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Sample records for amphiphilic block copolymers

  1. Microemulsions of ABA Amphiphilic Block Copolymers and Surfactants

    NASA Astrophysics Data System (ADS)

    Braun-Shmueli, Liora; Netanel, Ortal; Regev, Oren; Gottlieb, Moshe

    2001-03-01

    The system composed of oil (decane), water and an ABA amphiphilic block copolymer is capable of exhibiting an extremely rich phase and rheological behavior. In this paper we describe the rheological properties of a synthetic amphiphilic block copolymer dissolved in a water-in-oil microemulsion with and without the stabilizing effect of small molecular weight surfactant molecules. The block copolymer is an ABA type copolymer composed of poly(oxyethylene) (PEO) as the hydrophilic A block and poly(dimethyl siloxane) (PDMS) as the hydrophobic center B block. The resulting copolymer is insoluble in water and hardly soluble in decane (good solvent for the PDMS). In the presence of water in oil microemulsion stabilized by the small molecular weight surfactant AOT a one-phase region is maintained when the copolymer is added. Yet, peculiar rheological behavior is observed. For constant water-microemulsion concentration (φ) addition of polymer increases the system viscosity as expected. Yet, the lower φ the higher the viscosity and at high φ the effect of polymer addition is quite low. Furthermore, the insoluble block copolymer in oil turns into a gel-like one phase system upon addition of small amounts of either water or water and surfactant solution. Experiments show that a maximum in elasticity or viscosity is attained at a droplet concentration equivalent to about 80 polymer chains per drop. Small angle x-ray and neutron scattering experiments were carried out to elucidate the system morphology.

  2. Stabilization of amphiphilic block copolymer nanotubes and vesicles by photopolymerization

    NASA Astrophysics Data System (ADS)

    Kishore, R.; Jofre, A.; Hutchison, J. B.; Allegrini, M.; Locascio, L. E.; Helmerson, K.

    2006-12-01

    We create long polymer nanotubes by directly pulling on the membrane of polymersomes using either optical tweezers or a micropipette. The polymersomes are composed of amphiphilic diblock copolymers and the nanotubes formed have an aqueous core connected to the aqueous interior of the polymersome. Stabilized membranes of nanotubes and vesicles were formed by the directed selfassembly of poly(ethylene oxide)-block-polybutadiene, followed by photopolymerization, initiated by UV light, to a maximum double bond conversion of 15%. The photopolymerized nanotubes are extremely robust. The applicability of photopolymerization for biophysics and bioanalytical science is demonstrated by electrophoresing DNA molecules through a stabilized nanotube with an integrated vesicle reservoir.

  3. Water Diffusion Dependence on Amphiphilic Block Design in (Amphiphilic-Hydrophobic) Diblock Copolymer Membranes.

    PubMed

    Dorenbos, Gert

    2016-06-30

    Polyelectrolyte membranes (PEMs) are applied in polyelectrolyte fuel cells (PEFC). The proton conductive pathways within PEMs are provided by nanometer-sized water containing pores. Large-scale application of PEFC requires the production of low-cost membranes with high proton conductivity and therefore good connected pore networks. Pore network formation within four alternative model diblock (hydrophobic_amphiphilic) copolymers in the presence of water is studied by dissipative particle dynamics. Each hydrophobic block contains 50 consecutively connected hydrophobic (A) fragments, and amphiphilic blocks contain 40 hydrophobic A beads and 10 hydrophilic C beads. For one amphiphilic block the C beads are distributed uniformly along the backbone. For the other architectures C beads are located at the end of the side chains attached at regular intervals along the backbone. Water diffusion through the pores is modeled by Monte Carlo tracer diffusion through mapped morphologies. Diffusion is highest for the grafted architectures and increases with increase of length of the side chains. A consistent picture emerges in which diffusion strongly increases with the value of ⟨Nbond⟩ within the amphiphilic block, where ⟨Nbond⟩ is the average number of bonds between hydrophobic A beads and the nearest C bead. PMID:27266679

  4. Water Diffusion Dependence on Amphiphilic Block Design in (Amphiphilic-Hydrophobic) Diblock Copolymer Membranes.

    PubMed

    Dorenbos, Gert

    2016-06-30

    Polyelectrolyte membranes (PEMs) are applied in polyelectrolyte fuel cells (PEFC). The proton conductive pathways within PEMs are provided by nanometer-sized water containing pores. Large-scale application of PEFC requires the production of low-cost membranes with high proton conductivity and therefore good connected pore networks. Pore network formation within four alternative model diblock (hydrophobic_amphiphilic) copolymers in the presence of water is studied by dissipative particle dynamics. Each hydrophobic block contains 50 consecutively connected hydrophobic (A) fragments, and amphiphilic blocks contain 40 hydrophobic A beads and 10 hydrophilic C beads. For one amphiphilic block the C beads are distributed uniformly along the backbone. For the other architectures C beads are located at the end of the side chains attached at regular intervals along the backbone. Water diffusion through the pores is modeled by Monte Carlo tracer diffusion through mapped morphologies. Diffusion is highest for the grafted architectures and increases with increase of length of the side chains. A consistent picture emerges in which diffusion strongly increases with the value of ⟨Nbond⟩ within the amphiphilic block, where ⟨Nbond⟩ is the average number of bonds between hydrophobic A beads and the nearest C bead.

  5. Brownian dynamics simulation of amphiphilic block copolymers with different tail lengths, comparison with theory and comicelles.

    PubMed

    Hafezi, Mohammad-Javad; Sharif, Farhad

    2015-11-01

    Study on the effect of amphiphilic copolymers structure on their self assembly is an interesting subject, with important applications in the area of drug delivery and biological system treatments. Brownian dynamics simulations were performed to study self-assembly of the linear amphiphilic block copolymers with the same hydrophilic head, but hydrophobic tails of different lengths. Critical micelle concentration (CMC), gyration radius distribution, micelle size distribution, density profiles of micelles, shape anisotropy, and dynamics of micellization were investigated as a function of tail length. Simulation results were compared with predictions from theory and simulation for mixed systems of block copolymers with long and short hydrophobic tail, reported in our previous work. Interestingly, the equilibrium structural and dynamic parameters of pure and mixed block copolymers were similarly dependant on the intrinsic/apparent hydrophobic block length. Log (CMC) was, however; proportional to the tail length and had a different behavior compared to the mixed system. The power law scaling relation of equilibrium structural parameters for amphiphilic block copolymers predicts the same dependence for similar hydrophobic tail lengths, but the power law prediction of CMC is different, which is due to its simplifying assumptions as discussed here.

  6. Amphiphilic block copolymers in oil-water-surfactant mixtures: efficiency boosting, structure, phase behaviour and mechanism

    NASA Astrophysics Data System (ADS)

    Gompper, G.; Richter, D.; Strey, R.

    2001-10-01

    The effect of amphiphilic block copolymers on the phase behaviour and structure of ternary microemulsions in water, oil and non-ionic surfactant mixtures is reviewed. Recent experiments have revealed that the addition of small amounts of polyethylenepropylene-polyethyleneoxide block copolymer to the ternary systems leads to a dramatic increase in the volumes of oil and water solubilized into a bicontinuous microemulsion for a given surfactant volume fraction. While phase diagrams directly show the power of the amphiphilic block copolymers as efficiency boosters, the theoretical analysis in terms of bending energy discloses the mechanism for the efficiency boosting as due to the variation of the surfactant film curvature elasticity by tethered polymers in the form of mushrooms at the interface. Neutron scattering experiments employing a high-precision two-dimensional contrast variation technique confirm this picture and demonstrate that the polymer molecules uniformly decorate the surfactant film.

  7. Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups.

    PubMed

    Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo

    2014-10-01

    Novel amphiphilic block copolymers bearing pendant hydroxyl groups polylactide-b-poly(3,3-bis(Hydroxymethyl-triazolylmethyl) oxetane)-b-polylactide (PLA-b-PHMTYO-b-PLA) were synthesized via a facile and efficient method. First, the block copolymer intermediates polylactide-b-poly(3,3-Diazidomethyloxetane)-b-polylactide (PLA-b-PBAMO-b-PLA) were synthesized through ring-opening polymerization of lactide using PBAMO as a macroinitiator. Following "Click" reaction of PLA-b-PBAMO-b-PLA with propargyl alcohol provided the targeted amphiphilic block copolymers PLA-b-PHMTYO-b-PLA with pendant hydroxyl groups. The composition and structure of prepared copolymers were characterized by (1)H nuclear magnetic resonance ((1)H NMR) spectroscopy, Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). The self-assembly behavior of the copolymers in water was investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and static light scattering (SLS). The results showed that the novel copolymers PLA-b-PHMTYO-b-PLA self-assembled into spherical micelles with diameters ranging from 100 nm to 200 nm in aqueous solution. These copolymers also exhibited low critical micellar concentrations (CMC: 6.9 × 10(-4)mg/mL and 3.9 × 10(-5)mg/mL, respectively). In addition, the in vitro cytotoxicity of these copolymers was determined in the presence of L929 cells. The results showed that the block copolymers PLA-b-PHMTYO-b-PLA exhibited better biocompatibility. Therefore, these well-defined copolymers are expected to find some applications in drug delivery or tissue engineering. PMID:25175206

  8. Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups.

    PubMed

    Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo

    2014-10-01

    Novel amphiphilic block copolymers bearing pendant hydroxyl groups polylactide-b-poly(3,3-bis(Hydroxymethyl-triazolylmethyl) oxetane)-b-polylactide (PLA-b-PHMTYO-b-PLA) were synthesized via a facile and efficient method. First, the block copolymer intermediates polylactide-b-poly(3,3-Diazidomethyloxetane)-b-polylactide (PLA-b-PBAMO-b-PLA) were synthesized through ring-opening polymerization of lactide using PBAMO as a macroinitiator. Following "Click" reaction of PLA-b-PBAMO-b-PLA with propargyl alcohol provided the targeted amphiphilic block copolymers PLA-b-PHMTYO-b-PLA with pendant hydroxyl groups. The composition and structure of prepared copolymers were characterized by (1)H nuclear magnetic resonance ((1)H NMR) spectroscopy, Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). The self-assembly behavior of the copolymers in water was investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and static light scattering (SLS). The results showed that the novel copolymers PLA-b-PHMTYO-b-PLA self-assembled into spherical micelles with diameters ranging from 100 nm to 200 nm in aqueous solution. These copolymers also exhibited low critical micellar concentrations (CMC: 6.9 × 10(-4)mg/mL and 3.9 × 10(-5)mg/mL, respectively). In addition, the in vitro cytotoxicity of these copolymers was determined in the presence of L929 cells. The results showed that the block copolymers PLA-b-PHMTYO-b-PLA exhibited better biocompatibility. Therefore, these well-defined copolymers are expected to find some applications in drug delivery or tissue engineering.

  9. Anti-Biofouling Properties of Comblike Block Copolymers with Amphiphilic Side Chains

    SciTech Connect

    Krishnan,S.; Ayothi, R.; Hexemer, A.; Finlay, J.; Sohn, K.; Perry, R.; Ober, C.; Kramer, E.; Callow, M.; et al.

    2006-01-01

    Surfaces of novel block copolymers with amphiphilic side chains were studied for their ability to influence the adhesion of marine organisms. The surface-active polymer, obtained by grafting fluorinated molecules with hydrophobic and hydrophilic blocks to a block copolymer precursor, showed interesting bioadhesion properties. Two different algal species, one of which adhered strongly to hydrophobic surfaces, and the other, to hydrophilic surfaces, showed notably weak adhesion to the amphiphilic surfaces. Both organisms are known to secrete adhesive macromolecules, with apparently different wetting characteristics, to attach to underwater surfaces. The ability of the amphiphilic surface to undergo an environment-dependent transformation in surface chemistry when in contact with the extracellular polymeric substances is a possible reason for its antifouling nature. Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) was used, in a new approach based on angle-resolved X-ray photoelectron spectroscopy (XPS), to determine the variation in chemical composition within the top few nanometers of the surface and also to study the surface segregation of the amphiphilic block. A mathematical model to extract depth-profile information from the normalized NEXAFS partial electron yield is developed.

  10. Rheology, Morphology and Phase Behavior in Amphiphilic Block Copolymer/microemulsion Systems

    NASA Astrophysics Data System (ADS)

    Gottlieb, Moshe; Braun, Liora; Zhang, Zeng-Rong

    2000-03-01

    Joining together by means of covalent bonds hydrophobic and hydrophilic entities on the same molecule gives rise to materials with interesting properties in aqueous systems or in the presence of mixed solvents such as water/oil microemulsions. In this paper we describe the rheological properties of a synthetic amphiphilic block copolymer dissolved in a water-in-oil microemulsion. The block copolymer is an ABA type copolymer composed of poly(oxyethylene) (PEO) as the hydrophilic A block and poly(dimethyl siloxane) (PDMS) as the hydrophobic center B block. Different polymers have been prepared with a B block of D_p=160 and three different sizes of the A blocks with D_p= 10, 45, and 120 respectively. The resulting copolymer is insoluble in water and hardly soluble in decane (good solvent for the PDMS). In the presence of water in oil microemulsion stabilized by the small molecular weight surfactant AOT a one-phase region is maintained when the copolymer is added. Yet, peculiar rheological behavior is observed. For constant water-microemulsion concentration (φ) addition of polymer increases the system viscosity as expected. Yet, the lower φ the higher the viscosity and at high φ the effect of polymer addition is quite low.

  11. Stable nanoemulsions prepared via interfacial solidification of amphiphilic polyether-polyester block copolymers.

    PubMed

    Kim, Trang Huyen Le; Jun, Hwiseok; Kim, Jee Seon; Nam, Yoon Sung

    2015-04-01

    Oil-in-water (O/W) emulsions are generally stabilized by water-soluble surfactants, which anchor to the surface of oil droplets dispersed in an aqueous solution. Our recent work introduced a new approach to stabilize nanoemulsions through the formation of a semi-solid interphase at the O/W interface using a water-insoluble amphiphilic block copolymer, methoxy poly(ethylene glycol)-block-poly(ɛ-caprolactone). However, the approach is not applicable to relatively non-polar oils due to the quick precipitation of the hydrophobic PCL block within the oil phase. Here we report on successful stabilization of non-polar liquid paraffin nanoemulsions using an amphiphilic copolymers having a new hydrophobic block comprising ɛ-caprolactone and L-lactide. The new block copolymer was reorganized at the O/W interface of liquid paraffin, generating stable nano-sized emulsions via the formation of a robust semi-solid polymeric barrier. The prepared nanoemulsions show excellent dispersion stability even under a high level of mechanical stresses during freeze/thaw cycles.

  12. Stable nanoemulsions prepared via interfacial solidification of amphiphilic polyether-polyester block copolymers.

    PubMed

    Kim, Trang Huyen Le; Jun, Hwiseok; Kim, Jee Seon; Nam, Yoon Sung

    2015-04-01

    Oil-in-water (O/W) emulsions are generally stabilized by water-soluble surfactants, which anchor to the surface of oil droplets dispersed in an aqueous solution. Our recent work introduced a new approach to stabilize nanoemulsions through the formation of a semi-solid interphase at the O/W interface using a water-insoluble amphiphilic block copolymer, methoxy poly(ethylene glycol)-block-poly(ɛ-caprolactone). However, the approach is not applicable to relatively non-polar oils due to the quick precipitation of the hydrophobic PCL block within the oil phase. Here we report on successful stabilization of non-polar liquid paraffin nanoemulsions using an amphiphilic copolymers having a new hydrophobic block comprising ɛ-caprolactone and L-lactide. The new block copolymer was reorganized at the O/W interface of liquid paraffin, generating stable nano-sized emulsions via the formation of a robust semi-solid polymeric barrier. The prepared nanoemulsions show excellent dispersion stability even under a high level of mechanical stresses during freeze/thaw cycles. PMID:25585162

  13. Nanoparticle-directed self-assembly of amphiphilic block-copolymers

    NASA Astrophysics Data System (ADS)

    Park, So-Jung

    2011-03-01

    The self-assembly of nanoparticles and amphiphilic polymers provides a powerful tool for the fabrication of functional composite materials for a range of applications spanning from nanofabrication to medicine. Here, we present how the incorporation of nanoparticles affects the self-assembly behavior of amphiphilic block-copolymers and how to control the morphology of nanoparticle-encapsulating polymer assemblies. Based on the approach, we have prepared various types of well-defined nanoparticle-encapsulating polymeric nanostructures, including polymersomes packed with magnetic nanoparticles and unique cavity-like quantum dot assembles. We found that the incorporation of nanoparticles drastically affects the self-assembly structure of block-copolymers by modifying the relative volume ratio between the hydrophobic block and the hydrophilic block. In addition, the nanoparticle-polymer and nanoparticle-solvent interactions impact the arrangement and the hybridization of nanoparticles in polymer matrix. These findings should form the basis for the design rules of the self-assembly of nanoparticles and polymer amphiphiles, which will allow one to create new hybrid structures with predesigned morphology and properties. Furthermore, we demonstrated that the morphology of nanoparticle-encapsulating polymer assemblies significantly affects their properties such as magnetic relaxation properties, underscoring the importance of the overall self-assembly structure and the nanoparticle arrangement in polymer matrixes. This work was supported by the NSF career award, the ARO young investigator award, and the MRSEC seed award (University of Pennsylvania).

  14. Solubilization of the novel anionic amphiphilic photosensitizer TPCS 2a by nonionic Pluronic block copolymers.

    PubMed

    Lilletvedt, M; Smistad, G; Tønnesen, H H; Høgset, A; Kristensen, S

    2011-06-14

    The influence of four nonionic Pluronic block copolymers (L44, F68, P123 and F127) on the solubilization and aggregation of the novel anionic amphiphilic photosensitizer TPCS(2a), intended for use in the technology of photochemical internalization (PCI), was evaluated in aqueous media as part of pharmaceutical preformulation studies. The evaluation was performed by use of UV-Vis spectroscopy for diluted samples of TPCS(2a) (3×10(-6)M), and capillary viscosimetry, freezing point depression measurements and atomic force microscopy (AFM) at pharmaceutical relevant concentrations (2; 10 or 30 mg/ml TPCS(2a)). The critical micelle concentration (CMC) of the Pluronics in presence of TPCS(2a) was determined spectrophotometrically. The Pluronic block copolymers solubilized the photosensitizer above CMC at ambient temperature by formation of vehicle-drug complexes apparently organized in networks of varying viscosity and morphology, which were sensitive towards the addition of neutral and charged excipients. PMID:21530656

  15. Preparation, development and in vitro release evaluation of amphotericin B-loaded amphiphilic block copolymer vectors.

