and poly(20‐(hydroxymethyl)‐pregna‐1,4‐dien‐3‐one methacrylate)‐b‐poly(N‐isopropylacrylamide) or poly(MAC‐HPD)‐b‐poly(NIPAAM) were synthesized via consecutive reversible addition‐fragmentation chain‐transfer polymerizations of VBCPG or MAC‐HPD and NIPAAM. The chemical structures of these diblock copolymers were characterized by ¹H nuclear magnetic resonance spectroscopy. These amphiphilic diblock copolymers could self‐assemble into micelles in aqueous solution, and the morphologies of micelles were investigated by transmission electron microscopy. By comparison with the lower critical solution temperatures (LCST) of poly(NIPAAM) homopolymer in deionized water (32 °C), a higher LCST of the chiral amphiphilic diblock copolymer (poly(VBCPG)‐b‐poly(NIPAAM)) was observed and the LCST increased with the relative length of the poly(VBCPG) block in the copolymer from 35 to 47 °C, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7690–7701, 2008     

Self‐assembly of oligo(p‐phenylenevinylene)‐block‐poly(ethylene oxide) in polar media and solubilization of an oligo(p‐phenylenevinylene) homooligomer inside the assembly

Rod–coil amphiphilic diblock copolymers, consisting of oligo(p‐phenylenevinylene) (OPV) as a rod and hydrophobic block and poly(ethylene oxide) (PEO) as a coil and hydrophilic block, were synthesized by a convergent method. The aggregation behavior of the block copolymers in a selective solvent (tetrahydrofuran/H₂O) was probed with the absorption and emission of the OPV block. With increasing H₂O concentration, the absorption maximum was blueshifted, the emission from the molecularly dissolved OPV decreased, and that from the aggregated OPV increased. This indicated that the OPV blocks formed H‐type aggregates in which the OPV blocks aligned in a parallel orientation with one another. The transmission electron microscopy observation revealed that the block copolymers with PEO weight fractions of 41 and 62 wt % formed cylindrical aggregates with a diameter of 6–8 nm and a length of several hundreds nanometers, whereas the block copolymer with 79 wt % PEO formed distorted spherical aggregates with an average diameter of 13 nm. Furthermore, the solubilization of an OPV homooligomer with the block copolymer was studied. When the total polymer concentration was less than 0.1 wt %, the block copolymer solubilized OPV with a 50 mol % concentration. The structure of the aggregates was a cylinder with a relatively large diameter distribution. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1569–1578, 2005     

Homo‐ and diblock copolymers of poly(furfuryl glycidyl ether) by living anionic polymerization: Toward reversibly core‐crosslinked micelles

We report the synthesis and characterization of well‐defined homo‐ and diblock copolymers containing poly(furfuryl glycidyl ether) (PFGE) via living anionic ring‐opening polymerization using different initiators. The obtained materials were characterized by SEC, MALDI‐TOF MS, and ¹H NMR spectroscopy and molar masses of up to 9400 g/mol were obtained for PFGE homopolymers. If the amphiphilic diblock copolymer PEG‐block‐PFGE was dissolved in water, micelles with a PFGE core and a PEG corona were formed. Hereby, the hydrophobic PFGE core domains were used for the incorporation of a suitable bismaleimide and heating to 60 °C induced the crosslinking of the micellar core via Diels‐Alder chemistry. This process was further shown to be reversible. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Multiple morphologies of the aggregates from self‐assembly of diblock copolymer with relatively long corona‐forming block in dilute aqueous solution

Reported here is self‐assembly behavior in selective solvent of diblock copolymers with relatively long corona‐forming block compared to core‐forming block. Three diblock copolymers, poly(ethylene glycol) monomethyl ether‐b‐poly(methacryloyl‐L ‐leucine methyl ester), also denoted as MPEG‐b‐PMALM copolymer, were prepared by fixing MPEG block with an average number of repeating units of 115, whereas varying PMALM block with an average number of repeating unit of 44, 23, 9, respectively. Multiple morphologies, such as sphere, cylinder, vesicle, and their coexisted structures from self‐assembly of these diblock copolymers in aqueous media by changing block nonselective solvent and initial polymer concentration used in preparation, were demonstrated directly via TEM observation. These results herein might, therefore, demonstrate as an example that a wide range of morphologies can be accessed not only from “crew‐cut micelles” but also from “star‐micelles” by controlling over preparation strategies. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 364–371, 2010     

Supramolecular Diblock Copolymers Featuring Well‐defined Telechelic Building Blocks

