Asymmetric Triblock Copolymers Research Articles

Improved Elastic Recovery from ABC Triblock Terpolymers.

The promise of ABC triblock terpolymers for improving the mechanical properties of thermoplastic elastomers is demonstrated by comparison with symmetric ABA/CBC analogs having similar molecular weights and volume fraction of B and A/C domains. The ABC architecture enhances elasticity (up to 98% recovery over 10 cycles) in part through essentially full chain bridging between discrete hard domains leading to the minimization of mechanically unproductive loops. In addition, the unique phase space of ABC triblocks also enables the fraction of hard-block domains to be higher (fhard ≈ 0.4) while maintaining elasticity, which is traditionally only possible with non-linear architectures or highly asymmetric ABA triblock copolymers. These advantages of ABC triblock terpolymers provide a tunable platform to create materials with practical applications while improving our fundamental understanding of chain conformation and structure-property relationships in block copolymers.

Triblock Copolymer Toughening of a Carbon Fibre-Reinforced Epoxy Composite for Bonded Repair.

Epoxy resins are the most widely used systems for structural composite applications; however, they lack fracture toughness, impact strength and peel strength due to high cross-linking densities. Use of conventional toughening agents to combat this can lead to reductions in mechanical, thermal and processability properties desirable for bonded composite applications. In this work, an asymmetric triblock copolymer of poly(styrene)–b–poly(butadiene)–b–poly(methylmethacrylate) was used to modify an epoxy resin system, with the materials processed using both vacuum bag and positive pressure curing techniques. Interlaminar fracture toughness testing showed improvements in initiation fracture toughness of up to 88%, accompanied by a 6 °C increase in glass transition temperature and manageable reductions in gel-time. Shear testing resulted in a 121% increase in ultimate shear strain with only an 8% reduction in shear strength. Performance improvements were attributed to nano-structuring within the toughened resin system, giving rise to matrix cavitation and dissipation of crack front strain energy upon loading.

Stimuli-responsive properties of special micellar nanocarriers and their application for delivery of vitamin E and its analogues

Stimuli-responsive micelles were formed by asymmetric diblock and triblock copolymers, which comprised chemically complementary (methoxy)poly(ethylene oxide) and poly(acrylic acid) blocks of different length. They were used as nanocarriers to encapsulate and deliver in vivo a poorly soluble homolog of α-tocopheryl acetate (α-TOCAh), commonly known as an analogue of vitamin E. Self-assembly of the copolymer macromolecules into special micellar structures in aqueous solutions depended on the solution pH. The micellar structures arising at pH < 5 due to hydrogen bonds between the blocks and the subsequent segregation of the hydrophobic bound segments in the aqueous medium were stable in the temperature range 20–60 °C and with dilution of the solution. The micelle formation/destruction in the copolymer solutions at pH alteration was shown to be an equilibrium process. Various morphological forms of micelles depending on the copolymer structure and the blocks’ asymmetry were revealed by the TEM method. All types of micelles showed high binding degrees (about 100%) of α-TOCAh, which did not depend on the encapsulation pathway (“in situ” or “ex situ”). Encapsulation of α-TOCAh resulted in hydrophobization of the micelle surface, thereby enhancing the aggregation of micelles in aqueous solution. Encapsulated α-tocopheryl acetate was in vivo fully digested by the animals (white mice) and showed increased biological activity, which allowed reducing its therapeutic dose by 25 times.

Morphology Reentry with a Change in Degree of Chain Asymmetry in Neat Asymmetric Linear A1BA2 Triblock Copolymers

We report experimental results on relationship between polymer chain architecture and morphology of microdomains of asymmetric linear triblock copolymers, S1BS2 (S: polystyrene; B: polybutadiene). For this purpose, we synthesized various asymmetric triblock copolymers having different lengths of two end-blocks. The morphology was examined by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Although total molecular weight, composition, and thermal annealing temperature were kept constant, the morphology was found to change with a degree of chain asymmetry. One typical example exhibits a morphological change as cylinder → lamella → cylinder with a decrease in length of the shorter S2 end-block chains, while keeping the total molecular weight and the total polystyrene composition constant. This curious morphological behavior exhibiting a re-entrant type change is qualitatively in accord with the self-consistent field theory (SCFT) results by Matsen [J. Chem. Phys. 2000, 113, 55...