    PubMed

    Pippa, Natassa; Mariaki, Maria; Pispas, Stergios; Demetzos, Costas

    2014-10-01

    The aim of this work is to design and develop a suitable polymeric formulation incorporating amphotericin B (Ampho B) in order to overcome its water insolubility problem. To this end, we have chosen the poly(isoprene-b-ethylene oxide) amphiphilic block copolymer (IEO) family. We investigate the self assembly behavior and the stability kinetics of IEO copolymer based nanostructures formed in HPLC grade water and in phosphate buffer saline (PBS). The IEO block copolymer samples investigated have different molecular weights and compositions. A gamut of light scattering techniques (static, dynamic and electrophoretic) were used in order to extract information on the size, ζ-potential and morphological characteristics of the structures formed, as a function of the molar ratio of incorporated lipophilic drug Ampho B. The amphiphilic character and the colloidal stability of the particular polymeric drug vectors indicate that these nanostructures can be utilized as effective containers for the particular hydrophobic drug. The incorporation of Ampho B led to alteration of the physicochemical and morphological characteristics of the pure polymeric carriers. It is observed that the in vitro release of Ampho B from the prepared vectors IEO-b:Ampho B was quite slow, while the IEO-a carriers did not release Ampho B.

  16. Polydispersity-Driven Block Copolymer Amphiphile Self-Assembly into Prolate-Spheroid Micelles

    SciTech Connect

    Schmitt, Andrew L.; Repollet-Pedrosa, Milton H.; Mahanthappa, Mahesh K.

    2013-09-26

    The aqueous self-assembly behavior of polydisperse poly(ethylene oxide-b-1,4-butadiene-b-ethylene oxide) (OBO) macromolecular triblock amphiphiles is examined to discern the implications of continuous polydispersity in the hydrophobic block on the resulting aqueous micellar morphologies of otherwise monodisperse polymer surfactants. The chain length polydispersity and implicit composition polydispersity of these samples furnishes a distribution of preferred interfacial curvatures, resulting in dilute aqueous block copolymer dispersions exhibiting coexisting spherical and rod-like micelles with vesicles in a single sample with a O weight fraction, w{sub O}, of 0.18. At higher w{sub O} = 0.51-0.68, the peak in the interfacial curvature distribution shifts and we observe the formation of only American football-shaped micelles. We rationalize the formation of these anisotropically shaped aggregates based on the intrinsic distribution of preferred curvatures adopted by the polydisperse copolymer amphiphiles and on the relief of core block chain stretching by chain-length-dependent intramicellar segregation.

  17. Amphiphilic Spider Silk-Like Block Copolymers with Tunable Physical Properties and Morphology for Biomedical Applications

    NASA Astrophysics Data System (ADS)

    Huang, Wenwen; Krishnaji, Sreevidhya; Kaplan, David; Cebe, Peggy

    2013-03-01

    Silk-based materials are important candidates for biomedical applications because of their excellent biocompatibility and biodegradability. To generate silk amphiphilic biopolymers with potential use in guided tissue repair and drug delivery, a novel family of spider silk-like block copolymers was synthesized by recombinant DNA technology. Block copolymer thermal properties, structural conformations, protein-water interactions, and self-assembly morphologies were studied with respect to well controlled protein amino acid sequences. A theoretical model was used to predict the heat capacity of the protein and protein-water complex. Using thermal analysis, two glass transitions were observed: Tg1 is related to conformational changes caused by bound water removal, while Tg2 (>Tg1) is the glass transition of dry protein. Real-time infrared spectroscopy and X-ray diffraction confirmed that different secondary structural changes occur during the two Tg relaxations. Using scanning electron microscopy, fibrillar networks and hollow vesicles are observed, depending on protein block copolymer sequence. This study provides a deeper understanding of the relationship between protein physical properties and amino acid sequence, with implications for design of other protein-based materials. Support was provided from the NSF CBET-0828028 and the MRI Program under DMR-0520655 for thermal analysis instrumentation.

  18. Synthesis and characterization of an elastin-mimetic amphiphilic block copolymer protein

    NASA Astrophysics Data System (ADS)

    Lee, Terrence Anita-Talley

    2000-10-01

    The overall goal in material science is to be able to control the molecular architecture of a material and thus its end properties. There is no method that offers greater control than the biological synthesis of proteins. From the DNA sequence to the final synthesized protein, the entire process is finitely controlled. This present work describes methods developed and used to synthesize protein polymers by manipulating this process. From the initial DNA sequence chosen, the end properties that the protein polymer will have are dictated. An amphiphilic diblock copolymer was designed based on environmentally responsive elastin-mimetic peptide sequences [(Val/Ile)-Pro-Gly-Xaa-Gly] (Xaa = Ala or Glu for the hydrophilic block, Val or Phe for the hydrophobic block) and synthesized using a genetic engineering approach. Differential scanning calorimetry measurements in aqueous solution revealed that reversible hydrophobic folding and assembly of the copolymer occurs above the inverse temperature transition, Tt, of the hydrophobic block. This process results in the formation of 50 nm protein-based micellar aggregates, which were characterized by electron microscopy and temperature-dependent dynamic light scattering techniques. The distribution of micellar aggregates can be altered reproducibly through variation of environmental conditions including pH and temperature. The uniform and defined macromolecular architecture of this protein copolymer permits greater control over the physical properties of the micelles, which therefore may facilitate applications in controlled release of small molecules.

  19. Terminal groups control self-assembly of amphiphilic block copolymers in solution.

    PubMed

    Grzelakowski, M; Kita-Tokarczyk, K

    2016-03-28

    The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability. PMID:26948963

  20. Towards the development of polycaprolactone based amphiphilic block copolymers: molecular design, self-assembly and biomedical applications.

    PubMed

    Li, Zibiao; Tan, Beng Hoon

    2014-12-01

    Polycaprolactone (PCL) and its copolymers are a type of hydrophobic aliphatic polyester based on hydroxyalkanoic acids. They possess exceptional qualities: biocompatibility; FDA approval for clinical use; biodegradability by enzyme and hydrolysis under physiological conditions and low immunogenicity. These critical properties have facilitated their value as sutures, drug delivery vehicles and tissue engineering scaffolds in pharmaceutical and biomedical applications. However, the hydrophobicity of PCL and its copolymers remains a concern for further biological and biomedical applications. One promising approach is to design and synthesize well-controlled PCL-based amphiphilic block copolymers. This review summarizes recent advances in the synthesis and self-assembly of PCL-containing amphiphilic block copolymers and their bio-related applications including drug delivery and tissue engineering.

  1. Terminal groups control self-assembly of amphiphilic block copolymers in solution

    NASA Astrophysics Data System (ADS)

    Grzelakowski, M.; Kita-Tokarczyk, K.

    2016-03-01

    The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability.The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability. Electronic supplementary information (ESI) available: Fig. S1: Particle diameters for hydrated NH2-ABA-NH2 polymers with different degrees of functionalization; Fig. S2: TEM characterization of compound micelles from BA-OH polymer after extrusion; Fig. S3: Cryo-TEM and stopped flow characterization of lipid vesicles; Fig. S4 and S5: NMR spectra for ABA and BA polymers

  2. Controlling Phase Separation of Tough Interpenetrating Polymer Networks via Addition of Amphiphilic Block Copolymers

    NASA Astrophysics Data System (ADS)

    Rohde, Brian; Krishnamoorti, Ramanan; Robertson, Megan

    Interpenetrating polymer networks (IPNs) offer a unique way to combine the mechanical properties of two thermoset systems. Often used to create a material that possesses both high toughness and tensile properties, here we use polydicyclopentadiene, cured via ring opening metathesis polymerization, to contribute high toughness and diglycidyl ether of bisphenol A cured via anhydride chemistry to contribute high tensile strength and modulus. As the uncompatibilized system reacts in the presence of one another, mesoscopic phase separation occurs and dictates the overall efficacy of combining mechanical properties. To control phase separation and drive the system towards more mechanically robust nanostructed IPNs, amphiphilic block copolymers of polybutadiene- b-polyethylene oxide, where one block possesses strong affinity to polyDCPD and the other the DGEBA, were added to the system. Here we present a systematic study of the influence of block copolymer composition in the overall blend on degree of phase separation and morphology using a combination of small-angle x-ray scattering (SAXS) and scanning electron microscopy (SEM) techniques. The resultant mechanical properties are then explored in an effort to link mechanical properties to blend morphology.

  3. Effects of X-shaped reduction-sensitive amphiphilic block copolymer on drug delivery

    PubMed Central

    Xiao, Haijun; Wang, Lu

    2015-01-01

    To study the effects of X-shaped amphiphilic block copolymers on delivery of docetaxel (DTX) and the reduction-sensitive property on drug release, a novel reduction-sensitive amphiphilic copolymer, (PLGA)2-SS-4-arm-PEG2000 with a Gemini-like X-shape, was successfully synthesized. The formation of nanomicelles was proved with respect to the blue shift of the emission fluorescence as well as the fluorescent intensity increase of coumarin 6-loaded particles. The X-shaped polymers exhibited a smaller critical micelle concentration value and possessed higher micellar stability in comparison with those of linear ones. The size of X-shaped (PLGA)2-SS-4-arm-PEG2000 polymer nanomicelles (XNMs) was much smaller than that of nanomicelles prepared with linear polymers. The reduction sensitivity of polymers was confirmed by the increase of micellar sizes as well as the in vitro drug release profile of DTX-loaded XNMs (DTX/XNMs). Cytotoxicity assays in vitro revealed that the blank XNMs were nontoxic against A2780 cells up to a concentration of 50 µg/mL, displaying good biocompatibility. DTX/XNMs were more toxic against A2780 cells than other formulations in both dose- and time-dependent manners. Cellular uptake assay displayed a higher intracellular drug delivery efficiency of XNMs than that of nanomicelles prepared with linear polymers. Besides, the promotion of tubulin polymerization induced by DTX was visualized by immunofluorescence analysis, and the acceleration of apoptotic process against A2780 cells was also imaged using a fluorescent staining method. Therefore, this X-shaped reduction-sensitive (PLGA)2-SS-4-arm-PEG2000 copolymer could effectively improve the micellar stability and significantly enhance the therapeutic efficacy of DTX by increasing the cellular uptake and selectively accelerating the drug release inside cancer cells. PMID:26346880

  4. Effects of X-shaped reduction-sensitive amphiphilic block copolymer on drug delivery.

    PubMed

    Xiao, Haijun; Wang, Lu

    2015-01-01

    To study the effects of X-shaped amphiphilic block copolymers on delivery of docetaxel (DTX) and the reduction-sensitive property on drug release, a novel reduction-sensitive amphiphilic copolymer, (PLGA)2-SS-4-arm-PEG2000 with a Gemini-like X-shape, was successfully synthesized. The formation of nanomicelles was proved with respect to the blue shift of the emission fluorescence as well as the fluorescent intensity increase of coumarin 6-loaded particles. The X-shaped polymers exhibited a smaller critical micelle concentration value and possessed higher micellar stability in comparison with those of linear ones. The size of X-shaped (PLGA)2-SS-4-arm-PEG2000 polymer nanomicelles (XNMs) was much smaller than that of nanomicelles prepared with linear polymers. The reduction sensitivity of polymers was confirmed by the increase of micellar sizes as well as the in vitro drug release profile of DTX-loaded XNMs (DTX/XNMs). Cytotoxicity assays in vitro revealed that the blank XNMs were nontoxic against A2780 cells up to a concentration of 50 µg/mL, displaying good biocompatibility. DTX/XNMs were more toxic against A2780 cells than other formulations in both dose- and time-dependent manners. Cellular uptake assay displayed a higher intracellular drug delivery efficiency of XNMs than that of nanomicelles prepared with linear polymers. Besides, the promotion of tubulin polymerization induced by DTX was visualized by immunofluorescence analysis, and the acceleration of apoptotic process against A2780 cells was also imaged using a fluorescent staining method. Therefore, this X-shaped reduction-sensitive (PLGA)2-SS-4-arm-PEG2000 copolymer could effectively improve the micellar stability and significantly enhance the therapeutic efficacy of DTX by increasing the cellular uptake and selectively accelerating the drug release inside cancer cells. PMID:26346880

  5. Micellization of amphiphilic block copolymers in binary and ternary solvent mixtures.

    PubMed

    Sarkar, Biswajit; Ravi, Venkataramanan; Alexandridis, Paschalis

    2013-01-15

    Amphiphilic block copolymers of the poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) family (commercially available as Pluronics or Poloxamers) are well-known for self-assembling in water (selective solvent for PEO) into micelles with a PPO-rich core and a hydrated PEO corona. The micellization of two PEO-PPO-PEO block copolymers (Pluronic P105: EO(37)PO(56)EO(37) and Pluronic F127: EO(100)PO(65)EO(100)) has been studied in binary mixed solvents consisting of water and one of the following organic solvents: ethanol, glycerol, D(+)-glucose monohydrate, propylene carbonate, or triacetin, and also in ternary mixtures of water with 50/50 wt% ethanol+glycerol or 50/50 wt% ethanol+propylene carbonate. Glycerol, glucose, propylene carbonate and triacetin were found to promote micellization when added to water. Glycerol and glucose interact favorably with water, and reduce the block copolymer critical micelle concentration (cmc) by dehydrating the PEO-PPO interface as well as changing the bulk solvent properties. Propylene carbonate and triacetin act by locating at the PEO-PPO interface and increasing its hydrophobicity. The addition of ethanol to water provides better solvent conditions for the block copolymers compared to plain water, and disfavors the formation of micelles. In the case of ternary solvents consisting of water, ethanol (that prevents micelle formation), and glycerol or propylene carbonate (that favor micelle formation), the observed changes in the cmc are subtle. For Pluronic P105, the cmc increase is greater for ethanol+propylene carbonate (50/50 wt%) than for ethanol+glycerol (50/50 wt%). For Pluronic F127, the cmcs remain the same as in plain water, i.e., the effects of the two organic solvents compensate each other. The difference between the free energy of micellization in plain water and that in solvent mixtures varies linearly with the cosolvent concentration, and collapses into a single line for each solvent mixture type when normalized with

  6. Osmotically driven formation of double emulsions stabilized by amphiphilic block copolymers.

    PubMed

    Bae, Jinhye; Russell, Thomas P; Hayward, Ryan C

    2014-07-28

    Double emulsions are valuable for the formation of multi-compartmental structures. A variety of pathways to prepare double emulsions have been developed, but high-throughput routes to droplets of controlled size and architecture remain scarce. A new single-step process is introduced for preparation of water-in-oil-in-water double emulsions by a previously unexplained process of self-emulsification. We show that the origin of this process is the osmotic stress resulting from the presence of salt impurities within the amphiphilic block copolymers used for emulsion stabilization. Further, we utilize osmotically driven emulsification to tailor the structures of multiple emulsions, which upon solvent evaporation can yield multi-compartmental capsules or hierarchically structured porous films. PMID:24931713

  7. ABC triblock surface active block copolymer with grafted ethoxylated fluoroalkyl amphiphilic side chains for marine antifouling/fouling-release applications.

    PubMed

    Weinman, Craig J; Finlay, John A; Park, Daewon; Paik, Marvin Y; Krishnan, Sitaraman; Sundaram, Harihara S; Dimitriou, Michael; Sohn, Karen E; Callow, Maureen E; Callow, James A; Handlin, Dale L; Willis, Carl L; Kramer, Edward J; Ober, Christopher K

    2009-10-20

    An amphiphilic triblock surface-active block copolymer (SABC) possessing ethoxylated fluoroalkyl side chains was synthesized through the chemical modification of a polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene polymer precursor. Bilayer coatings on glass slides consisting of a thin layer of the amphiphilic SABC spray coated on a thick layer of a polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) thermoplastic elastomer were prepared for biofouling assays with the green alga Ulva and the diatom Navicula. Dynamic water contact angle analysis and X-ray photoelectron spectroscopy (XPS) were used to characterize the surfaces. Additionally, the effect of the Young's modulus of the coating on the release properties of sporelings (young plants) of the green alga Ulva was examined through the use of two different SEBS thermoplastic elastomers possessing modulus values of an order of magnitude in difference. The amphiphilic SABC was found to reduce the settlement density of zoospores of Ulva as well as the strength of attachment of sporelings. The attachment strength of the sporelings was further reduced for the amphiphilic SABC on the "low"-modulus SEBS base layer. The weaker adhesion of diatoms, relative to a PDMS standard, further highlights the antifouling potential of this amphiphilic triblock hybrid copolymer.

  8. Highly protein-resistant coatings and suspension cell culture thereon from amphiphilic block copolymers prepared by RAFT polymerization.

    PubMed

    Haraguchi, Kazutoshi; Kubota, Kazuomi; Takada, Tetsuo; Mahara, Saori

    2014-06-01

    Novel amphiphilic block copolymers composed of hydrophobic (poly(2-methoxyethyl acrylate): M) and hydrophilic (poly(N,N-dimethylacrylamide): D) segments were synthesized by living radical polymerization: a reversible addition-fragmentation chain-transfer polymerization. Two types of amphiphilic block copolymers, triblock (MDM) and 4-arm block ((MD)4) copolymers with specific compositions (D/M = (750-1500)/250), were prepared by a versatile one-pot synthesis. These copolymers show good adhesion to various types of substrates (e.g., polystyrene, polycarbonate, polypropylene, Ti, and glass), and the surface coating showed high protein repellency and a low contact angle for water, regardless of the substrate. The two opposing characteristics of high protein repellency and good substrate adhesion were achieved by the combined effects of the molecular architecture of the block copolymers, the high molecular weight, and the characteristics of each segment, that is, low protein adsorption capability of both segments and low glass transition temperature of the hydrophobic segment. Further, a polystyrene dish coated with the MDM block copolymer could be sterilized by γ-ray irradiation and used as a good substrate for a suspension cell culture that exhibits low cell adhesion and good cell growth. PMID:24773089

  9. Highly protein-resistant coatings and suspension cell culture thereon from amphiphilic block copolymers prepared by RAFT polymerization.

    PubMed

    Haraguchi, Kazutoshi; Kubota, Kazuomi; Takada, Tetsuo; Mahara, Saori

    2014-06-01

    Novel amphiphilic block copolymers composed of hydrophobic (poly(2-methoxyethyl acrylate): M) and hydrophilic (poly(N,N-dimethylacrylamide): D) segments were synthesized by living radical polymerization: a reversible addition-fragmentation chain-transfer polymerization. Two types of amphiphilic block copolymers, triblock (MDM) and 4-arm block ((MD)4) copolymers with specific compositions (D/M = (750-1500)/250), were prepared by a versatile one-pot synthesis. These copolymers show good adhesion to various types of substrates (e.g., polystyrene, polycarbonate, polypropylene, Ti, and glass), and the surface coating showed high protein repellency and a low contact angle for water, regardless of the substrate. The two opposing characteristics of high protein repellency and good substrate adhesion were achieved by the combined effects of the molecular architecture of the block copolymers, the high molecular weight, and the characteristics of each segment, that is, low protein adsorption capability of both segments and low glass transition temperature of the hydrophobic segment. Further, a polystyrene dish coated with the MDM block copolymer could be sterilized by γ-ray irradiation and used as a good substrate for a suspension cell culture that exhibits low cell adhesion and good cell growth.