We report supramolecular AB diblock copolymers comprised of well‐defined telechelic building blocks. Helical motifs, formed via reversible addition‐fragmentation chain‐transfer (RAFT) or anionic polymerization, are assembled with coil‐forming and sheet‐featuring blocks obtained via atom‐transfer radical polymerization (ATRP) or ring‐opening metathesis polymerization (ROMP). Interpolymer hydrogen bonding or metal‐coordination achieves dynamic diblock architectures featuring hybrid topologies of coils, helices, and/or π‐stacked sheets that, on a basic level, mimic protein structural motifs in fully synthetic systems. The intrinsic properties of each block (e.g., circular dichroism and fluorescence) remain unaffected in the wake of self‐assembly. This strategy to develop complex synthetic polymer scaffolds from functional building blocks is significant in a field striving to produce architectures reminiscent of biosynthesis, yet fully synthetic in nature. This is the first plug‐and‐play approach to fabricate hybrid π‐sheet/helix, π‐sheet/coil, and helix/coil architectures via directional self‐assembly.     

Tuning nanoscopic self‐assembly of diblock copolymer blends on a two‐dimensional interface

Spreading amphiphilic diblock copolymers on a two‐dimensional liquid interface has been observed to produce nanoscale features via self‐assembly. Here, we develop a model that incorporates the effects of polymer entanglement and surface diffusion in polymer blends to quantitatively predict the size of experimentally observed structures. Simulations show that different polymers in the blend cooperate to self‐assemble into nanoscale features of varying sizes. Characteristic nanoscopic dimensions can be tuned by adjusting two easily controllable macroscopic quantities: the blend composition and the initial surface concentration. Theoretical predictions are in agreement with experimentally measured feature dimensions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Synthesis,characterization, and micellization of PCL‐g‐PEG copolymers by combination of ROP and “Click” chemistry via “Graft onto” method

Biodegradable and biocompatible PCL‐g‐PEG amphiphilic graft copolymers were prepared by combination of ROP and “click” chemistry via “graft onto” method under mild conditions. First, chloro‐functionalized poly(ε‐caprolactone) (PCL‐Cl) was synthesized by the ring‐opening copolymerization of ε‐caprolactone (CL) and α‐chloro‐ε‐caprolactone (CCL) employing scandium triflate as high‐efficient catalyst with near 100% monomer conversion. Second, the chloro groups of PCL‐Cl were quantitatively converted into azide form by NaN₃. Finally, copper(I)‐catalyzed cycloaddition reaction was carried out between azide‐functionalized PCL (PCL‐N₃) and alkyne‐terminated poly(ethylene glycol) (A‐PEG) to give PCL‐g‐PEG amphiphilic graft copolymers. The composition and the graft architecture of the copolymers were characterized by ¹H NMR, FTIR, and GPC analyses. These amphiphilic graft copolymers could self‐assemble into sphere‐like aggregates in aqueous solution with diverse diameters, which decreased with the increasing of grafting density. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of phenylenevinylene and naphthylenevinylene homopolymers and block copolymers by ring‐opening metathesis polymerization

Homopolymers and copolymers containing phenylenevinylenes and naphthylenevinylenes can be synthesized by ring‐opening metathesis polymerization of strained monomers such as tetraoctyloxy‐substituted cyclophanedienes and naphthalenophanedienes initiated by the third‐generation Grubbs’ initiator. The resulting homopolymers exhibited low polydispersities. The block copolymers can also be synthesized by the sequential ring‐opening metathesis polymerization of two individual monomers. The structures of homopolymers and block copolymers were fully characterized by nuclear magnetic resonance spectroscopy. The molecular weight distribution of the block copolymers is relatively broad compared to their parent homopolymers possibly due to chain transfer reaction. The molar ratio of the two blocks can be tailored by the ratio of the monomers employed. The block copolymers exhibited a more efficient energy transfer in the solid state between the different blocks than those carried out in solution. The optical and electrochemical properties of the polymers were investigated and exhibited the potential uses in optoelectronics devices. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 67–74     

Synthesis and Characterization of Novel Biodegradable Di‐ and Tri‐Block Copolymers Based on Ethylene Carbonate Polymer as Hydrophobic Segment

Synthesis of novel amphiphilic biodegradable block copolymers based on ethylene carbonate is reported in this study. Polyethylene glycol monomethyl ether (MeO‐PEO) and polyethylene glycol (PEG) of varying molar masses are used as macro‐initiator for ring‐opening polymerization of ethylene carbonate in the presence of sodium stannate trihydrate as a heterogeneous transesterification catalyst. Earlier elution of block copolymer from macro‐initiator in size exclusion chromatography (SEC) indicated the successful synthesis of the block copolymers. Ratios of both types of blocks are varied systematically. Liquid chromatography at critical conditions is used for the analysis of the non‐critical individual blocks, and if there are any critical segments that are not attached to the non‐critical block. To the best of our knowledge, this is the first report on the synthesis of ethylene carbonate‐based amphiphilic block copolymers. Chromatographic critical conditions of the ethylene carbonate polymer are also reported for the first time. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1887–1893