Nanopattern transformation of ABC triblock copolymer thin films induced by strong solvent selectivity and annealing

Nanopattern transformation behaviors of polyisoprene-block-polystyrene-block-poly(2-vinylpyridine) (PI-b-PS-b-P2VP) asymmetric ABC triblock copolymer were investigated systematically with various control parameters, including different solvents for polymer solution and annealing conditions in this paper. Ordered nanopattern of PI-b-PS-b-P2VP with hexagonal cylinders could be obtained when PI-b-PS-b-P2VP toluene solution was spin-coated on silicon substrate followed by toluene vapor annealing process. When the film with hexagonal and cylindrical nanopattern was exposed to saturated toluene vapor, the order-order transition of cylindrical nanopattern to parallel nanopattern was observed due to the strong selectivity of toluene to PS and PI blocks. Furthermore, fingerprint nanopattern could also be obtained by solvent annealing in tetrahydrofuran vapor. The nanopattern transformation was due to different selectivity of solvents and incompatibilities of the three blocks of PI-b-PS-b-P2VP under various solvent annealing conditions.

Nanostructured polymer blends based on polystyrene-b- polybutadiene-b -poly(methyl methacrylate) triblock copolymers modified with polystyrene and/or poly(methyl methacrylate) homopolymers

Morphologies of polymer blends based on polystyrene-b-polybutadiene-b-poly (methyl methacrylate) (SBM) triblock copolymer were predicted adopting the phase diagram proposed by Stadler and co-workers for neat SBM block copolymer, and experimentally proved using atomic force microscopy. All investigated polymer blends based on SBM triblock copolymer modified with polystyrene (PS) and/or poly(methyl methacrylate) (PMMA) homopolymers showed expected nanostructures. For polymer blends of symmetric SBM-1 triblock copolymer with PS homopolymer, cylinders in cylinders core-shell morphology and perforated lamellae morphology were obtained. Moreover, modifying the same SBM-1 triblock copolymer with both PS and PMMA homopolymers cylinders at cylinders morphology was reached. The predictions for morphologies of blends based on asymmetric SBM-2 triblock copolymer were also confirmed experimentally, visualizing a spheres over spheres structure. This work presented an easy way of using PS and/or PMMA homopolymers for preparing nanostructured polymer blends based on SBM triblock copolymers with desired morphologies, similar to those of neat SBM block copolymers.

Compositions of Anticancer Drug with Micellar Nanocarriers and Their Cytotoxicity

Asymmetric diblock (DBC) and triblock (TBC) copolymers contained biocompatible chemically complementary polyacrylamide and poly(ethylene oxide) (PAAm-b-PEO-b-PAAm) or its monomethyl ether (MEPEO-b-PAAm), and also partially hydrolyzed triblock copolymer derivative (TBChydr) were used to create micelles of a special type. The micelles obtained are characterized by small CMCs and large values of the Gibbs micellization energy, thus indicating a high stability of DBC, TBC and TBChydr micelles in aqueous solutions and the capabilities of their use to encapsulate and deliver poorly soluble and/or toxic drugs in living organism. Morphological features and size of DBC and TBC micelles were determined by TEM. The electron images demonstrated spherical micelles of a polymolecular type, monomolecular type and separate micelle aggregates. TBC and TBChydr micelles were used to examine in vitro anticancer activity of their compositions with doxorubicin (Dox). The created micelle systems showed the enhanced cytotoxicity as compared to individual Dox against murine leukemia cells of L1210 line, murine transformed fibroblasts of L929 line and human T-leukemia cells of Jurkat line and allow to achieve a high efficacy at low Dox concentrations (0,1÷3 µg·cm-3) that opens the great prospects for essential decrease in drug dose at chemotherapy.

Hollow carbon nanospheres using an asymmetric triblock copolymer structure directing agent.

We introduce a simple method to prepare hollow carbon nanospheres (HCNs) by using triblock copolymer poly(styrene-b-2-vinylpyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) micelles as a new class of soft-templates. Simply by changing the solvent we can prepare ultra-small sized micelles of the triblock copolymer PS-b-P2VP-b-PEO soft template to obtain HCNs with ultra-small diameters (43 nm) and hollow cores (19 nm). Furthermore, we use these HCNs to make electric double-layer capacitors (EDLCs) that exhibit superior performance.

Triblock copolymers for nano-sized drug delivery systems

Triblock copolymers have been widely used as a material for developing drug delivery systems (DDS). In terms of architecture, triblock copolymers could be classified into symmetric and asymmetric triblock copolymers. Different types of nano-sized structures such as star micelles, flower-like micelles, and polymer vesicles could be prepared from these block copolymers, which would be very potential in delivering various types of agents such as chemical drugs, genes, and contrast agents. Additionally, the nano-sized carriers have been fabricated for environmentally sensitive (pH-sensitive or temperature sensitive) DDS or for enhancing the gene delivery efficiency. Due to their versatility in structures and drug delivery capacity, the application of triblock copolymers would definitely be expanded in near future.