  10. Formation of nanoscale networks: selectively swelling amphiphilic block copolymers with CO2-expanded liquids

    NASA Astrophysics Data System (ADS)

    Gong, Jianliang; Zhang, Aijuan; Bai, Hua; Zhang, Qingkun; Du, Can; Li, Lei; Hong, Yanzhen; Li, Jun

    2013-01-01

    Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO2-expanded liquid (CXL), CO2-methanol. The phase behavior of the CO2-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO2, forming homogeneous CXL under the experimental conditions. When treated with the CO2-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a temperature range of 45-60 °C. The formation mechanism of the network, involving plasticization of PS and selective swelling of P4VP, was proposed. Because the diblock copolymer diffusion process is controlled by the activated hopping of individual block copolymer chains with the thermodynamic barrier for moving PVP segments from one to another, the formation of the network structures is achieved in a short time scale and shows ``thermodynamically restricted'' character. Furthermore, the resulting polymer networks were employed as templates, for the preparation of polypyrrole networks, by an electrochemical polymerization process. The prepared porous polypyrrole film was used to fabricate a chemoresistor-type gas sensor which showed high sensitivity towards ammonia.Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO2-expanded liquid (CXL), CO2-methanol. The phase behavior of the CO2-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO2, forming homogeneous CXL under the experimental conditions. When treated with the CO2-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a

  11. Perfluorinated Moieties Increase the Interaction of Amphiphilic Block Copolymers with Lipid Monolayers.

    PubMed

    Schwieger, Christian; Blaffert, Jacob; Li, Zheng; Kressler, Jörg; Blume, Alfred

    2016-08-16

    The interaction of amphiphilic and triphilic block copolymers with lipid monolayers has been studied. Amphiphilic triblock copolymer PGMA20-PPO34-PGMA20 (GP) is composed of a hydrophobic poly(propylene oxide) (PPO) middle block that is flanked by two hydrophilic poly(glycerol monomethacrylate) (PGMA) side blocks. The attachment of a perfluoro-n-nonyl residue (F9) to either end of GP yields a triphilic polymer with the sequence F9-PGMA20-PPO34-PGMA20-F9 (F-GP). The F9 chains are fluorophilic, i.e., they have a tendency to demix in hydrophilic as well as in lipophilic environments. We investigated (i) the adsorption of both polymers to differently composed lipid monolayers and (ii) the compression behavior of mixed polymer/lipid monolayers. The lipid monolayers are composed of phospholipids with PC or PE headgroups and acyl chains of different length and saturation. Both polymers interact with lipid monolayers by inserting their hydrophobic moieties (PPO, F9). The interaction is markedly enhanced in the presence of F9 chains, which act as membrane anchors. GP inserts into lipid monolayers up to a surface pressure of 30 mN/m, whereas F-GP inserts into monolayers at up to 45 mN/m, suggesting that F-GP also inserts into lipid bilayer membranes. The adsorption of both polymers to lipid monolayers with short acyl chains is favored. Upon compression, a two-step squeeze-out of F-GP occurs, with PPO blocks being released into the aqueous subphase at 28 mN/m and the F9 chains being squeezed out at 48 mN/m. GP is squeezed out in one step at 28 mN/m because of the lack of F9 anchor groups. The liquid expanded (LE) to liquid condensed (LC) phase transition of DPPC and DMPE is maintained in the presence of the polymers, indicating that the polymers can be accommodated in LE- and LC-phase monolayers. These results show how fluorinated moieties can be included in the rational design of membrane-binding polymers. PMID:27442444

  12. Gold nanocluster-conjugated amphiphilic block copolymer for tumor-targeted drug delivery.

    PubMed

    Chen, Tong; Xu, Shuang; Zhao, Tong; Zhu, Ling; Wei, Dongfeng; Li, Yuanyuan; Zhang, Haixia; Zhao, Chunyan

    2012-11-01

    Two kinds of core-shell structured multifunctional nanocarriers of gold nanoclusters (Au NCs) as core and folate (FA)-conjugated amphiphilic hyperbranched block copolymer as shell based on poly(L-lactide) (PLA) inner arm and FA-conjugated sulfated polysaccharide (GPPS-FA) outer arm (Au NCs-PLA-GPPS-FA) were synthesized for targeted anticancer drug delivery. The structure and properties of Au NCs-PLA-GPPS-FA copolymers were characterized and determined by ¹H NMR spectrum, FT-IR spectra, dynamic light scattering (DLS), fluorescence spectroscopy, and transmission electron microscopic (TEM) analyses. The anticancer drug, camptothecin (CPT) was used as a hydrophobic model anticancer drug. In vitro, two kinds of the nanocarriers presented a relatively rapid release in the first stage (up to 1 h) followed by a sustained release period (up to 15 h), and then reached a plateau at pH 5.3, 7.4, and 9.6. The release results indicated that CPT release from two kinds of the nanocarriers at pH 9.6 was much greater than that at both pH 5.3 and 7.4. The cytotoxicity studies showed that the CPT-loaded nanocarriers provided high anticancer activity against Hela cells. Furthermore, nanocarriers gained specificity to target some cancer cells because of the enhanced cell uptake mediated by FA moiety. The fluorescent images studies showed that the nanocarriers could track at the cellular level for advance therapy. The results indicated that the Au NCs-PLA-GPPS-FA copolymers not only had great potential as tumor-targeted drug delivery carrier, but also had an assistant role in the treatment of cancer.

  13. Synthesis of biodegradable amphiphilic Y-shaped block co-polymers via ring-opening polymerization for drug delivery.

    PubMed

    Jia, Lin; Yan, Lifeng; Li, Yang

    2011-01-01

    A series of novel Y-shaped biodegradable block co-polymers of poly(ε-caprolactone) (PCL) and poly(ethyl ethylene phosphate) (PEEP) (PCL-(PEEP)2) were synthesized via ring-opening polymerization (ROP) of EEP with bis-hydroxy-functional ROP initiator (init-PCL-(OH)2). The init-PCL-(OH)2 was synthesized by ROP of CL using 4-hydroxybutyl acrylate (HBA) as initiator and L-tartaric acid as catalyst in bulk, and subsequently the resulting vinyl-terminated PCL was end-capped by acetyl chloride, followed by Michael addition using excess diethanolamine. The Y-shaped co-polymers and their intermediates were characterized by (1)H-, (13)C-, (31)P-NMR, FT-IR and gel-permeation chromatography. The results indicated that the molecular weight of the Y-shaped co-polymers increased with the increasing of the molar ratios of EEP to init-PCL-(OH)2 in the feed, while the PCL chain length was kept constant. The amphiphilic block co-polymers could self-assemble into micelles in aqueous solution, which was demonstrated by dynamic light scattering, (1)H-NMR and atomic force microscopy. A study of controlled release of indomethacin indicated that the amphiphilic block co-polymers could potentially provide novel vehicles for drug delivery.

  14. Amphiphilic copolymer of poly(ethylene glycol)-block-polypyridine; synthesis, physicochemical characterization, and adsorption onto silica nanoparticle.

    PubMed

    Matsukuma, Daisuke; Maejima, Yukie; Ikenaga, Yusuke; Sanbai, Taketomo; Ueno, Koji; Otsuka, Hidenori

    2014-09-01

    In this study, we newly synthesized amphiphilic block copolymers composed of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic pyridine segments (PEG-b-Py). Chain transfer agent terminated PEG was subsequently chain-extended with 3-(4-pyridyl)-propyl acrylate to obtain PEG-b-Py by reversible additional-fragmentation chain transfer (RAFT) polymerization. Particularly, the effect of varying PEG molecular weight (M(n)) of the block copolymers (M(n) = 2000 (2k), and 5000 (5k)) was investigated in terms of critical micelle concentration (cmc), pyrene solubilization, micelle size distribution, and association number per micelle. Based on the amphiphilic balance, PEG-b-Pys formed core-shell type polymer micelle. The cmc value of PEG2k-b-Py was lower than that of PEG5k-b-Py, suggesting the degree of phase separation was strongly depended on PEG M(n). Furthermore, the adsorption of PEG-b-Py copolymer onto silica nanoparticles as dispersant was studied to estimate the effect of PEG M(n) in the copolymers and their solubility in the medium on the adsorption. Adsorbed density of PEG2k-b-Py copolymer onto silica nanoparticle was higher than that of PEG5k-b-Py, which was significantly correlated with the degree of phase-separation based on the amphiphilic balance. The adsorbed amount of copolymer was further changed as a function of solvent polarity, phase separation predicting the presence of the acid-base interaction between Py and silanol group existed on silica nanoparticles. The resultant dispersion stability was highly correlated with the graft density of copolymer onto silica surface. As a result, PEG2k-b-Py coated silica nanoparticles in aqueous media (with high solvent polarity) showed high dispersion stability. These fundamental investigations for the surface modification of the nanoparticle provide the insight into the highly stable colloidal dispersion as well as the design of dispersant molecular structure.

  15. Molecular interactions and solubilization of structurally related meso-porphyrin photosensitizers by amphiphilic block copolymers (Pluronics).

    PubMed

    Sobczyński, Jan; Smistad, Gro; Hegge, Anne Bee; Kristensen, Solveig

    2015-01-01

    The influence of four Pluronics block copolymers (i.e. F68, P123, F127, and L44) on the aggregation and solubilization of five structurally related meso-tetraphenyl porphyrin photosensitizers (PS) as model compounds for use in Photodynamic Therapy of cancer (PDT) was evaluated. Interactions between the PSs and Pluronics were studied at micromolar concentration by means of UV-Vis absorption spectrometry and by kinematic viscosity (υ) and osmolarity measurements at millimolar concentrations. Pluronic micelles were characterized by size and zeta potential (ζ) measurements. The morphology of selected PS-Pluronic assemblies was studied by atomic force microscopy (AFM). While hydrophobic 5,10,15,20-Tetrakis(4-hydroxyphenyl) porphine (THPP) seemed to be solubilized in the Pluronic micellar cores, amphiphilic di(monoethanolammonium) meso-tetraphenyl porphine disulphonate (TPPS2a) was likely bound to the micellar palisade layer. Hydrophilic PSs like 5,10,15,20-Tetrakis (4-trimethylaniliniumphenyl) porphine (TAPP) seemed to form complexes with Pluronic unimers and to be distributed among the micellar coronas. TPPS2a aggregated into a network which could be broken at Pluronic concentration [Formula: see text] cmc, but would reconstitute in the presence of tonicity adjusting agents, e.g. sodium chloride (NaCl) or glucose. PMID:25027806

  16. Amphiphilic block copolymers as flexible membrane materials generating structural and functional mimics of green bacterial antenna complexes.

    PubMed

    Collins, A M; Timlin, J A; Anthony, S M; Montaño, G A

    2016-08-11

    We describe the ability of a short-chain amphiphilic block copolymer to self-assemble to form an artificial supramolecular light-harvesting system. Specifically, we demonstrate that the 2.5 kDa, poly(ethylene oxide)-block-poly(butadiene) (PEO-b-PBD), exhibits sufficient morphological flexibility as a membrane material and enables generation of mimics of three-dimensional chlorosomes as well as supported membrane bilayers containing energy acceptors. This overall architecture replicates green bacterial light-harvesting function whereby these assemblies exhibit long-range order and three-dimensional morphology similar to native chlorosomes and are capable of energy transfer internally and to external acceptors, located in a supporting biomimetic polymer membrane. Unlike native green bacterial systems that use multiple lipids as a matrix to generate the appropriate environment for chlorosome assembly and function, the described system matrix is comprised entirely of a single polymer amphiphile. This work demonstrates the potential of short-chain amphiphilic block copolymers in generating self-assembled, bio-mimetic membrane architectures, and in doing so, generates scalable, spatial-energetic landscapes for photonic applications. Finally, the results presented provide evidence of minimal requirements to induce chlorosome-like organization and function. PMID:27481550

  17. Interfacial reactivity of block copolymers: understanding the amphiphile-to-hydrophile transition.

    PubMed

    Napoli, Alessandro; Bermudez, Harry; Hubbell, Jeffrey A

    2005-09-27

    Block copolymers offer an interesting platform to study chemically triggered transitions in self-assembled structures. We have previously reported the oxidative degradation of vesicles made of poly(propylene sulfide)-poly(ethylene glycol) (PPS-PEG) copolymers. Here we propose a mechanism for vesicle degradation deduced from copolymer conformational changes occurring at the air/water interface in a Langmuir trough together with a reactive subphase. The hydrophobic PPS block is converted into hydrophilic poly(propylene sulfoxide) and poly(propylene sulfone) by oxidation upon exposure to 1% aqueous H(2)O(2) subphase. As a result, a dramatic increase in area per molecule at constant surface pressure (Pi) was observed, followed by an apparent decrease (recorded as decrease in area at constant Pi) due to copolymer dissolution. For monolayers at the air/water surface, the large interfacial tensions present suppress increases in local curvature for alleviating the increased hydrophilicity of the copolymer chains. By contrast, vesicles can potentially rearrange molecules in their bilayers to accommodate a changing hydrophilic-lipophilic balance (HLB). Similar time scales for monolayer rearrangement and vesicle degradation imply a common copolymer chain solubilization mechanism, which in vesicles lead to an eventual transition to aggregates of higher curvature, such as cylindrical and spherical micelles. Subtle differences in response to the applied surface pressure for the diblock compared to the triblock suggest an effect of the different chain mobility. PMID:16171345

  18. Cooperation of Amphiphilicity and Crystallization for Regulating the Self-Assembly of Poly(ethylene glycol)-block-poly(lactic acid) Copolymers.

    PubMed

    Wang, Zhen; Cao, Yuanyuan; Song, Jiaqi; Xie, Zhigang; Wang, Yapei

    2016-09-20

    Tuning the amphiphilicity of block copolymers has been extensively exploited to manipulate the morphological transition of aggregates. The introduction of crystallizable moieties into the amphiphilic copolymers also offers increasing possibilities for regulating self-assembled structures. In this work, we demonstrate a detailed investigation of the self-assembly behavior of amphiphilic poly(ethylene glycol)-block-poly(l-lactic acid) (PEG-b-PLLA) diblock copolymers with the assistance of a common solvent in aqueous solution. With a given length of the PEG block, the molecular weight of the PLA block has great effect on the morphologies of self-assembled nanoaggregates as a result of varying molecular amphiphilicity and polymer crystallization. Common solvents including N,N-dimethylformamide, dioxane, and tetrahydrofuran involved in the early stage of self-assembly led to the change in chain configuration, which further influences the self-assembly of block copolymers. This study expanded the scope of PLA-based copolymers and proposed a possible mechanism of the sphere-to-lozenge and platelet-to-cylinder morphological transitions. PMID:27496056

  19. Amphiphilic block copolymer modified magnetic nanoparticles for microwave-assisted extraction of polycyclic aromatic hydrocarbons in environmental water.

    PubMed

    Li, Nan; Qi, Li; Shen, Ying; Li, Yaping; Chen, Yi

    2013-11-01

    In this work, amphiphilic block copolymer poly(tert-butyl methacrylate)-block-poly(glycidyl methacrylate) (PtBMA-b-PGMA) modified Fe3O4 magnetic nanoparticles (Fe3O4 MNPs) were synthesized, and served as an adsorbent for microwave-assisted extraction of polycyclic aromatic hydrocarbons (PAHs). The PtBMA-b-PGMA block copolymers with different block ratios were prepared by two-step atom transfer radical polymerization (ATRP) and the extraction abilities of their corresponding Fe3O4@PtBMA-b-PGMA were investigated. The key factors affecting the extraction efficiency of the adsorbent, including microwave conditions, amount of adsorbent, type and volume of desorption solvent, were studied in detail. In comparison with vortex, which is a conventional method used for assisting extraction, the proposed microwave-assisted method allowed better extraction efficiency and required a shorter extraction time. The calibration curves of PAHs were obtained in the range of 0.05-120 μg/L (r>0.9985) and the limits of detection (S/N=3) were in the range of 2.4-6.3 ng/L. The recoveries of PAHs spiked in environmental water samples were between 62.5% and 104% with relative standard deviations (RSDs) ranging from 0.84% to 9.02%. The proposed technique combining microwave-assisted extraction and magnetic separation was demonstrated to be a fast, convenient and sensitive pretreating method for PAHs.

  20. Methotrexate-Loaded Four-Arm Star Amphiphilic Block Copolymer Elicits CD8+ T Cell Response against a Highly Aggressive and Metastatic Experimental Lymphoma.

    PubMed

    Hira, Sumit Kumar; Ramesh, Kalyan; Gupta, Uttam; Mitra, Kheyanath; Misra, Nira; Ray, Biswajit; Manna, Partha Pratim

    2015-09-16

    We have synthesized a well-defined four-arm star amphiphilic block copolymer [poly(DLLA)-b-poly(NVP)]4 [star-(PDLLA-b-PNVP)4] that consists of D,L-lactide (DLLA) and N-vinylpyrrolidone (NVP) via the combination of ring-opening polymerization (ROP) and xanthate-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization. Synthesis of the polymer was verified by 1H NMR spectroscopy and gel permeation chromatography (GPC). The amphiphilic four-arm star block copolymer forms spherical micelles in water as demonstrated by transmission electron microscopy (TEM) and 1H NMR spectroscopy. Pyrene acts as a probe to ascertain the critical micellar concentration (cmc) by using fluorescence spectroscopy. Methotrexate (MTX)-loaded polymeric micelles of star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer were prepared and characterized by fluorescence and TEM studies. Star-(PDLLA15-b-PNVP10)4 copolymer was found to be significantly effective with respect to inhibition of proliferation and lysis of human and murine lymphoma cells. The amphiphilic block copolymer causes cell death in parental and MTX-resistant Dalton lymphoma (DL) and Raji cells. The formulation does not cause hemolysis in red blood cells and is tolerant to lymphocytes compared to free MTX. Therapy with MTX-loaded star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer micelles prolongs the life span of animals with neoplasia by reducing the tumor load, preventing metastasis and augmenting CD8+ T cell-mediated adaptive immune responses.

  1. Structure-rheology relationship in weakly amphiphilic block copolymer Langmuir monolayers.

    PubMed

    Li Destri, Giovanni; Miano, Fausto; Marletta, Giovanni

    2014-04-01

    The linear viscoelastic behavior in the low-frequency regime at the water/air interface of three different polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) copolymer monolayers, with block length ratio varying from 66-33 to 50-50 and 25-75 in molecular units, was studied and related to the interfacial behavior, characterized by means of Langmuir isotherms, and their structure, characterized by means of the atomic force microscopy technique. The two monolayers with the highest PMMA amount showed a single phase transition at about 12 mN/m, the viscoelastic behavior changing from a predominantly elastic to a viscoelastic one. This change in the viscoelastic properties was ascribed to the beginning of entanglement among the PMMA coronas of the predominantly circular quasi-2D micelles formed by the two copolymer systems. Conversely, the polymer with the lowest PMMA amount, despite having the same PMMA block length of the PS-PMMA 50-50 block copolymer, was found to behave as a viscoelastic system at any surface pressure value. This characteristic behavior cannot therefore be simply related to the molecular weight difference, but it has been put in connection to the irregular micelle structure observed in this case, consisting of a mixture of spherical and wormlike micelles, and to the different conformation adopted by the PMMA block. By blending this copolymer with an immiscible elastic homopolymer, namely poly(2-vinylpyridine), it was possible to tune the micelle nanostructure, obtaining regular circular quasi-2D micelles, with viscoelastic properties as expected for the PMMA-rich copolymer monolayers. To the best of our knowledge, this study shows for the first time the explicit dependence upon the relative block length and, in turn, upon the nanostructure of the quasi-2D micelles, of the viscoelastic properties of Langmuir monolayers and suggests that molecular weight and intermolecular interactions are not the only parameters governing the polymer conformation and

  2. Light-triggered reversible "one-to-two" morphological transition in a "latent double-amphiphilic" linear-hyperbranched supramolecular block copolymer.

    PubMed

    Jiang, Wenfeng; Liu, Yong; Yu, Chunyang; Li, Shanlong; Li, Yongjin; Zhou, Yongfeng

    2016-07-01

    This study reports a new category of stimuli-responsive morphological transitions, i.e., from one morphology (e.g., vesicles) to another two different ones (e.g., nanosheets and nanofibers), by investigating the light-responsive self-assembly behaviour of a "latent double-amphiphilic" linear-hyperbranched supramolecular block copolymer. PMID:27211799

  3. Self-Assembly of Charged Amphiphilic Diblock Copolymers with Insoluble Blocks of Decreasing Hydrophobicity: From Kinetically Frozen Colloids to Macrosurfactants

    SciTech Connect

    M Jacquin; P Muller; H Cottet; O Theodoly

    2011-12-31

    We have investigated the self-assembly properties in aqueous solution of amphiphilic diblock copolymers with insoluble blocks of different hydrophobicity and demonstrated that the condition to obtain dynamic micelles is to design samples with insoluble blocks of low enough hydrophobicity. We focus here on results with new water-soluble amphiphilic diblock copolymers poly(diethyleneglycol ethylether acrylate)-b-poly(acrylic acid), or PDEGA-b-PAA. The physical characteristics of PDEGA-b-PAA micelles at high ionization have been determined by small angle neutron scattering (SANS). We show that PDEGA-b-PAA samples form micelles at thermodynamic equilibrium. The critical micelle concentrations (CMCs) decrease strongly with ionic strength and temperature due to a solvent quality decrease for, respectively, the corona and the core. This behavior of reversible aggregation is remarkable as compared to the behavior of kinetically frozen aggregation that has been widely observed with samples of similar architecture and different hydrophobic blocks, for example, poly(styrene)-b-poly(acrylic acid), PS-b-PAA, and poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA. We have measured the interfacial tension between water and the homopolymers PDEGA and PBA at, respectively, 3 and 20 mN/m at room temperature, which permits one to estimate the energy cost to extract a unimer from a micelle. The results are consistent with a micelle association that is fast for PDEGA-b-PAA and kinetically frozen PBA-b-PAA. Hence, PDEGA-b-PAA samples form a new system of synthetic charged macrosurfactant with unique properties of fast dynamic association, tunable charge, and water solubility even at temperatures and NaCl concentrations as high as 65 C and 1 M.

  4. The influence of pendant hydroxyl groups on enzymatic degradation and drug delivery of amphiphilic poly[glycidol-block-(epsilon-caprolactone)] copolymers.

    PubMed

    Mao, Jing; Gan, Zhihua

    2009-11-10

    An amphiphilic diblock copolymer PG-b-PCL with well-controlled structure and pendant hydroxyl groups along hydrophilic block was synthesized by sequential anionic ring-opening polymerization. The micellization and drug release of PG-b-PCL copolymers using pyrene as a fluorescence probe were investigated for determining the influences of copolymer composition and lipase concentration on drug loading capacity and controlled release behavior. The biodegradation of PG-b-PCL copolymers was studied with microspheres as research samples. It has been concluded that the polar hydroxyl groups along each repeat unit of hydrophilic PG block in PG-b-PCL copolymer have great influences on drug encapsulation, drug release, and enzymatic degradation of micelles and microspheres.

  5. Self-Assembly of Amphiphilic Block Copolymers Containing Poly(n-octadecyl acrylate) Block in Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Akiba, Isamu; Akino, Yusuke; Masunaga, Hiroyasu; Sakurai, Kazuo

    2010-11-01

    Synchrotron small-angle X-ray scattering (SAXS) experiments were carried out for poly(acrylic acid)-block-poly(n-octadecyl acrylate) (PAA-b-PODA) and PAA-b-PODA-b-PAA micelles in aqueous solutions. SAXS results indicated that PAA-b-PODA and PAA-b-PODA-b-PAA formed core-shell micelles with disk-like morphology below melting temperature of PODA in aqueous solutions. The thickness of PAA-b-PODA (diblock copolymer) micelle was larger than that of PAA-b-PODA-b-PAA (triblock copolymer) micelle. The difference of sizes between these micelles was related to difference of molecular architectures of PAA-b-PODA and PAA-b-PODA-b-PAA. PAA-b-PODA micelle showed morphological transition from disk to spherical shape with elevating temperature. On the contrary, PAA-b-PODA-b-PAA micelle maintained disk-like shape above melting temperature, although enlargement of micelle thickness is caused.

  6. Unimolecular micelles of amphiphilic cyclodextrin-core star-like block copolymers for anticancer drug delivery.

    PubMed

    Xu, Zhigang; Liu, Shiying; Liu, Hui; Yang, Cangjie; Kang, Yuejun; Wang, Mingfeng

    2015-11-11

    Well-defined star-like amphiphilic polymers composed of a β-cyclodextrin core, from which 21 hydrophobic poly(lactic acid) arms and hydrophilic poly(ethylene glycol) arms are grafted sequentially, form robust and uniform unimolecular micelles that are biocompatible and efficient in the delivery of anticancer drugs. PMID:26121632

  7. Chemical Analysis and Aqueous Solution Properties of Charged Amphiphilic Block Copolymers PBA-b-PAA Synthesized by MADIX

    SciTech Connect

    Jacquin,M.; Muller, P.; Talingting-Pabalan, R.; Cottet, H.; Berret, J.; Futterer, T.; Theodoly, O.

    2007-01-01

    We have linked the structural and dynamic properties in aqueous solution of amphiphilic charged diblock copolymers poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA, synthesized by controlled radical polymerization, with the physico-chemical characteristics of the samples. Despite product imperfections, the samples self-assemble in melt and aqueous solutions as predicted by monodisperse microphase separation theory. However, the PBA core are abnormally large; the swelling of PBA cores is not due to AA (the Flory parameter ?PBA/PAA, determined at 0.25, means strong segregation), but to h-PBA homopolymers (content determined by liquid chromatography at the point of exclusion and adsorption transition, LC-PEAT). Beside the dominant population of micelles detected by scattering experiments, capillary electrophoresis CE analysis permitted detection of two other populations, one of h-PAA, and the other of free PBA-b-PAA chains, that have very short PBA blocks and never self-assemble. Despite the presence of these free unimers, the self-assembly in solution was found out of equilibrium: the aggregation state is history dependant and no unimer exchange between micelles occurs over months (time-evolution SANS). The high PBA/water interfacial tension, measured at 20 mN/m, prohibits unimer exchange between micelles. PBA-b-PAA solution systems are neither at thermal equilibrium nor completely frozen systems: internal fractionation of individual aggregates can occur.

  8. Highly stable phase change material emulsions fabricated by interfacial assembly of amphiphilic block copolymers during phase inversion.

    PubMed

    Park, Hanhee; Han, Dong Wan; Kim, Jin Woong

    2015-03-10

    This study introduced a robust and promising approach to fabricate highly stable phase change material (PCM) emulsions consisting of n-tetradecane as a dispersed phase and a mixture of meso-2,3-butanediol (m-BDO) and water as a continuous phase. We showed that amphiphilic poly(ethylene oxide)-b-poly(ε-caprolactone) block copolymers assembled to form a flexible but tough polymer membrane at the interface during phase inversion from water-in-oil emulsion to oil-in-water emulsion, thus remarkably improving the emulsion stability. Although the incorporation of m-BDO into the emulsion lowered the phase changing enthalpy, it provided a useful means to elevate the melting temperature of the emulsions near to 15 °C. Interestingly, supercooling was commonly observed in our PCM emulsions. We attributed this to the fact that the PCM molecules confined in submicron-scale droplets could not effectively nucleate to grow molecular crystals. Moreover, the presence of m-BDO in the continuous phase rather dominated the heat emission of the emulsion system during freezing, which made the supercooling more favorable. PMID:25674921

  9. Linear-g-hyperbranched and cyclodextrin-based amphiphilic block copolymer as a multifunctional nanocarrier.

    PubMed

    Zhao, Yamei; Tian, Wei; Yang, Guang; Fan, Xiaodong

    2014-01-01

    In this paper, a novel, multifunctional polymer nanocarrier was designed to provide adequate volume for high drug loading, to afford a multiregion encapsulation ability, and to achieve controlled drug release. An amphiphilic, triblock polymer (ABC) with hyperbranched polycarbonsilane (HBPCSi) and β-cyclodextrin (β-CD) moieties were first synthesized by the combination of a two-step reversible addition-fragmentation transfer polymerization into a pseudo-one-step hydrosilylation and quaternization reaction. The ABC then self-assembled into stable micelles with a core-shell structure in aqueous solution. These resulting micelles are multifunctional nanocarriers which possess higher drug loading capability due to the introduction of HBPCSi segments and β-CD moieties, and exhibit controlled drug release based on the diffusion release mechanism. The novel multifunctional nanocarrier may be applicable to produce highly efficient and specialized delivery systems for drugs, genes, and diagnostic agents. PMID:25550733

  10. Amphiphilic block-graft copolymer templates for organized mesoporous TiO2 films in dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Lim, Jung Yup; Lee, Chang Soo; Lee, Jung Min; Ahn, Joonmo; Cho, Hyung Hee; Kim, Jong Hak

    2016-01-01

    Amphiphilic block-graft copolymers composed of poly(styrene-b-butadiene-b-styrene) (SBS) backbone and poly(oxyethylene methacrylate) (POEM) side chains are synthesized and combined with hydrophilically preformed TiO2 (Pre-TiO2), which works as a structural binder as well as titania source. This results in the formation of crack free, 6-μm-thick, organized mesoporous TiO2 (OM-TiO2) films via one-step doctor-blading based on self-assembly of SBS-g-POEM as well as preferential interaction of POEM chains with Pre-TiO2. SBS-g-POEM with different numbers of ethylene oxide repeating units, SBS-g-POEM(500) and SBS-g-POEM(950), are used to form OM-TiO2(500) and OM-TiO2(950), respectively. The efficiencies of dye-sensitized solar cells (DSSCs) with a quasi-solid-state polymer electrolyte reach 5.7% and 5.8% at 100 mW/cm2 for OM-TiO2(500) and OM-TiO2(950), respectively. The surface area of OM-TiO2(950) was greater than that of OM-TiO2(500) but the light reflectance was lower in the former, which is responsible for similar efficiency. Both DSSCs exhibit much higher efficiency than one (4.8%) with randomly-organized particulate TiO2 (Ran-TiO2), which is attributed to the higher dye loading, reduced charge recombination and improved pore infiltration of OM-TiO2. When utilizing poly((1-(4-ethenylphenyl)methyl)-3-butyl-imidazolium iodide) (PEBII) and mesoporous TiO2 spheres as the solid electrolyte and the scattering layer, the efficiency increases up to 7.5%, one of the highest values for N719-based solid-state DSSCs.

  11. Amphiphilic poly(D- or L-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) block copolymers: controlled synthesis, characterization, and stereocomplex formation.

    PubMed

    Spasova, Mariya; Mespouille, Laetitia; Coulembier, Olivier; Paneva, Dilyana; Manolova, Nevena; Rashkov, Iliya; Dubois, Philippe

    2009-05-11

    Novel well-defined amphiphilic poly(D-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) (PDLA-b-PDMAEMA) and poly(L-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) (PLLA-b-PDMAEMA) copolymers were obtained. The synthesis strategy consisted of a three-step procedure: (i) controlled ring-opening polymerization (ROP) of (D- or L-)lactide initiated by Al(O(i)Pr)(3), followed by (ii) quantitative conversion of the polylactide (PLA) hydroxyl end-groups with bromoisobutyryl bromide and (iii) atom transfer radical polymerization (ATRP) of DMAEMA. The PLA block molecular weight was kept below 5000 g/mol. The macromolecular parameters of the (co)polymers were determined by (1)H NMR spectroscopy and size exclusion chromatography (SEC). The stereocomplexes of PDLA-b-PDMAEMA/PLLA-b-PDMAEMA diblock copolymers were prepared via solvent casting. The stereocomplex formation was evidenced by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. The obtained stereocomplexes had melting temperature of about 65 degrees C above that of the individual copolymers and exhibited diffraction patterns assigned to the stereocomplex crystallites. In addition, for the first time it was shown that the replacement of one of the PLA partners with high molecular weight PLLA or PDLA did not hamper the stereocomplex formation. The presence of PDMAEMA blocks proved to impart hydrophilicity of the synthesized copolymers and related stereocomplexes, as determined by static water contact angle measurements. PMID:19331403

  12. Micellization Coupled with Facilitation of J-Aggregation for Poly(1,3-Cyclohexadiene) - Based Amphiphilic Block Copolymers

    SciTech Connect

    Lin, Jiaping; Ding, Weiwei; Hong, Kunlun; Mays, Jimmy; Xu, Zhongde; Yuan, Yizhong

    2008-01-01

    Self-assembly and its influence on the photophysical properties of polystyrene-b-sulfonated poly (1,3-cyclohexadiene) (PS-b-sPCHD) were investigated using transmission electron microscopy (TEM), laser light scattering (LLS) technique, and fluorescence spectroscopy. The amphiphilic PS-b-sPCHD copolymers can associate to form micelles with insoluble PS segments as the core surrounded by soluble sPCHD segments in aqueous media. J-aggregation of the chromophores in sPCHD segments is significantly facilitated in the micellization, resulting in a remarkable change in the photophysical properties of PS-b-sPCHD.

  13. Novel pH-responsive polymeric micelles prepared through self-assembly of amphiphilic block copolymer with poly-4-vinylpyridine block synthesized by mechanochemical solid-state polymerization.

    PubMed

    Kondo, Shin-ichi; Asano, Yuna; Koizumi, Natsumi; Tatematsu, Kenjiro; Sawama, Yuka; Sasai, Yasushi; Yamauchi, Yukinori; Kuzuya, Masayuki; Kurosawa, Shigeru

    2015-01-01

    We fabricated polymeric micelles containing 5-fluorouracil (5-FU) or fluorescein using the amphiphilic block copolymer, poly-4-vinylpyridine-b-6-O-methacryloyl galactopyranose. Although the polymeric micelles were stable at pH 7.4, they readily decomposed at pH 5, resulting in near complete release of 5-FU. Uptake of polymeric micelles containing fluorescein by HepG2 and HCT116 cells was also investigated. With both cell types, strong fluorescence was observed after a 12-h incubation, but the fluorescence weakened after 24 h of incubation. The fluorescein incorporated into the polymeric micelles was released into acidic organelles (endosome and/or lysosome), from which it diffused throughout the cell. The cytotoxicity of polymeric micelles containing 5-FU was evaluated against HepG2 cells using a CCK-8 assay. The results suggest that polymeric micelles containing 5-FU are more cytotoxic to HepG2 cells than free 5-FU. PMID:26133065

  14. Theranostic unimolecular micelles based on brush-shaped amphiphilic block copolymers for tumor-targeted drug delivery and positron emission tomography imaging.

    PubMed

    Guo, Jintang; Hong, Hao; Chen, Guojun; Shi, Sixiang; Nayak, Tapas R; Theuer, Charles P; Barnhart, Todd E; Cai, Weibo; Gong, Shaoqin

    2014-12-24

    Brush-shaped amphiphilic block copolymers were conjugated with a monoclonal antibody against CD105 (i.e., TRC105) and a macrocyclic chelator for (64)Cu-labeling to generate multifunctional theranostic unimolecular micelles. The backbone of the brush-shaped amphiphilic block copolymer was poly(2-hydroxyethyl methacrylate) (PHEMA) and the side chains were poly(L-lactide)-poly(ethylene glycol) (PLLA-PEG). The doxorubicin (DOX)-loaded unimolecular micelles showed a pH-dependent drug release profile and a uniform size distribution. A significantly higher cellular uptake of TRC105-conjugated micelles was observed in CD105-positive human umbilical vein endothelial cells (HUVEC) than nontargeted micelles due to CD105-mediated endocytosis. In contrast, similar and extremely low cellular uptake of both targeted and nontargeted micelles was observed in MCF-7 human breast cancer cells (CD105-negative). The difference between the in vivo tumor accumulation of (64)Cu-labeled TRC105-conjugated micelles and that of nontargeted micelles was studied in 4T1 murine breast tumor-bearing mice, by serial positron emission tomography (PET) imaging and validated by biodistribution studies. These multifunctional unimolecular micelles offer pH-responsive drug release, noninvasive PET imaging capability, together with both passive and active tumor-targeting abilities, thus making them a desirable nanoplatform for cancer theranostics.

  15. Theranostic Unimolecular Micelles Based on Brush-Shaped Amphiphilic Block Copolymers for Tumor-Targeted Drug Delivery and Positron Emission Tomography Imaging

    PubMed Central

    2015-01-01

    Brush-shaped amphiphilic block copolymers were conjugated with a monoclonal antibody against CD105 (i.e., TRC105) and a macrocyclic chelator for 64Cu-labeling to generate multifunctional theranostic unimolecular micelles. The backbone of the brush-shaped amphiphilic block copolymer was poly(2-hydroxyethyl methacrylate) (PHEMA) and the side chains were poly(l-lactide)-poly(ethylene glycol) (PLLA-PEG). The doxorubicin (DOX)-loaded unimolecular micelles showed a pH-dependent drug release profile and a uniform size distribution. A significantly higher cellular uptake of TRC105-conjugated micelles was observed in CD105-positive human umbilical vein endothelial cells (HUVEC) than nontargeted micelles due to CD105-mediated endocytosis. In contrast, similar and extremely low cellular uptake of both targeted and nontargeted micelles was observed in MCF-7 human breast cancer cells (CD105-negative). The difference between the in vivo tumor accumulation of 64Cu-labeled TRC105-conjugated micelles and that of nontargeted micelles was studied in 4T1 murine breast tumor-bearing mice, by serial positron emission tomography (PET) imaging and validated by biodistribution studies. These multifunctional unimolecular micelles offer pH-responsive drug release, noninvasive PET imaging capability, together with both passive and active tumor-targeting abilities, thus making them a desirable nanoplatform for cancer theranostics. PMID:24628452

  16. Novel RAFT amphiphilic brush copolymer steric stabilisers for cubosomes: poly(octadecyl acrylate)-block-poly(polyethylene glycol methyl ether acrylate).