Micellar nanocarriers for anticancer drug melanin

ABSTRACTThe effective biocompatible and partially biodegradable micellar nanocarriers for encapsulation of the anticancer drug eumelanin were created. Such nanocarries are the products of self-assembly of asymmetric diblock and triblock copolymers, which comprised chemically complementary (methoxy)poly(ethylene oxide) and poly(acrylic acid) blocks of a variable length. A chemical structure and solubility of the eumelanin, the vital activity product of black yeast “Nadsoniella nigra sp. X-1, was characterized. Peculiarities of the micellization process, morphology, size and stability of the developed micellar nanocarries were highlighted. The eumelanin encapsulation into micellar nanocarries with different morphology and a state of the obtained drug/micelle systems were studied and discussed.

Asymmetric Triblock Copolymer Nanocarriers for Controlled Localization and pH-Sensitive Release of Proteins.

Designing nanocarriers to release proteins under specific conditions is required to improve therapeutic approaches, especially in treating cancer and protein deficiency diseases. We present here supramolecular assemblies based on asymmetric poly(ethylene glycol)-b-poly(methylcaprolactone)-b-poly(2-(N,Ndiethylamino)ethyl methacrylate) (PEG-b-PMCL-b-PDMAEMA) copolymers for controlled localization and pH-sensitive release of proteins. Copolymers self-assembled in soft nanoparticles with a core domain formed by PMCL, and a hydrophilic domain based on PEG mainly embedded inside, and the branched PDMAEMA exposed at the particle surface. We selected as model proteins to be attached to the nanoparticles bovine serum albumin (BSA) and acid sphingomyelinase (ASM), the latter being an ideal candidate for protein replacement therapy. The hydrophilic/hydrophobic ratio, nanoparticle size, and the nature of biomolecules are key factors for modulating protein localization and attachment efficiency. The predominant outer shell of PDMAEMA allows efficient pH-triggered release of BSA and ASM, and in acidic conditions >70% of the bound proteins were released. Uptake of protein-attached nanoparticles by HELA cells, together with low toxicity and pH-responsive release, supports such protein-bound nanoparticles as efficient stimuli-responsive candidates for protein therapy.

Enthalpy-driven selective loading of CdSe0.75S0.25 nanoalloys in triblock copolymer polystyrene-b-polyisoprene-b-polystyrene

CdSe0.75S0.25 nanoalloys were blended with asymmetric triblock copolymer of polystyrene-b-polyisoprene-b-polystyrene(PS-SIS) in tetrahydrofuran. The fraction of styrene block varies from 14 to 22% with respect to isoprene by mass. The morphology of the copolymer cast film experiences a phase change from cylinder to lamella. CdSe0.75S0.25 nanoalloys were prepared by two-phase method. The surface of the nanoalloys was capped by either oleic acid (OA) or n-tri-octylphosphonic acid (TOPO) in situ. The mean diameter of the alloyed particles is around 12nm in both systems. The chemical nature of the nanoalloy surface was found to influence the dispersion of the particles over polymer volume. The size of the nanoalloy domains in PS is 50nm, on average, consisting of approximately 0.7wt% nanoalloys. However, the size of the nanoalloy domains is smaller when they are loaded into PS-SIS. The structure formation is predominantly determined by enthalpic compatibilization. Atomic force microscopy results suggest that the nanoalloys capped with TOPO sequester into PS-rich domains and enlarge the domain. On the other hand, the ones capped with OA prefer to locate in polyisoprene domains. The increase of particles over 1.0wt% distorts the lamella structure.

Synthesis of Mesoporous Transition-Metal Phosphates by Polymeric Micelle Assembly.

Mesoporous iron phosphate (FePO4 ) was synthesized through assembly of polymeric micelles made of asymmetric triblock co-polymer (polystyrene-b-poly-2-vinylpyridine-b-ethylene oxide; PS-PVP-PEO). The phosphoric acid solution stimulates the formation of micelles with core-shell-corona architecture. The negatively charged PO4 (3-) ions dissolved in the solution strongly interact with the positively charged PVP(+) units through an electrostatic attraction. Also, the presence of PO4 (3-) ions realizes a bridge between the micelle surface and the metal ions. The removal of polymeric template forms the robust framework of iron phosphate with 30 nm pore diameter and 15 nm wall thickness. Our method is applicable to other mesoporous metal phosphates by changing metal sources. The obtained materials were fully characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), N2 adsorption-desorption, Raman spectroscope, and other techniques.

Research Update: Triblock copolymers as templates to synthesize inorganic nanoporous materials

This review focuses on the application of triblock copolymers as designed templates to synthesize nanoporous materials with various compositions. Asymmetric triblock copolymers have several advantages compared with symmetric triblock copolymers and diblock copolymers, because the presence of three distinct domains can provide more functional features to direct the resultant nanoporous materials. Here we clearly describe significant contributions of asymmetric triblock copolymers, especially polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (abbreviated as PS-b-P2VP-b-PEO).