    PubMed

    Chong, Josephine Y T; Mulet, Xavier; Postma, Almar; Keddie, Daniel J; Waddington, Lynne J; Boyd, Ben J; Drummond, Calum J

    2014-09-21

    Copolymers, particularly Pluronics®, are typically used to sterically stabilise colloidal nanostructured particles composed of a lyotropic liquid crystalline bicontinuous cubic phase (cubosomes). There is a need to design and assess new functionalisable stabilisers for these colloidal drug delivery systems. Six amphiphilic brush copolymers, poly(octadecyl acrylate)-block-poly(polyethylene glycol methyl ether acrylate) (P(ODA)-b-P(PEGA-OMe)), synthesised by reversible addition-fragmentation chain transfer (RAFT), were assessed as novel steric stabilisers for cubosomes. It was found that increasing the density of PEG on the nanostructured particle surface by incorporating a PEG brush design (i.e., brush copolymer), provided comparable and/or increased stabilisation effectiveness compared to a linear PEG structure, Pluronic® F127, which is extensively used for steric stabilisation of cubosomes. Assessment was conducted both prior to and following the removal of the dodecyl trithiocarbonate end-group, by free radical-induced reduction. The reduced (P(ODA)-b-P(PEGA-OMe) copolymers were more effective steric stabilisers for phytantriol and monoolein colloidal particle dispersions than their non-reduced analogues. High throughput characterisation methodologies, including an accelerated stability assay (ASA) and synchrotron small angle X-ray scattering (SAXS), were implemented in this study for the rapid assessment of steric stabiliser effectiveness and lyotropic liquid crystalline phase identification. Phytantriol cubosomes stabilised with P(ODA)-b-P(PEGA-OMe) copolymers exhibited a double diamond cubic phase (Q(2)(D)), whilst monoolein cubosomes exhibited a primitive cubic phase (Q(2)(P)), analogous to those formed using Pluronic® F127. PMID:25058647

  17. Role of Amphiphilic Block Copolymer Composition on Pore Characteristics of Micelle-Templated Mesoporous Cobalt Oxide Films.

    PubMed

    Wang, Siyang; Tangvijitsakul, Pattarasai; Qiang, Zhe; Bhaway, Sarang M; Lin, Kehua; Cavicchi, Kevin A; Soucek, Mark D; Vogt, Bryan D

    2016-04-26

    Block copolymer templating is a versatile approach for the generation of well-defined porosity in a wide variety of framework chemistries. Here, we systematically investigate how the composition of a poly(methoxy poly[ethylene glycol] methacrylate)-block-poly(butyl acrylate) (PMPEG-PBA) template impacts the pore characteristics of mesoporous cobalt oxide films. Three templates with a constant PMPEG segment length and different hydrophilic block volume fractions of 17%, 51%, and 68% for the PMPEG-PBA are cooperatively assembled with cobalt nitrate hexahydrate and citric acid. Irrespective of template composition, a spherical nanostructure is templated and elliptical mesostructures are obtained on calcination due to uniaxial contraction of the film. The average pore size increases from 11.4 ± 2.8 to 48.5 ± 4.3 nm as the length of the PBA segment increases as determined from AFM. For all three templates examined, a maximum in porosity (∼35% in all cases) and surface area is obtained when the precursor solids contain 35-45 wt % PMPEG-PBA. This invariance suggests that the total polymer content drives the structure through interfacial assembly. The composition for maximizing porosity and surface area with the micelle-templating approach results from a general decrease in porosity with increasing cobalt nitrate hexahydrate content and the increasing mechanical integrity of the framework to resist collapse during template removal/crystallization as the cobalt nitrate hexahydrate content increases. Unlike typical evaporation induced self-assembly with sol-gel chemistry, the hydrophilic/hydrophobic composition of the block copolymer template is not a critical component to the mesostructure developed with micelle-templating using metal nitrate-citric acid as the precursor. PMID:27040316

  18. Protein based Block Copolymers

    PubMed Central

    Rabotyagova, Olena S.; Cebe, Peggy; Kaplan, David L.

    2011-01-01

    Advances in genetic engineering have led to the synthesis of protein-based block copolymers with control of chemistry and molecular weight, resulting in unique physical and biological properties. The benefits from incorporating peptide blocks into copolymer designs arise from the fundamental properties of proteins to adopt ordered conformations and to undergo self-assembly, providing control over structure formation at various length scales when compared to conventional block copolymers. This review covers the synthesis, structure, assembly, properties, and applications of protein-based block copolymers. PMID:21235251

  19. Micellar transitions in solvent-annealed thin films of an amphiphilic block copolymer controlled with tunable surface fields.

    PubMed

    Chang, Chih-Yao; Lee, Yu-Chi; Wu, Pin-Jiun; Liou, Jiun-You; Sun, Ya-Sen; Ko, Bao-Tsan

    2011-12-01

    We investigated the response of symmetric poly(styrene-block-4vinylpyridine) P(S-b-4VP) diblock copolymer micelles to surface fields of variable strength at free surfaces and substrate interfaces when the micelles as spun were subjected to solvent annealing. Free surface interactions were controlled with solvent annealing in solvents of varied selectivity. On exposure to vapors of a solvent strongly selective for PS, the micelles retained their spherical shape but grew into cylindrical micelles or lamellar nanostructures via fusion on exposure to slightly selective or neutral solvent vapors. Giant 2D disks that completely wetted PS-grafted substrates resulted when spherical micelles were exposed to vapors of a highly selective solvent for P4VP. The interfacial interactions were controlled through subjecting them to UV/ozone (UVO) substrates initially coated with an end-grafted layer of short PS chains, with which the grafted PS chains became oxidized, degraded, or totally removed through UVO treatment for a controlled duration. When thin films were annealed in vapors of THF, the structural transition from spherical to cylindrical micelles depended on the interfacial field. On applying selective UVO exposure of optimal duration, we fabricated a substrate with two interfacial chemistries that promoted varied micellar species (spherical and cylindrical micelles) with a sharp boundary developed within thin films through solvent annealing for a controlled duration.

  20. Optoelectronics using block copolymers.

    SciTech Connect

    Botiz, I.; Darling, S. B.; Center for Nanoscale Materials

    2010-05-01

    Block copolymers, either as semiconductors themselves or as structure directors, are emerging as a promising class of materials for understanding and controlling processes associated with both photovoltaic energy conversion and light emitting devices.

  1. Modulating the self-assembly of amphiphilic X-shaped block copolymers with cyclodextrins: structure and mechanisms.

    PubMed

    González-Gaitano, Gustavo; Müller, Céline; Radulescu, Aurel; Dreiss, Cécile A

    2015-04-14

    Inclusion complexes between cyclodextrins and polymers-so-called pseudopolyrotaxanes (PPR)-are at the origin of fascinating supramolecular structures, which are finding increasing uses in biomedical and technological fields. Here we explore the impact of both native and a range of modified cyclodextrins (CD) on the self-assembly of X-shaped poly(ethylene oxide)-poly(propylene oxide) block copolymers, so-called Tetronics or poloxamines, by focusing on Tetronic 904 (T904, Mw 6700). The effects are markedly dependent on the type and arrangement of the substituents on the macrocycle. While native CDs drive the formation of a solid PPR, most substituted CDs induce micellar breakup, with dimethylated β-CD (DIMEB) having the strongest impact and randomly substituted CDs a much weaker disruptive effect. Using native α-CD as a "molecular trap", we perform competitive binding experiments-where two types of CDs thread together onto the polymer chains-to establish that DIMEB indeed has the highest propensity to form an inclusion complex with the polymer, while hydroxypropylated CDs do not thread. 1D (1)H NMR and ROESY experiments confirm the formation of a soluble PPR with DIMEB in which the CD binds preferentially to the PO units, thus providing the drive for the observed demicellization. A combination of dynamic light scattering (DLS) and small-angle neutron scattering (SANS) is used to extract detailed structural parameters on the micelles. A binding model is proposed, which exploits the chemical shifts of selected protons from the CD in conjunction with the Hill equation, to prove that the formation of the PPR is a negatively cooperative process, in which threaded DIMEBs hamper the entrance of subsequent macrocycles.

  2. Modulating the self-assembly of amphiphilic X-shaped block copolymers with cyclodextrins: structure and mechanisms.

    PubMed

    González-Gaitano, Gustavo; Müller, Céline; Radulescu, Aurel; Dreiss, Cécile A

    2015-04-14

    Inclusion complexes between cyclodextrins and polymers-so-called pseudopolyrotaxanes (PPR)-are at the origin of fascinating supramolecular structures, which are finding increasing uses in biomedical and technological fields. Here we explore the impact of both native and a range of modified cyclodextrins (CD) on the self-assembly of X-shaped poly(ethylene oxide)-poly(propylene oxide) block copolymers, so-called Tetronics or poloxamines, by focusing on Tetronic 904 (T904, Mw 6700). The effects are markedly dependent on the type and arrangement of the substituents on the macrocycle. While native CDs drive the formation of a solid PPR, most substituted CDs induce micellar breakup, with dimethylated β-CD (DIMEB) having the strongest impact and randomly substituted CDs a much weaker disruptive effect. Using native α-CD as a "molecular trap", we perform competitive binding experiments-where two types of CDs thread together onto the polymer chains-to establish that DIMEB indeed has the highest propensity to form an inclusion complex with the polymer, while hydroxypropylated CDs do not thread. 1D (1)H NMR and ROESY experiments confirm the formation of a soluble PPR with DIMEB in which the CD binds preferentially to the PO units, thus providing the drive for the observed demicellization. A combination of dynamic light scattering (DLS) and small-angle neutron scattering (SANS) is used to extract detailed structural parameters on the micelles. A binding model is proposed, which exploits the chemical shifts of selected protons from the CD in conjunction with the Hill equation, to prove that the formation of the PPR is a negatively cooperative process, in which threaded DIMEBs hamper the entrance of subsequent macrocycles. PMID:25785814

  3. Synthesis of amphiphilic diblock copolymer for surface modification of Ethylene-Norbornene Copolymers

    NASA Astrophysics Data System (ADS)

    Levinsen, Simon; Svendsen, Winnie Edith; Horsewell, Andy; Almdal, Kristoffer

    2014-03-01

    The aim of this work is to produce polymer modifiers in order to develop hydrophilic polymeric surfaces for use in microfluidics. The use of hydrophilic polymers in microfluidics will have many advantages e.g. preventing protein absorbance. Here we present an amphiphilic diblock copolymer consisting of a bulk material compatible block and a hydrophilic block. To utilize the possibility of incorporating diblock copolymers into ethylene-norbornene copolymers, we have in this work developed a model poly(ethylene-1-butene) polymer compatible with the commercial available ethylene-norbornene copolymer TOPAS. Through matching of the radius of gyration for the model polymer and TOPAS the miscibility was achieved. The poly(ethylene-1-butene) polymer was synthesized from a hydrogenated anionic polymerized polybutadiene polymer. As hydrophilic block poly(ethylene oxide) was subsequently added also with anionic polymerization. Recent miscibility results between the model polymer and TOPAS will be presented, as well ongoing efforts to study the hydrophilic surface.

  4. Novel 4-arm poly(ethylene glycol)-block-poly(anhydride-esters) amphiphilic copolymer micelles loading curcumin: preparation, characterization, and in vitro evaluation.

    PubMed

    Lv, Li; Shen, Yuanyuan; Li, Min; Xu, Xiaofen; Li, Mingna; Guo, Shengrong; Huang, Shengtang

    2013-01-01

    A novel 4-arm poly(ethylene glycol)-block-poly(anhydride-esters) amphiphilic copolymer (4-arm PEG-b-PAE) was synthesized by esterization of 4-arm poly(ethylene glycol) and poly(anhydride-esters) which was obtained by melt polycondensation of α -, ω -acetic anhydride terminated poly(L-lactic acid). The obtained 4-arm PEG-b-PAE was characterized by (1)H-NMR and gel permeation chromatography. The critical micelle concentration of 4-arm PEG-b-PAE was 2.38 μg/mL. The curcumin-loaded 4-arm PEG-b-PAE micelles were prepared by a solid dispersion method and the drug loading content and encapsulation efficiency of the micelles were 7.0% and 85.2%, respectively. The curcumin-loaded micelles were spherical with a hydrodynamic diameter of 151.9 nm. Curcumin was encapsulated within 4-arm PEG-b-PAE micelles amorphously and released from the micelles, faster in pH 5.0 than pH 7.4, presenting one biphasic drug release pattern with rapid release at the initial stage and slow release later. The hemolysis rate of the curcumin-loaded 4-arm PEG-b-PAE micelles was 3.18%, which was below 5%. The IC50 value of the curcumin-loaded micelles against Hela cells was 10.21 μg/mL, lower than the one of free curcumin (25.90 μg/mL). The cellular uptake of the curcumin-loaded micelles in Hela cell increased in a time-dependent manner. The curcumin-loaded micelles could induce G2/M phase cell cycle arrest and apoptosis of Hela cells.

  5. Block copolymer battery separator

    DOEpatents

    Wong, David; Balsara, Nitash Pervez

    2016-04-26

    The invention herein described is the use of a block copolymer/homopolymer blend for creating nanoporous materials for transport applications. Specifically, this is demonstrated by using the block copolymer poly(styrene-block-ethylene-block-styrene) (SES) and blending it with homopolymer polystyrene (PS). After blending the polymers, a film is cast, and the film is submerged in tetrahydrofuran, which removes the PS. This creates a nanoporous polymer film, whereby the holes are lined with PS. Control of morphology of the system is achieved by manipulating the amount of PS added and the relative size of the PS added. The porous nature of these films was demonstrated by measuring the ionic conductivity in a traditional battery electrolyte, 1M LiPF.sub.6 in EC/DEC (1:1 v/v) using AC impedance spectroscopy and comparing these results to commercially available battery separators.

  6. Structural Analysis of Hydrophobe-Uptake Micelle of an Amphiphilic Alternating Copolymer in Aqueous Solution.

    PubMed

    Morishima, Ken; Terao, Ken; Sato, Takahiro

    2016-08-01

    We investigated the structure of the hydrophobe-uptake micelle of an alternating amphiphilic copolymer in aqueous solutions, by combining light scattering and small-angle X-ray scattering (SAXS). When the copolymer micelle includes the hydrophobe (1-dodecanol), the unicore flower micelle transforms into the multicore flower necklace, and the flower necklace is slightly stiffer than the hydrophobe-free flower necklace of the same copolymer. Moreover, the hydrophobe is included not in the hydrophobic core region but in the intermingled region of the hydrophobic group and the loop chain of the unit flower micelle. Therefore, the structure of the hydrophobe-uptake micelle of the amphiphilic alternating copolymer is quite different from that of hydrophobe-uptake spherical micelles of low molar mass surfactants and of amphiphilic block copolymers, where the hydrophobe is included in the hydrophobic region of the micelles.

  7. Chain exchange in block copolymer micelles

    NASA Astrophysics Data System (ADS)

    Lu, Jie; Bates, Frank; Lodge, Timothy

    2014-03-01

    Block copolymer micelles are aggregates formed by self-assembly of amphiphilic copolymers dispersed in a selective solvent, driven by unfavorable interactions between the solvent and the core-forming block. Due to the relatively long chains being subject to additional thermodynamic and dynamic constraints (e.g., entanglements, crystallinity, vitrification), block copolymer micelles exhibit significantly slower equilibration kinetics than small molecule surfactants. As a result, details of the mechanism(s) of equilibration in block copolymer micelles remain unclear. This present works focuses on the chain exchange kinetics of poly(styrene-b-ethylenepropylene) block copolymers in squalane (C30H62) using time-resolved small angle neutron scattering (TR-SANS). A mixture of h-squalane and d-squalane is chosen so that it contrast matches a mixed 50/50 h/d polystyrene micelle core. When the temperature is appropriate and isotopically labeled chains undergo mixing, the mean core contrast with respect to the solvent decreases, and the scattering intensity is therefore reduced. This strategy allows direct probing of chain exchange rate from the time dependent scattering intensity I(q, t).

  8. Block copolymer investigations

    NASA Astrophysics Data System (ADS)

    Yufa, Nataliya A.

    The research presented in this thesis deals with various aspects of block copolymers on the nanoscale: their behavior at a range of temperatures, their use as scaffolds, or for creation of chemically striped surfaces, as well as the behavior of metals on block copolymers under the influence of UV light, and the healing behavior of copolymers. Invented around the time of World War II, copolymers have been used for decades due to their macroscopic properties, such as their ability to be molded without vulcanization, and the fact that, unlike rubber, they can be recycled. In recent years, block copolymers (BCPs) have been used for lithography, as scaffolds for nano-objects, to create a magnetic hard drive, as well as in photonic and other applications. In this work we used primarily atomic force microscopy (AFM) and transmission electron microscopy (TEM), described in Chapter II, to conduct our studies. In Chapter III we demonstrate a new and general method for positioning nanoparticles within nanoscale grooves. This technique is suitable for nanodots, nanocrystals, as well as DNA. We use AFM and TEM to demonstrate selective decoration. In Chapters IV and V we use AFM and TEM to study the structure of polymer surfaces coated with metals and self-assembled monolayers. We describe how the surfaces were created, exhibit their structure on the nanoscale, and prove that their macroscopic wetting properties have been altered compared to the original polymer structures. Finally, Chapters VI and VII report out in-situ AFM studies of BCP at high temperatures, made possible only recently with the invention of air-tight high-temperature AFM imaging cells. We locate the transition between disordered films and cylinders during initial ordering. Fluctuations of existing domains leading to domain coarsening are also described, and are shown to be consistent with reptation and curvature minimization. Chapter VII deals with the healing of PS-b-PMMA following AFM-tip lithography or

  9. Synthesis of antibacterial amphiphilic elastomer based on polystyrene-block-polyisoprene-block-polystyrene via thiol-ene addition.

    PubMed

    Keleş, Elif; Hazer, Baki; Cömert, Füsun B

    2013-04-01

    A new type of amphiphilic antibacterial elastomer has been described. Thermoplastic elastomer, polystyrene-block-polyisoprene-block-polystyrene (PS-b-PI-b-PS) triblock copolymer was functionalized in toluene solution by free radical mercaptan addition in order to obtain an amphiphilic antibacterial elastomer. Thiol terminated PEG was grafted through the double bonds of PS-b-PI-b-PS via free radical thiol-ene coupling reaction. The antibacterial properties of the amphiphilic graft copolymers were observed. The original and the modified polymers were used to create microfibers in an electro-spinning process. Topology of the electrospun micro/nanofibers were studied by using scanning electron microscopy (SEM). The chemical structures of the amphiphilic comb type graft copolymers were elucidated by the combination of elemental analysis, (1)H NMR, (13)C NMR, GPC and FTIR.

  10. Synthetic Cell Elements from Block Copolymers. Dynamic Aspects

    NASA Astrophysics Data System (ADS)

    Discher, Dennis

    2003-03-01

    Amphiphilic block copolymers can self-assemble in water into various stable morphologies which resemble key cell structures, notably filaments and membranes. Filamentous worms of copolymer, microns-long, will be introduced, and related dynamics of copolymer vesicle polymersomes will be detailed. Fluorescence visualization of single worms stretched under flow demonstrates their stability as well as a means to control flexibility. Polymersome membranes have been more thoroughly studied, especially copolymer molecular weight effects. We summarize results suggestive of a transition from Rouse-like behavior to entangled chains. Viewed together, the results ask the question: what physics are needed next to mimic cell activities such as crawling?

  11. Synthesis and self-assembly of amphiphilic poly(acrylicacid)-poly(ɛ-caprolactone)-poly(acrylicacid) block copolymer as novel carrier for 7-ethyl-10-hydroxy camptothecin.

    PubMed

    Djurdjic, Beti; Dimchevska, Simona; Geskovski, Nikola; Petrusevska, Marija; Gancheva, Valerya; Georgiev, Georgi; Petrov, Petar; Goracinova, Katerina

    2015-01-01

    The process of molecular self-assembly plays a crucial role in formulation of polymeric nanoparticulated drug delivery carriers as it creates the possibility for enhanced drug encapsulation and carrier surface engineering. This study aimed to develop a novel self-assembled polymeric micelles for targeted delivery in tumor cells in order to overcome not only various drawbacks of 7-ethyl-10-hydroxy camptothecin (SN-38) but also various reported limitations of other drug delivery systems, especially low drug loading and premature release. Custom synthesized amphiphilic triblock copolymer poly(acrylic acid)-poly(ɛ-caprolactone)-poly(acrylic acid) (PAA(13)-PCL(35)-PAA(13)) was used to prepare kinetically stable micelles by nanoprecipitation and modified nanoprecipitation procedure. Core-shell micelles with diameter of 120-140 nm, negative zeta potential and satisfactory drug loading were produced. The prepared formulations were stable in pH range of 3-12 and in media with NaCl concentration <1 mol/l. Screening mixed level factorial 3 × 2(2) design identified that the process temperature as well as the type of organic solvent has influence upon the efficacy of encapsulation, particle size, dissolution rate and burst release. Fourier transform infrared and differential scanning calorimetry analyses confirmed the entrapment of the active substance into the micelles. The kinetic analysis of dissolution studies revealed that the main mechanism of drug release from the prepared formulations is Fickian diffusion. Growth inhibition studies as well as DNA fragmentation assay performed on SW-480 cell lines clearly demonstrated increased growth inhibition effect and presence of fragmented DNA in cells treated with loaded micelles compared to SN-38 solution. Altogether, these results point out to potential biomedical and clinical application of PAA-PCL-PAA systems in the future.

  12. Synthesis and characterization of a poly(dimethylsiloxane)-poly(ethylene oxide) block copolymer for fabrication of amphiphilic surfaces on microfluidic devices.

    PubMed

    Klasner, Scott A; Metto, Eve C; Roman, Gregory T; Culbertson, Christopher T

    2009-09-01

    A poly(dimethylsiloxane)-poly(ethylene oxide) (PDMS-PEO) vinyl terminated block copolymer has been synthesized via a simple hydrosilylation reaction between hydride-terminated PDMS and PEO divinyl ether. This prepolymer can be subsequently cross-linked into an elastomer in a second hydrosilylation reaction involving a methylhydrosiloxane-dimethylsiloxane copolymer, forming a material suitable for the purposes of fabricating microfluidic devices. The presence of the PEO block in the prepolymer chain results in a much more hydrophilic material following cross-linking. The surface water contact angle of the PDMS-PEO material is 65 degrees +/- 3 (n = 6), as opposed to approximately 110 degrees for native PDMS. Droplets of water straddled by air within molded channels of the PDMS-PEO are concave in shape with contact angles where the fluid meets the side walls of 32 degrees +/- 4 (n = 8), while droplets in PDMS microchannels are more convex with contact angles of 95 degrees +/- 6 (n = 6). The length of the PDMS-PEO prepolymer chain and the multifunctional hydride cross-linker chains appear to dictate the durability of the elastomeric material. Young's modulus measurements yielded values of 0.94 +/- 0.08, 2.6 +/- 0.8, and 1.91 +/- 0.06 MPa for a [5% vinyl excess prepolymer and 10-fold excess of cross-linker], [10% vinyl excess prepolymer and 5-fold excess of cross-linker], and 10:1 PDMS, respectively, confirming that the elasticity of the cross-linked PDMS-PEO is similar to that of PDMS (Sylgard 184:10:1 mixture of elastomeric base to elastomer curing agent). The PDMS-PEO material still possesses enough PDMS character to allow molded channel architectures to be sealed between two pieces of the block copolymer by conformal contact. As a result of the more hydrophilic nature of the material, the channels of devices fabricated from this polymer are self-filling when using aqueous buffers, making it more user-friendly than PDMS for applications calling for background

  13. Skin delivery by block copolymer nanoparticles (block copolymer micelles).

    PubMed

    Laredj-Bourezg, Faiza; Bolzinger, Marie-Alexandrine; Pelletier, Jocelyne; Valour, Jean-Pierre; Rovère, Marie-Rose; Smatti, Batoule; Chevalier, Yves

    2015-12-30

    Block copolymer nanoparticles often referred to as "block copolymer micelles" have been assessed as carriers for skin delivery of hydrophobic drugs. Such carriers are based on organic biocompatible and biodegradable materials loaded with hydrophobic drugs: poly(lactide)-block-poly(ethylene glycol) copolymer (PLA-b-PEG) nanoparticles that have a solid hydrophobic core made of glassy poly(d,l-lactide), and poly(caprolactone)-block-poly(ethylene glycol) copolymer (PCL-b-PEG) nanoparticles having a liquid core of polycaprolactone. In vitro skin absorption of all-trans retinol showed a large accumulation of retinol in stratum corneum from both block copolymer nanoparticles, higher by a factor 20 than Polysorbate 80 surfactant micelles and by a factor 80 than oil solution. Additionally, skin absorption from PLA-b-PEG nanoparticles was higher by one order of magnitude than PCL-b-PEG, although their sizes (65nm) and external surface (water-swollen PEG layer) were identical as revealed by detailed structural characterizations. Fluorescence microscopy of histological skin sections provided a non-destructive picture of the storage of Nile Red inside stratum corneum, epidermis and dermis. Though particle cores had a different physical states (solid or liquid as measured by (1)H NMR), the ability of nanoparticles for solubilization of the drug assessed from their Hildebrand solubility parameters appeared the parameter of best relevance regarding skin absorption.

  14. A Simple Way to Enhance Doxil® Therapy: Drug Release from Liposomes at the Tumor Site by Amphiphilic Block Copolymer

    PubMed Central

    Zhao, Yi; Alakhova, Daria Y.; Kim, Jong Oh; Bronich, Tatiana K.; Kabanov, Alexander V.

    2013-01-01

    The antitumor efficacy of Doxil® is hindered by the poor release of the active drug from the liposome at the tumor sites. This study investigates a possibility to enhance drug release from the liposomes and increase therapeutic efficacy of Doxil® by administering Pluronic block copolymers once the liposomal drug accumulates in the tumor sites. In our study, the fluorescence de-quenching experiments were designed to investigate the drug release from liposome by Pluronic P85. MTT cytotoxicity assay and confocal microscopy images were carried out to determine whether Pluronic P85 could facilitate release of Dox from Doxil®. Anti-tumor growth and distribution of drug were evaluated when Pluronic P85 was injected 1 hr, 48 hrs, or 96 hrs after the Doxil® administration in A2780 human ovarian cancer xenografts. Addition of Pluronic P85 resulted in release of Dox from the liposomes accompanied with significant increases of Dox delivery and cytotoxic effect in cancer cells. The greatest anti-tumor effect of single injection of Doxil® was achieved when Pluronic P85 was administered 48 hrs after Doxil®. The Confocal tile scanning images of tumor section showed that copolymer treatment induced the release of the drug in the tumors from the vessels regions to the bulk of the tumor. No release of the drug remaining in circulation was observed. Our study has demonstrated a simple approach for localized release of Dox from liposome by Pluronic P85 at the tumor site, which was therapeutically beneficial. PMID:23474033

  15. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

    2012-11-13

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  16. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G.; Matzger, Adam J.; Benin, Annabelle I.; Willis, Richard R.

    2012-12-04

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  17. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

    2014-11-11

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  18. Thin film assembly of spider silk-like block copolymers.

    PubMed

    Krishnaji, Sreevidhya T; Huang, Wenwen; Rabotyagova, Olena; Kharlampieva, Eugenia; Choi, Ikjun; Tsukruk, Vladimir V; Naik, Rajesh; Cebe, Peggy; Kaplan, David L

    2011-02-01

    We report the self-assembly of monolayers of spider silk-like block copolymers. Langmuir isotherms were obtained for a series of bioengineered variants of the spider silks, and stable monolayers were generated. Langmuir-Blodgett films were prepared by transferring the monolayers onto silica substrates and were subsequently analyzed by atomic force microscopy (AFM). Static contact angle measurements were performed to characterize interactions across the interface (thin film, water, air), and molecular modeling was used to predict 3D conformation of spider silk-like block copolymers. The influence of molecular architecture and volume fraction of the proteins on the self-assembly process was assessed. At high surface pressure, spider silk-like block copolymers with minimal hydrophobic block (f(A) = 12%) formed oblate structures, whereas block copolymer with a 6-fold larger hydrophobic domain (f(A) = 46%) formed prolate structures. The varied morphologies obtained with increased hydrophobicity offer new options for biomaterials for coatings and related options. The design and use of bioengineered protein block copolymers assembled at air-water interfaces provides a promising approach to compare 2D microstructures and molecular architectures of these amphiphiles, leading to more rationale designs for a range of nanoengineered biomaterial needs as well as providing a basis of comparison to more traditional synthetic block copolymer systems. PMID:21207952

  19. Use of amphiphilic triblock copolymers for enhancing removal efficiency of organic pollutant from contaminated media

    NASA Astrophysics Data System (ADS)

    Lee, Jun Hyup; Lee, Byungsun; Son, Intae; Kim, Jae Hong; Kim, Chunho; Yoo, Ji Yong; Wu, Jong-Pyo; Kim, Younguk

    2015-11-01

    We have studied amphiphilic triblock copolymers poly(ethylene glycol)- b-poly(propylene glycol)- b-poly(ethylene glycol) (PEG- b-PPG- b-PEG) and poly(propylene glycol)- b-poly(ethylene glycol)- b-poly(propylene glycol) (PPG- b-PEG- b-PPG) as possible substitutes for sodium dodecyl sulfate as anionic surfactants for the removal of hydrophobic contaminants. The triblock copolymers were compared with sodium dodecyl sulfate in terms of their abilities to remove toluene as hydrophobic contaminant in fuel, and the effects of polymer structure, PEG content, and concentration were studied. The PEG- b-PPG- b-PEG copolymer containing two hydrophilic PEG blocks was more effective for the removal of hydrophobic contaminant at extremely high concentration. We also measured the removal capabilities of the triblock copolymers having various PEG contents and confirmed that removal capability was greatest at 10% PEG content regardless of polymer structure. As with sodium dodecyl sulfate, the removal efficiency of a copolymer has a positive correlation with its concentration. Finally, we proposed the amphiphilic triblock copolymer of PPG- b-PEG- b-PPG bearing 10% PEG content that proved to be the most effective substitute for sodium dodecyl sulfate.

  20. Comparing Fluid and Elastic Block Copolymer Shells

    NASA Astrophysics Data System (ADS)

    Rozairo, Damith; Croll, Andrew B.

    2014-03-01

    Emulsions can be stabilized with the addition of an amphiphilic diblock copolymer, resulting in droplets surrounded and protected by a polymer monolayer. Such droplets show considerable promise as advanced cargo carriers in pharmaceuticals or cosmetics due to their strength and responsiveness. Diblock copolymer interfaces remain mostly fluid and may not be able to attain the mechanical performance desired by industry. To strengthen block copolymer emulsion droplets we have developed a novel method for creating thin elastic shells using polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-PAA-PS). Characterization of the fluid filled elastic shells is difficult with traditional means which lead us to develop a new and general method of mechanical measurement. Specifically, we use laser scanning confocal microscopy to achieve a high resolution measure of the deformation of soft spheres under the influence of gravity. To prove the resilience of the technique we examine both a polystyrene-b-poly(ethylene oxide) (PS-PEO) stabilized emulsion and the PS-PAA-PS emulsion. The mechanical measurement allows the physics of the polymer at the interface to be examined, which will ultimately lead to the rational development of these technologies.

  1. Oxidation effect on templating of metal oxide nanoparticles within block copolymers

    SciTech Connect

    Akcora, Pinar; Briber, Robert M.; Kofinas, Peter

    2009-06-30

    Amphiphilic norbornene-b-(norbornene dicarboxylic acid) diblock copolymers with different block ratios were prepared as templates for the incorporation of iron ions using an ion exchange protocol. The disordered arrangement of iron oxide particles within these copolymers was attributed to the oxidation of the iron ions and the strong interactions between iron oxide nanoparticles, particularly at high iron ion concentrations, which was found to affect the self-assembly of the block copolymer morphologies.

  2. Toughness in block copolymer modified epoxies

    NASA Astrophysics Data System (ADS)

    Declet-Perez, Carmelo

    One of the major shortcomings preventing the widespread use of epoxy resins in engineering applications is the inherent brittleness of these materials. The incorporation of small amounts of amphiphilic block copolymers into the formulation is one of the most promising strategies to toughen epoxies. These molecules are known to form nanostructures in the epoxy resin that can be preserved upon curing. This strategy is very attractive since significant enhancements in toughness can be obtained without detrimental effects on other properties of the matrix. Despite many examples of successful implementation, an in-depth understanding of the factors that lead to toughness in block copolymer modified epoxies is still elusive. The goal of this dissertation is to understand, first, the deformation mechanisms leading to toughness and, second, how different formulation parameters affect these processes. In this work we used two types of block copolymer modifiers, which produced nanostructures with different physical properties. These block copolymers self-assembled into well-dispersed spherical micelles with either rubbery or glassy cores in various epoxy formulations. Both of these modifiers toughened different epoxy formulations, although to different extents. The rubbery core micelles consistently outperformed the glassy core micelles by roughly a factor of two. While the toughening afforded by the rubbery core micelles was consistent with the current understanding of toughening, the results from the glassy core micelles could not be explained with the same reasoning. In order to understand the deformation mechanisms leading to different levels of toughness, we performed small-angle x-ray scattering experiments while simultaneously deforming our material. This combination of techniques, referred to as in-situ SAXS, allowed us to monitor changes in the structure of the block copolymer micelles as a result of the applied load. With this technique, we showed that the rubbery

  3. Anomalous Micellization of Pluronic Block Copolymers

    NASA Astrophysics Data System (ADS)

    Leonardi, Amanda; Ryu, Chang Y.

    2014-03-01

    Poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, commercially known as Pluronics, are a unique family of amphiphilic triblock polymers, which self-assemble into micelles in aqueous solution. These copolymers have shown promise in therapeutic, biomedical, cosmetic, and nanotech applications. As-received samples of Pluronics contain low molecular weight impurities (introduced during the manufacturing and processing), that are ignored in most applications. It has been observed, however, that in semi-dilute aqueous solutions, at concentrations above 1 wt%, the temperature dependent micellization behavior of the Pluronics is altered. Anomalous behavior includes a shift of the critical micellization temperature and formation of large aggregates at intermediate temperatures before stable sized micelles form. We attribute this behavior to the low molecular weight impurities that are inherent to the Pluronics which interfere with the micellization process. Through the use of Dynamic Light Scattering and HPLC, we compared the anomalous behavior of different Pluronics of different impurity levels to their purified counterparts.

  4. Functionalized block copolymers as adhesion promoters

    SciTech Connect

    Kent, M.S.; Saunders, R.

    1995-03-01

    The goal of this work is to develop novel functionalized block copolymers to promote adhesion at inorganic substrate/polymer interfaces. We envision several potential advantages of functionalized block copolymers over small molecule coupling agents. Greater control over the structure of the interphase region should result through careful design of the backbone of the copolymer. The number of chains per area, the degree of entanglement between the copolymer and the polymer matrix, the number of sites per chain able to attach to the substrate, and the hydrophobicity of the interphase region can all be strongly affected by the choice of block lengths and the monomer sequence. In addition, entanglement between the copolymer and the polymer matrix, if achieved, should contribute significantly to adhesive strength. Our program involves four key elements: the synthesis of suitable functionalized block copolymers, characterization of the conformation of the copolymers at the interface by neutron reflectivity and atomic force microscopy, characterization of the degree of bonding by spectroscopy, and measurement of the mechanical properties of the interface. In this paper we discuss block copolymers designed as adhesion promoters for the copper/epoxy interface. We have synthesized a diblock with one block containing imidazole groups to bond to copper and a second block containing secondary amines to react with the epoxy matrix. We have also prepared a triblock copolymer containing a hydrophobic middle block. Below we describe the synthesis of the block copolymers by living, ring-opening metathesis polymerization (ROMP) and the first characterization data obtained by neutron reflectivity.

  5. Amphiphilic copolymers for liquid bandage application studies.

    PubMed

    Zhang, Zhiqi; Conway, Anthony; Salamone, Ann Beal; Crumpler, Eric T; Zhang, Xueji; Li, Chen-zhong

    2010-06-01

    This research pertains to a new class of liquid bandage polymers which are promising for assisting advanced wound healing by serving as substrates to promote cell viability and proliferation. Amphiphilic nitrogen-containing polymer poly (3-methacryloyloxypropyltris (trimethylsiloxy)silane-co-N-isopropylacrylamide) (poly (TRIS-co-NIPAM)) was synthesized and investigated with further comparison to several different wound care polymers including commercialized 3M Nexcare No Sting Liquid Bandage. Cell viability on different polymers was tested on fetal human skin fibroblasts (HSFs) and neonatal human epidermal keratinocytes (HEKs). Test results were quantified by Sulforhodamine B (SRB) in vitro cytotoxicity assay. It was demonstrated that both HSFs and HEKs survive better on the poly (TRIS-co-NIPAM) film as the cell seeding substrate compared to other candidate polymer formulations, as well as to the commercial 3M No Sting Liquid Bandage polymer. Thus we conclude that wound healing could be accelerated by this new class of liquid bandage polymer, particularly for early-stage wounds..

  6. Imide/arylene ether block copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Hergenrother, P. M.; Bass, R. G.

    1991-01-01

    Two series of imide/arylene either block copolymers were prepared using an arylene ether block and either an amorphous or semi-crystalline imide block. The resulting copolymers were characterized and selected physical and mechanical properties were determined. These results, as well as comparisons to the homopolymer properties, are discussed.

  7. Pattern transfer using block copolymers.

    PubMed

    Gu, Xiaodan; Gunkel, Ilja; Russell, Thomas P

    2013-10-13

    To meet the increasing demand for patterning smaller feature sizes, a lithography technique is required with the ability to pattern sub-20 nm features. While top-down photolithography is approaching its limit in the continued drive to meet Moore's law, the use of directed self-assembly (DSA) of block copolymers (BCPs) offers a promising route to meet this challenge in achieving nanometre feature sizes. Recent developments in BCP lithography and in the DSA of BCPs are reviewed. While tremendous advances have been made in this field, there are still hurdles that need to be overcome to realize the full potential of BCPs and their actual use.