Fddd network phase in ABA triblock copolymer melts

Using self-consistent field theory, we investigate the stability of the orthorhombic Fddd network phase (O70) in ABA triblock copolymer melt systems. Consistent with previous findings, we observe that the gross topology of phase behavior is unchanged with varying chain asymmetry. However, the mean field critical point is displaced from the diblock copolymer value of fA = 0.5 (fA is the A segment volume fraction) to larger values as the triblock copolymer symmetry is broken with unequal A block lengths. This deviation significantly shifts the order-order phase boundaries, resulting in an appreciable region of O70 stability in the phase diagram of asymmetric ABA triblock copolymers. More importantly, the stability of the O70 phase extends to the intermediate segregation regime for select chain asymmetries. Both features are desirable for achieving a synthetic realization of the phase in binary AB block copolymer systems. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016

Concentration-induced structural transition of block polymer self-assemblies on a nanoparticle surface: computer simulation

Film structure of asymmetric triblock copolymers assembled on different degrees of hydrophobic NP surfaces was controlled by concentration.

Additives Induced Structural Transformation of ABC Triblock Copolymer Particles.

Here we report the structural control of polystyrene-b-polyisoprene-b-poly(2-vinylpyridine) (PS-b-PI-b-P2VP) asymmetric ABC triblock copolymer particles under 3D confinement by tuning the interactions among blocks. The additives, including 3-n-pentadecylphenol, homopolystyrene, and solvents, which can modulate the interactions among polymer blocks, play significant roles in the particle morphology. Moreover, the structured particles can be disassembled into isolated micellar aggregates with novel morphologies or mesoporous particles with tunable pore shape. Interestingly, the formed pupa-like PS-b-PI-b-P2VP particles display interesting dynamic stretch-retraction behavior when the solvent property is changed after partial cross-linking of the P2VP block. We further prove that such dynamic behavior is closely related to the density of cross-linking. The strategies presented here are believed to be promising routes to rationally design and fabricate block copolymer particles with desirable shape and internal structure.

Morphology re‐entry in asymmetric PS‐PI‐PS' triblock copolymer and PS homopolymer blends

ABSTRACTHere, we report the morphology variation in a series of PS‐b‐PI‐b‐PS' asymmetric triblock copolymer and PS homopolymer (hPS) blends, where PS' and PS are polystyrene blocks with a molecular weight ratio of approximately 0.11 and PI is poly(isoprene). We find that adding a small amount of hPS results in significant order–order transition (OOT) boundary deflection toward higher PS volume fractions fPS, which is accompanied by morphology re‐entry. For example, the neat triblock copolymer with a PS + PS' volume fraction of fPS = 0.38 exhibits a lamellar microphase; adding a small amount of hPS reverts the morphology into a hexagonal phase with PS cylinders, while further increasing the hPS fraction leads to normal OOTs from PS cylinders to lamellae, to PI cylinders and finally to spheres. The morphology variation reported here is significantly different from that reported in binary blends of diblock or symmetric triblock copolymer with homopolymer. While the domain features of the LAM structure can be correctly reproduced by self‐consistent field theory (SCFT), the observed morphology re‐entry is absent in the theoretical SCFT phase diagram. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 169–179

Dual soft-template system based on colloidal chemistry for the synthesis of hollow mesoporous silica nanoparticles.

A new dual soft-template system comprising the asymmetric triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) is used to synthesize hollow mesoporous silica (HMS) nanoparticles with a center void of around 17 nm. The stable PS-b-P2VP-b-PEO polymeric micelle serves as a template to form the hollow interior, while the CTAB surfactant serves as a template to form mesopores in the shells. The P2VP blocks on the polymeric micelles can interact with positively charged CTA(+) ions via negatively charged hydrolyzed silica species. Thus, dual soft-templates clearly have different roles for the preparation of the HMS nanoparticles. Interestingly, the thicknesses of the mesoporous shell are tunable by varying the amounts of TEOS and CTAB. This study provides new insight on the preparation of mesoporous materials based on colloidal chemistry.

Asymmetric block copolymers for supramolecular templating of inorganic nanospace materials.

This review focuses on polymeric micelles consisting of asymmetric block copolymers as designed templates for several inorganic nanospace materials with a wide variety of compositions. The presence of chemically distinct domains of asymmetric triblock and diblock copolymers provide self-assemblies with more diverse morphological and functional features than those constructed by EOn POm EOn type symmetric triblock copolymers, thereby affording well-designed nanospace materials. This strategy can produce unprecedented nanospace materials, which are very difficult to prepare through other conventional organic templating approaches. Here, the recent development on the synthesis of inorganic nanospace materials are mainly focused on, such as hollow spheres, tubes, and porous oxides, using asymmetric triblock copolymers.