  8. Block versus Random Amphiphilic Glycopolymer Nanopaticles as Glucose-Responsive Vehicles.

    PubMed

    Guo, Qianqian; Zhang, Tianqi; An, Jinxia; Wu, Zhongming; Zhao, Yu; Dai, Xiaomei; Zhang, Xinge; Li, Chaoxing

    2015-10-12

    To explore the effect of polymer structure on their self-assembled aggregates and their unique characteristics, this study was devoted to developing a series of amphiphilic block and random phenylboronic acid-based glycopolymers by RAFT polymerization. The amphiphilic glycopolymers were successfully self-assembled into spherically shaped nanoparticles with narrow size distribution in aqueous solution. For block and random copolymers with similar monomer compositions, block copolymer nanoparticles exhibited a more regular transmittance change with the increasing glucose level, while a more evident variation of size and quicker decreasing tendency in I/I0 behavior in different glucose media were observed for random copolymer nanoparticles. Cell viability of all the polymer nanoparticles investigated by MTT assay was higher than 80%, indicating that both block and random copolymers had good cytocompatibility. Insulin could be encapsulated into both nanoparticles, and insulin release rate for random glycopolymer was slightly quicker than that for the block ones. We speculate that different chain conformations between block and random glycopolymers play an important role in self-assembled nanoaggregates and underlying glucose-sensitive behavior. PMID:26397308

  9. Curvature-coupled hydration of Semicrystalline Polymer Amphiphiles yields flexible Worm Micelles but favors rigid Vesicles: polycaprolactone-based block copolymers

    PubMed Central

    Rajagopal, Karthikan; Mahmud, Abdullah; Christian, David A.; Pajerowski, J. David; Brown, Andre E.X.; Loverde, Sharon M.; Discher, Dennis E.

    2010-01-01

    Crystallization processes are in general sensitive to detailed conditions, but our present understanding of underlying mechanisms is insufficient. A crystallizable chain within a diblock copolymer assembly is expected to couple curvature to crystallization and thereby impact rigidity as well as preferred morphology, but the effects on dispersed phases have remained unclear. The hydrophobic polymer polycaprolactone (PCL) is semi-crystalline in bulk (Tm = 60°C) and is shown here to generate flexible worm micelles or rigid vesicles in water from several dozen polyethyleneoxide-based diblocks (PEO-PCL). Despite the fact that `worms' have a mean curvature between that of vesicles and spherical micelles, `worms' are seen only within a narrow, process-dependent wedge of morphological phase space that is deep within the vesicle phase. Fluorescence imaging shows worms are predominantly in one of two states – either entirely flexible with dynamic thermal undulations or fully rigid; only a few worms appear rigid at room temperature (T << Tm), indicating suppression of crystallization by both curvature and PCL hydration. Worm rigidification, which depends on molecular weight, is also prevented by copolymerization of caprolactone with just 10% racemic lactide that otherwise has little impact on bulk crystallinity. In contrast to worms, vesicles of PEO-PCL are always rigid and typically leaky. Defects between crystallite domains induce dislocation-roughening with focal leakiness although select PEO-PCL – which classical surfactant arguments would predict make worms – yield vesicles that retain encapsulant and appear smooth, suggesting a gel or glassy state. Hydration in dispersion thus tends to selectively soften high curvature microphases. PMID:21499509

  10. Discovering Complex Ordered Phases of Block Copolymers

    NASA Astrophysics Data System (ADS)

    Shi, An-Chang

    2012-02-01

    Block copolymers with their rich phase behavior and ordering transitions have become a paradigm for the study of structured soft materials. Understanding the structures and phase transitions in block copolymers has been one of the most active research areas in polymer science in the past two decades. One of the achievements is the self-consistent field theory (SCFT), which provides a powerful framework for the study of ordered phase of block copolymers. I will present a generic strategy to discover complex ordered phases of block copolymers within the SCFT framework. Specifically, a combination of real-space and reciprocal-space techniques is used to explore possible ordered phases in multiblock copolymer melts. These candidate phases can then be used to construct phase diagrams. Application of this strategy to linear and star ABC triblock copolymers has led to the discovery of a rich array of ordered phases.

  11. Method for making block siloxane copolymers

    DOEpatents

    Butler, N.L.; Jessop, E.S.; Kolb, J.R.

    1981-02-25

    A method for synthesizing block polysiloxane copolymers is disclosed. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

  12. Method for making block siloxane copolymers

    DOEpatents

    Butler, Nora; Jessop, Edward S.; Kolb, John R.

    1982-01-01

    A method for synthesizing block polysiloxane copolymers. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

  13. Affinity-mediated capture and release of amphiphilic copolymers for controlling antimicrobial activity.

    PubMed

    Takahashi, Haruko; Akiyoshi, Kazunari; Kuroda, Kenichi

    2015-08-14

    Capture and release of amphiphilic copolymers by a nano-sized polysaccharide gel (nanogel) was controlled by altering the hydrophobic binding affinity between the copolymer chains and nanogel. The antimicrobial activity of captured copolymer chains was suppressed, and regained upon release from the nanogel. PMID:26154063

  14. Novel Redox-Responsive Amphiphilic Copolymer Micelles for Drug Delivery: Synthesis and Characterization.

    PubMed

    Bae, Jungeun; Maurya, Abhijeet; Shariat-Madar, Zia; Murthy, S Narasimha; Jo, Seongbong

    2015-11-01

    A novel redox-responsive amphiphilic polymer was synthesized with bioreductive trimethyl-locked quinone propionic acid for a potential triggered drug delivery application. The aim of this study was to synthesize and characterize the redox-responsive amphiphilic block copolymer micelles containing pendant bioreductive quinone propionic acid (QPA) switches. The redox-responsive hydrophobic block (polyQPA), synthesized from QPA-serinol and adipoyl chloride, was end-capped with methoxy poly(ethylene glycol) of molecular weight 750 (mPEG750) to achieve a redox-responsive amphiphilic block copolymer, polyQPA-mPEG750. PolyQPA-mPEG750 was able to self-assemble as micelles to show a critical micelle concentration (CMC) of 0.039% w/v (0.39 mg/ml, 0.107 mM) determined by a dye solubilization method using 1,6-diphenyl-1,3,5-hexatriene (DPH) in phosphate-buffered saline (PBS). The mean diameter of polymeric micelles was found to be 27.50 nm (PI = 0.064) by dynamic light scattering. Furthermore, redox-triggered destabilization of the polymeric micelles was confirmed by (1)H-NMR spectroscopy and particle size measurements in a simulated redox state. PolyQPA-mPEG750 underwent triggered reduction to shed pendant redox-responsive QPA groups and its polymeric micelles were swollen to be dissembled in the presence of a reducing agent, thereby enabling the release of loaded model drug, paclitaxel. The redox-responsive polyQPA-mPEG750 polymer micelles would be useful as a drug delivery system allowing triggered drug release in an altered redox state such as tumor microenvironments with an altered redox potential and/or redox enzyme upregulation.

  15. Efficient cytosolic delivery mediated by polymersomes facilely prepared from a degradable, amphiphilic, and amphoteric copolymer

    NASA Astrophysics Data System (ADS)

    Huang, Zhonghui; Teng, Wei; Liu, Longshan; Wang, Lichun; Wang, Qinmei; Dong, Yugang

    2013-07-01

    To solve problems in polymersome preparation caused by liposolubility of copolymers and to improve the cytosolic delivery efficiency of polymersomes to drugs, a lipopolysaccharide-amine (LPSA) copolymer with amphotericity and amphiphilicity is developed. LPSA contains two hydrophilic oppositely charged blocks (anionic oxidized alginate (OA), cationic polyethyleneimine (PEI 1.8k)) and one hydrophobic block (cholesteryl), where OA is the backbone and cholesteryl-grafted PEI is the side chain. The two hydrophilic blocks first guarantee that LPSA will dissolve in water, and then help polymersome formation via electrostatic interactions to generate water insoluble interpolyelectrolyte complexes, which supplement the hydrophobic part to reach the right hydrophilicity/hydrophobicity ratio, and thus realize a one-step self-assembly of polymersomes in water. Our results show LPSA nanopolymersomes (LNPs) have low cytotoxicity and degradability, and an excellent ability to enter cells. TEM observation demonstrates that LNPs are entrapped in endosomes after endocytosis, and are then released to cytosols because of their strong endosomal escape capacity. As an example of cytosolic delivery to bioactive molecules, pDNA is delivered in mesenchymal stem cells, and more than 95% of cells express a large target protein, indicating that LNPs have high cytosolic delivery efficiency. Our study provides a novel, easy, and universal method to design copolymers for the preparation of polymersomes as efficient cytosolic delivery nanocarriers.

  16. Adsorption and aqueous lubricating properties of charged and neutral amphiphilic diblock copolymers at a compliant, hydrophobic interface.

    PubMed

    Røn, Troels; Javakhishvili, Irakli; Jankova, Katja; Hvilsted, Søren; Lee, Seunghwan

    2013-06-25

    We have investigated the adsorption and lubricating properties of neutral and charged amphiphilic diblock copolymers at a hydrophobic polydimethylsiloxane (PDMS) interface in an aqueous environment. The diblock copolymers consist of a hydrophilic block of either neutral poly(ethylene glycol) (PEG) or negatively charged poly(acrylic acid) (PAA) and of a hydrophobic block of polystyrene (PS) or poly(2-methoxyethyl acrylate) (PMEA), thus generating PEG-b-X or PAA-b-X, where X block is either PS or PMEA. The molecular weight ratios were roughly 1:1 with each block ca. 5 kDa. Comparing the neutral PEG and charged PAA buoyant blocks with all other conditions identical, the former showed superior adsorption onto nonpolar, hydrophobic PDMS surfaces from a neutral aqueous solution. PEG-based copolymers showed substantial adsorption for both PS and PMEA as the anchoring block, whereas PAA-based copolymers showed effective adsorption only when PMEA was employed as the anchoring block. For PAA-b-PS, the poor adsorption properties are chiefly attributed to micellization due to the high interfacial tension between the PS core and water. The poor lubricating properties of PAA-b-PS diblock copolymer for a PDMS-PDMS sliding contact was well correlated with the poor adsorption properties. PAA-b-PMEA copolymers, despite their sizable amount of adsorbed mass, showed insignificant lubricating effects. When the charges of the PAA-b-PMEA diblock copolymers were screened by either adding NaCl to the aqueous solution or by lowering the pH, both the adsorption and lubricity improved. We ascribe the poor adsorption and inferior aqueous lubricating properties of the PAA-based diblock copolymers compared to their PEG-based counterparts mainly to the electrostatic repulsion between charged PAA blocks, hindering the facile formation of the lubricating layer under cyclic tribological stress at the sliding PDMS-PDMS interface. PMID:23725290

  17. Triblock Copolymers with Grafted Fluorine-Free Amphiphilic Non-Ionic Side Chains for Antifouling and Fouling-Release Applications

    SciTech Connect

    Y Cho; H Sundaram; C Weinman; M Paik; M Dimitriou; J Finlay; M Callow; J Callow; E Kramer; C Ober

    2011-12-31

    Fluorine-free, amphiphilic, nonionic surface active block copolymers (SABCs) were synthesized through chemical modification of a polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene triblock copolymer precursor with selected amphiphilic nonionic Brij and other surfactants. Amphiphilicity was imparted by a hydrophobic aliphatic group combined with a hydrophilic poly(ethylene glycol) (PEG) group-containing moiety. The surfaces were characterized by dynamic water contact angle, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure (NEXAFS) analysis. In biofouling assays, settlement (attachment) of both spores of the green alga Ulva and cells of the diatom Navicula on SABCs modified with Brij nonionic side chains was significantly reduced relative to a PDMS standard, with a nonionic surfactant combining a PEG group and an aliphatic moiety demonstrating the best performance. Additionally, a fouling-release assay using sporelings (young plants) of Ulva and Navicula suggested that the SABC derived from nonionic Brij side chains also out-performed PDMS as a fouling-release material. Good antifouling and fouling-release properties were not demonstrated for the other two amphiphilic surfaces derived from silicone and aromatic group containing nonionic surfactants included in this study. The results suggest that small differences in chemical surface functionality impart more significant changes with respect to the antifouling settlement and fouling-release performance of materials than overall wettability behavior.

  18. Bulk modification of PDMS microchips by an amphiphilic copolymer.

    PubMed

    Xiao, Yan; Yu, Xiao-Dong; Xu, Jing-Juan; Chen, Hong-Yuan

    2007-09-01

    A simple and rapid bulk-modification method based on adding an amphiphilic copolymer during the fabrication process was employed to modify PDMS microchips. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was used as the additive substance. Compared to the native PDMS microchips, both the contact angle and the EOF of the bulk-modified PDMS microchips decreased. The effects of the additive loading and the pH on the EOF were investigated in detail. The bulk-modified PDMS microchips exhibited reproducible and stable EOF behavior. The application of the bulk-modified PDMS microchips was also studied and the results indicated that they could be successfully used to separate amino acids and to suppress protein adsorption.

  19. Block Copolymer Membranes for Biofuel Purification

    NASA Astrophysics Data System (ADS)

    Evren Ozcam, Ali; Balsara, Nitash

    2012-02-01

    Purification of biofuels such as ethanol is a matter of considerable concern as they are produced in complex multicomponent fermentation broths. Our objective is to design pervaporation membranes for concentrating ethanol from dilute aqueous mixtures. Polystyrene-b-polydimethylsiloxane-b-polystyrene block copolymers were synthesized by anionic polymerization. The polydimethylsiloxane domains provide ethanol-transporting pathways, while the polystyrene domains provide structural integrity for the membrane. The morphology of the membranes is governed by the composition of the block copolymer while the size of the domains is governed by the molecular weight of the block copolymer. Pervaporation data as a function of these two parameters will be presented.

  20. Block copolymer structures in nano-pores

    NASA Astrophysics Data System (ADS)

    Pinna, Marco; Guo, Xiaohu; Zvelindovsky, Andrei

    2010-03-01

    We present results of coarse-grained computer modelling of block copolymer systems in cylindrical and spherical nanopores on Cell Dynamics Simulation. We study both cylindrical and spherical pores and systematically investigate structures formed by lamellar, cylinders and spherical block copolymer systems for various pore radii and affinity of block copolymer blocks to the pore walls. The obtained structures include: standing lamellae and cylinders, ``onions,'' cylinder ``knitting balls,'' ``golf-ball,'' layered spherical, ``virus''-like and mixed morphologies with T-junctions and U-type defects [1]. Kinetics of the structure formation and the differences with planar films are discussed. Our simulations suggest that novel porous nano-containers can be formed by confining block copolymers in pores of different geometries [1,2]. [4pt] [1] M. Pinna, X. Guo, A.V. Zvelindovsky, Polymer 49, 2797 (2008).[0pt] [2] M. Pinna, X. Guo, A.V. Zvelindovsky, J. Chem. Phys. 131, 214902 (2009).

  1. Phase Behavior of Symmetric Sulfonated Block Copolymers

    SciTech Connect

    Park, Moon Jeong; Balsara, Nitash P.

    2008-08-21

    Phase behavior of poly(styrenesulfonate-methylbutylene) (PSS-PMB) block copolymers was studied by varying molecular weight, sulfonation level, and temperature. Molecular weights of the copolymers range from 2.9 to 117 kg/mol. Ordered lamellar, gyroid, hexagonally perforated lamellae, and hexagonally packed cylinder phases were observed in spite of the fact that the copolymers are nearly symmetric with PSS volume fractions between 0.45 and 0.50. The wide variety of morphologies seen in our copolymers is inconsistent with current theories on block copolymer phase behavior such as self-consistent field theory. Low molecular weight PSS-PMB copolymers (<6.2 kg/mol) show order-order and order-disorder phase transitions as a function of temperature. In contrast, the phase behavior of high molecular weight PSS-PMB copolymers (>7.7 kg/mol) is independent of temperature. Due to the large value of Flory-Huggins interaction parameter, x, between the sulfonated and non-sulfonated blocks, PSS-PMB copolymers with PSS and PMB molecular weights of 1.8 and 1.4 kg/mol, respectively, show the presence of an ordered gyroid phase with a 2.5 nm diameter PSS network. A variety of methods are used to estimate x between PSS and PMB chains as a function of sulfonation level. Some aspects of the observed phase behavior of PSS-PMB copolymers can be rationalized using x.

  2. Key roles for chain flexibility in block copolymer membranes that contain pores or make tubes.

    PubMed

    Srinivas, Goundla; Discher, Dennis E; Klein, Michael L

    2005-12-01

    Block copolymer amphiphiles that self-assemble into membranes present robust and functionalizable alternatives to biological assemblies. Coarse-grained molecular dynamics shows that thick bilayers of A-B copolymers accommodate protein-like channels and also tend to regulate transport. This occurs as flexible, hydrophilic A chains insert into the pore and obstruct water entry. A-B-A triblocks that exploit "hairpin" and "straight" conformations also show assembly into novel nanotubules and further highlight the key roles for chain flexibility in biomimetic block copolymer assemblies.

  3. Resilient self-assembling hydrogels from block copolypeptide amphiphiles

    NASA Astrophysics Data System (ADS)

    Nowak, Andrew Paul

    The ability to produce well defined synthetic polypeptides has been greatly improved by the discovery of transition metal species that mediate the controlled polymerization of N-carboxyanhydrides (NCAs). These metal species create a living polymerization system by producing control over chain length, low polydispersities, and the ability to form complex block architectures. We have applied this system to the synthesis of block copolypeptide amphiphiles. Initial block copolymers synthesized were composed of hydrophilic, cationic poly(L-Lysine) combined with hydrophobic, alpha-helical poly(L-Leucine). These Lysine- block-Leucine copolypeptides were found to form stiff, clear hydrogels at low concentration (˜1 wt%) in low ionic strength water. Based on this unexpected result we used the flexibility of our transition metal polymerization chemistry to better understand the nature and mechanisms of gel formation in these materials. Systematic changes to the original Lysine-block-Leucine copolypeptides were made by altering overall chain size, relative block length, polyelectrolyte charge, and hydrophobic secondary structure. Rheological characterization revealed that the strength of these hydrogels was primarily dependent on degree of polymerization, relative block length, and a well ordered secondary structure in the hydrophobic segment. The Lysine-block-Leucine hydrogels were formed by direct addition of water to dry polypeptide material which swelled to homogeneously fill the entire volume of liquid with no special processing. CryoTEM showed a percolating cellular network at ˜100nm that appears to be comprised of both membranes and fibers. Larger length scales studied with Laser Scanning Confocal Microscopy revealed a spontaneously formed microporous network with large (˜10mum) water rich voids. These hydrogels also displayed interesting mechanical properties including rapid recovery of solid like behavior after being sheared to a liquid and mechanical stability

  4. Electrostatic control of block copolymer morphology

    NASA Astrophysics Data System (ADS)

    Sing, Charles E.; Zwanikken, Jos W.; Olvera de La Cruz, Monica

    2014-07-01

    Energy storage is at present one of the foremost issues society faces. However, material challenges now serve as bottlenecks in technological progress. Lithium-ion batteries are the current gold standard to meet energy storage needs; however, they are limited owing to the inherent instability of liquid electrolytes. Block copolymers can self-assemble into nanostructures that simultaneously facilitate ion transport and provide mechanical stability. The ions themselves have a profound, yet previously unpredictable, effect on how these nanostructures assemble and thus the efficiency of ion transport. Here we demonstrate that varying the charge of a block copolymer is a powerful mechanism to predictably tune nanostructures. In particular, we demonstrate that highly asymmetric charge cohesion effects can induce the formation of nanostructures that are inaccessible to conventional uncharged block copolymers, including percolated phases desired for ion transport. This vastly expands the design space for block copolymer materials and is informative for the versatile design of battery electrolyte materials.

  5. Microspheres for protein delivery prepared from amphiphilic multiblock copolymers. 2. Modulation of release rate.

    PubMed

    Bezemer, J M; Radersma, R; Grijpma, D W; Dijkstra, P J; van Blitterswijk, C A; Feijen, J

    2000-07-01

    Amphiphilic multiblock copolymers, based on hydrophilic poly(ethylene glycol) (PEG) blocks and hydrophobic poly(butylene terephthalate) (PBT) blocks were used as matrix material for protein-loaded microspheres. The efficiency of lysozyme entrapment by a double emulsion method was found to depend on the swelling behavior of the polymers in water and decreased from 100% for polymers with a degree of swelling of less than 1.8 to 11% for PEG-PBT copolymers with a degree of swelling of 3.6. The particle size could be controlled by varying the concentration of the polymer solution used in the microsphere preparation. An increase in the polymer concentration resulted in a proportional increase in the particle size. The in vitro release profiles of the encapsulated model protein lysozyme could be precisely tailored by variation of the copolymer composition and the size of the microspheres. Both a slow continuous release of lysozyme, and a fast release which was completed within a few days could be obtained. The release behavior, attributed to a combination of diffusion and polymer degradation, could be described by a previously developed model. PMID:10825558

  6. Self-Assembly of Novel Amphiphilic 21-Arm, Star-Like Coil-Rod Diblock Copolymers at Interfaces

    NASA Astrophysics Data System (ADS)

    Lin, Zhiqun; Zhao, Lei; Pang, Xinchang; Feng, Chaowei

    2012-02-01

    A series of novel amphiphilic 21-arm, star-like diblock copolymers, poly(acrylic acid)-b-poly(3-hexylthiophene) (PAA-b-P3HT) based on β-cyclodextrin (β-CD) with well defined molecular architectures and ratio of two chemically distinct blocks were prepared, for the first time, via a combination of quasi-living Grignard metathesis method (GRIM), click reaction, and atom transfer radical polymerization (ATRP). The star-like PAA-b-P3HT diblock copolymers consist of hydrophilic coil-like PAA cores and hydrophobic rod-like P3HT shells with narrow molecular weight distribution and controllable molecular weight of each block. Owing to the compact structure, the amphiphilic star-like PAA-b-P3HT formed a unimolecular micelle. Vesicles based on these novel amphiphilic star-like, coil-rod diblock copolymers were readily produced at the oil/water interface by crosslinking hydrophilic coil-like PAA cores with a bifunctional crosslinker, ethylenediamine. They also self-assembled into a nanotubular structure at the air/water interface.

  7. Poly(2-methyl-2-oxazoline)-b-poly(tetrahydrofuran)-b-poly(2-methyl-2-oxazoline) amphiphilic triblock copolymers: synthesis, physicochemical characterizations, and hydrosolubilizing properties.

    PubMed

    Rasolonjatovo, Bazoly; Gomez, Jean-Pierre; Même, William; Gonçalves, Cristine; Huin, Cécile; Bennevault-Celton, Véronique; Le Gall, Tony; Montier, Tristan; Lehn, Pierre; Cheradame, Hervé; Midoux, Patrick; Guégan, Philippe

    2015-03-01

    Block copolymers assembled into micelles have gained a lot of attention to improve drug delivery. The recent drawbacks of the poly(ethylene oxide) blocks (PEO) contained in amphiphilic pluronics derivatives made of a central poly(propylene oxide) block surrounded by two PEO blocks were recently revealed, opening the way to the design of new amphiphilic block copolymers able to self-assemble in water and to entrap molecules of interest. Here, a family of p(methyloxazoline)-b-p(tetrahydrofuran)-b-p(methyloxazoline) triblock copolymers (called TBCP) is synthesized using cationic ring opening polymerization. Studies of micelle formation using dynamic light scattering, isothermal titration calorimetry (ITC), NMR diffusion-ordered spectroscopy (DOSY), and fluorescence experiments lead us to draw a relationship between copolymer structure and the physicochemical properties of the block copolymers (critical micellar concentration (CMC), Nagg, core diameter, shell thickness, etc.). The packing parameter of the block copolymers indicates the formation of a core-corona structure. Hydrosolubilizing properties of TBCPs were exemplified with curcumin selected as a highly insoluble drug model. Curcumin, a natural polyphenolic compound, has shown a large spectrum of biological and pharmacological activity, including anti-inflammatory, antimicrobial, antioxidant, and anticarcinogenic activities. An optimized formulation process reveals that the aggregation number is the parameter affecting drug encapsulation. Patch clamp experiments carried out to study the interaction of TBCP with the cell membrane demonstrate their permeation property suitable to promote the cellular internalization of curcumin. PMID:25517924

  8. Arbitrary lattice symmetries via block copolymer nanomeshes

    PubMed Central

    Majewski, Pawel W.; Rahman, Atikur; Black, Charles T.; Yager, Kevin G.

    2015-01-01

    Self-assembly of block copolymers is a powerful motif for spontaneously forming well-defined nanostructures over macroscopic areas. Yet, the inherent energy minimization criteria of self-assembly give rise to a limited library of structures; diblock copolymers naturally form spheres on a cubic lattice, hexagonally packed cylinders and alternating lamellae. Here, we demonstrate multicomponent nanomeshes with any desired lattice symmetry. We exploit photothermal annealing to rapidly order and align block copolymer phases over macroscopic areas, combined with conversion of the self-assembled organic phase into inorganic replicas. Repeated photothermal processing independently aligns successive layers, providing full control of the size, symmetry and composition of the nanoscale unit cell. We construct a variety of symmetries, most of which are not natively formed by block copolymers, including squares, rhombuses, rectangles and triangles. In fact, we demonstrate all possible two-dimensional Bravais lattices. Finally, we elucidate the influence of nanostructure on the electrical and optical properties of nanomeshes. PMID:26100566

  9. Rapid self-assembly of block copolymers to photonic crystals

    DOEpatents

    Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

    2016-07-05

    The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

  10. Surface Engineering of Styrene/PEGylated-Fluoroalkyl Styrene Block Copolymer Thin Films

    SciTech Connect

    Martinelle, E.; Menghetti, S; Galli, G; Glisenti, A; Krishnan, S; Paik, M; Ober, C; Smilgies, D; Fischer, D

    2009-01-01

    A series of diblock copolymers prepared from styrenic monomers was synthesized using atom transfer radical polymerization. One block was derived from styrene, whereas the second block was prepared from a styrene modified with an amphiphilic PEGylated-fluoroalkyl side chain. The surface properties of the resulting polymer films were carefully characterized using dynamic contact angle, XPS, and NEXAFS measurements. The polymer morphology was investigated using atomic force microscope and GISAXS studies. The block copolymers possess surfaces dominated by the fluorinated unit in the dry state and a distinct phase separated microstructure in the thin film. The microstructure of these polymers is strongly influenced by the thin film structure in which it is investigated.

  11. Effects of amphiphilic diblock copolymer on drug nanoparticle formation and stability

    PubMed Central

    Zhu, Zhengxi

    2013-01-01

    This study systematically compares the effects of amphiphilic diblock copolymer (di-BCP) on stabilizing hydrophobic drug nanoparticles formed by flash nanoprecipitation (FNP), and provides a guideline on choosing suitable di-BCPs. Four widely used di-BCPs, i.e., polystyrene-block-poly(ethylene glycol) (PS-b-PEG), polycaprolactone-block-poly(ethylene glycol) (PCL-b-PEG), polylactide-block-poly(ethylene glycol) (PLA-b-PEG), and poly(lactic-co-glycolic acid) (PLGA-b-PEG), and β-carotene as a model drug were used. The study showed that PLGA-b-PEG was the most suitable one, whose hydrophobic block was biodegradable and noncrystallizable as well as had relatively high glass transition temperature (Tg) and a right solubility parameter (δ). The molecular weight of PLGA block over the range from 5k to 15k showed an insignificant effect on controlling the particle size. Amorphous drug particles with a high drug loading of over 83 wt% can be achieved. Much remarkable evidence supported the nanoparticles with kinetically frozen and nonequilibrium packing structures of polymer chains rather than either the micelles or micellar nanoparticles with two well segregated polymer blocks. The thermodynamic effects of the drug and BCP on the particle stability, size and structures were discussed by using solubility parameters. PMID:24070569

  12. Mixing thermodynamics of block-random copolymers

    NASA Astrophysics Data System (ADS)

    Beckingham, Bryan Scott

    Random copolymerization of A and B monomers represents a versatile method to tune interaction strengths between polymers, as ArB random copolymers will exhibit a smaller effective Flory interaction parameter chi; (or interaction energy density X) upon mixing with A or B homopolymers than upon mixing A and B homopolymers with each other, and the ArB composition can be tuned continuously. Thus, the incorporation of a random copolymer block into the classical block copolymer architecture to yield "block-random" copolymers introduces an additional tuning mechanism for the control of structure-property relationships, as the interblock interactions and physical properties can be tuned continuously through the random block's composition. However, typical living or controlled polymerizations produce compositional gradients along the "random" block, which can in turn influence the phase behavior. This dissertation demonstrates a method by which narrow-distribution copolymers of styrene and isoprene of any desired composition, with no measurable down-chain gradient, are synthesized. This synthetic method is then utilized to incorporate random copolymers of styrene and isoprene as blocks into block-random copolymers in order to examine the resulting interblock mixing thermodynamics. A series of well-defined near-symmetric block and block-random copolymers (S-I, Bd-S, I-SrI, S-SrI and Bd-S rI diblocks, where S is polystyrene, I is polyisoprene and Bd is polybutadiene), with varying molecular weight and random-block composition are synthesized and the mixing thermodynamics---via comparison of their interaction energy densities, X---of their hydrogenated derivatives is examined through measurement of the order-disorder transition (ODT) temperature. Hydrogenated derivatives of I-SrI and S-SrI block-random copolymers, both wherein the styrene aromaticity is retained and derivatives wherein the styrene units are saturated to vinylcyclohexane (VCH), are found to hew closely to the

  13. Asymmetrical Self-assembly From Fluorinated and Sulfonated Block Copolymers in Aqueous Media

    SciTech Connect

    Wang, Xiaojun; Hong, Kunlun; Baskaran, Durairaj; Goswami, Monojoy; Sumpter, Bobby G; Mays, Jimmy

    2011-01-01

    Block copolymers of fluorinated isoprene and partially sulfonated styrene form novel tapered rods and ribbon-like micelles in aqueous media due to a distribution of sulfonation sites and a large Flory-Huggins interaction parameter. A combination of microscopy, light scattering, and simulation demonstrates the presence of these unique nanostructures. This study sheds light on the micellization behavior of amphiphilic block polymers by revealing a new mechanism of self-assembly.

  14. DNA block copolymers: functional materials for nanoscience and biomedicine.

    PubMed

    Schnitzler, Tobias; Herrmann, Andreas

    2012-09-18

    We live in a world full of synthetic materials, and the development of new technologies builds on the design and synthesis of new chemical structures, such as polymers. Synthetic macromolecules have changed the world and currently play a major role in all aspects of daily life. Due to their tailorable properties, these materials have fueled the invention of new techniques and goods, from the yogurt cup to the car seat belts. To fulfill the requirements of modern life, polymers and their composites have become increasingly complex. One strategy for altering polymer properties is to combine different polymer segments within one polymer, known as block copolymers. The microphase separation of the individual polymer components and the resulting formation of well defined nanosized domains provide a broad range of new materials with various properties. Block copolymers facilitated the development of innovative concepts in the fields of drug delivery, nanomedicine, organic electronics, and nanoscience. Block copolymers consist exclusively of organic polymers, but researchers are increasingly interested in materials that combine synthetic materials and biomacromolecules. Although many researchers have explored the combination of proteins with organic polymers, far fewer investigations have explored nucleic acid/polymer hybrids, known as DNA block copolymers (DBCs). DNA as a polymer block provides several advantages over other biopolymers. The availability of automated synthesis offers DNA segments with nucleotide precision, which facilitates the fabrication of hybrid materials with monodisperse biopolymer blocks. The directed functionalization of modified single-stranded DNA by Watson-Crick base-pairing is another key feature of DNA block copolymers. Furthermore, the appropriate selection of DNA sequence and organic polymer gives control over the material properties and their self-assembly into supramolecular structures. The introduction of a hydrophobic polymer into DBCs

  15. Composition and properties of porous blend membranes containing tertiary amine based amphiphilic copolymers with different sequence structures.

    PubMed

    Yao, Zhikan; Cui, Yue; Zheng, Ke; Zhu, Baoku; Zhu, Liping

    2015-01-01

    Four tertiary amine based amphiphilic copolymers with similar composition but different sequence structures in terms of diblock (Poly(dimethylamino-2-ethyl methacrylate-b-methyl methacrylate) (P(MMA-b-DMAEMA))), triblock (P(DMAEMA-b-MMA-b-DMAEMA)), four-armed diblock (P(MMA-b-DMAEMA)4) and random (P(MMA-r-DMAEMA)) were synthesized and used for fabricating functional porous membranes by blending method. The retention ratios and surface enrichment ratios of the copolymers in blend membranes were determined by hydrogen nuclear magnetic resonance ((1)H-NMR) and X-ray photoelectron spectroscopy (XPS). The composition of the formed membranes was investigated and the durability was experimentally tested. The hydrophilicity of the membranes was evaluated by water contact angle measurement. The performance of membranes under different conditions including water fluxes at different pH and various ionic strength, the adsorption capabilities for Cr(VI) and negatively charged dye sunset yellow at different pH was studied. The results show that tertiary amine based amphiphilic copolymers with block and multi-armed sequence structures enable the blend membranes with higher copolymer retention ratios, more surface tertiary amine groups contents and better composition stability as well as more sensitive to the variation of pH, ionic strength, higher equilibrium anions, and negatively charged dyes uptakes.

  16. Reduction-sensitive amphiphilic triblock copolymers self-assemble into stimuli-responsive micelles for drug delivery.

    PubMed

    Toughraï, Smahan; Malinova, Violeta; Masciadri, Raffaello; Menon, Sindhu; Tanner, Pascal; Palivan, Cornelia; Bruns, Nico; Meier, Wolfgang

    2015-04-01

    Polymeric nanostructures obtained through self-assembly of reduction-sensitive amphiphilic triblock copolymers were investigated as potential drug delivery systems. The characteristic feature of these polymers is their cleavable disulfide bond in the center of the hydrophobic block. Therefore, the triblock copolymers can be cleaved into amphiphilic diblock copolymers. A poly(2-hydroxyethyl methacrylate)-b-poly(butyl methacrylate)-S-S-poly(butyl methacrylate)-b-poly(2-hydroxyethyl methacrylate) (PHEMA-b-(PBMA-S-S-PBMA)-b-PHEMA) triblock copolymer was synthesized. It self-assembled into micelles which were used to encapsulate hydrophobic dye molecules (Nile Red, BodiPy 630/650) as model payloads. The self-assembled nanostructures disintegrated upon reduction of the disulfide bond, releasing their cargo and yielding larger particles that formed aggregates in solution after 24 h. A burst release of payload was shown within the first 15 min, followed by a constant release over several hours. As concentration gradients of reducing agents are commonly found in biological systems, the micelles could be used as redox-sensitive nanocarriers for the intracellular delivery of drugs.

  17. Fabrication of platinum nanoparticles in aqueous solution and solid phase using amphiphilic PB-b-PEO copolymer nanoreactors

    SciTech Connect

    Hoda, Numan; Budama, Leyla; Çakır, Burçin Acar; Topel, Önder; Ozisik, Rahmi

    2013-09-01

    Graphical abstract: TEM image of Pt nanoparticles produced by reducing by NaBH{sub 4} within PB-b-PEO micelles in aqueous media (scale bar 1 nm). - Highlights: • Pt nanoparticles were synthesized within amphiphilic diblock copolymer micelles. • The effects of reducing agents and precursor dose on Pt np size were investigated. • The effect on fabrication of Pt np by reducing in aqueous and solid phases was compared. • The size of nanoparticles was about 1.4 nm for all doses and reducing agents types. - Abstract: Fabrication of Pt nanoparticles using an amphiphilic copolymer template in aqueous solution was achieved via polybutadiene-block-polyethyleneoxide copolymer micelles, which acted as nanoreactors. In addition, Pt nanoparticles were synthesized using hydrogen gas as the reducing agent in solid state for the first time to compare against solution synthesis. The influences of loaded precursor salt amount to micelles and the type of reducing agent on the size of nanoparticles were investigated through transmission electron microscopy. It was found that increasing the ratio of precursor salt to copolymer and using different type of reducing agent, even in solid phase reduction, did not affect the nanoparticle size. The average size of Pt nanoparticles was estimated to be 1.4 ± 0.1 nm. The reason for getting same sized nanoparticles was discussed in the light of nucleation, growth process, stabilization and diffusion of nanoparticles within micelles.

  18. Periodically Grafted Amphiphilic Copolymers: Effects of Steric Crowding and Reversal of Amphiphilicity.

    PubMed

    Mandal, Joydeb; Ramakrishnan, S

    2015-06-01

    Two series of periodically clickable polyesters were prepared; one of them carries alkylene segments along its backbone, whereas the other carries poly(ethylene glycol) (PEG) segments. These polyesters were clicked with either MPEG-350 azide or docosyl (C22) azide to yield periodically grafted amphiphilic copolymers (PGACs) carrying either flexible hydrophilic or crystallizable hydrophobic backbone segments. The immiscibility between hydrocarbon and PEG segments causes both of these systems to fold in either a zigzag or hairpin-like conformation; the hairpin-like conformation appears to be preferred when flexible PEG segments are present in the backbone. The folded chains further reorganize in the solid state to develop a lamellar morphology that permits the collocation of the PEG and hydrocarbon (HC) segments within alternate domains; evidence for the self-segregation was gained from DSC, SAXS, and AFM studies. SAXS studies revealed the formation of an extended lamellar structure, whereas AFM images showed uniform layered morphology with layer heights that matched reasonably well with the interlamellar spacing obtained from the SAXS study. Labeling one representative PGAC, carrying crystallizable long alkylene segments in the backbone and pendant PEG-350 side chains, with a small mole fraction of pyrene fluorophore permitted the examination of the conformational transition that occurs upon going from a good to a poor solvent; this single-chain folded conformation, we postulate, is the intermediate that organizes into the lamellar morphology.

  19. An amphiphilic graft copolymer-based nanoparticle platform for reduction-responsive anticancer and antimalarial drug delivery

    NASA Astrophysics Data System (ADS)

    Najer, Adrian; Wu, Dalin; Nussbaumer, Martin G.; Schwertz, Geoffrey; Schwab, Anatol; Witschel, Matthias C.; Schäfer, Anja; Diederich, François; Rottmann, Matthias; Palivan, Cornelia G.; Beck, Hans-Peter; Meier, Wolfgang

    2016-08-01

    Medical applications of anticancer and antimalarial drugs often suffer from low aqueous solubility, high systemic toxicity, and metabolic instability. Smart nanocarrier-based drug delivery systems provide means of solving these problems at once. Herein, we present such a smart nanoparticle platform based on self-assembled, reduction-responsive amphiphilic graft copolymers, which were successfully synthesized through thiol-disulfide exchange reaction between thiolated hydrophilic block and pyridyl disulfide functionalized hydrophobic block. These amphiphilic graft copolymers self-assembled into nanoparticles with mean diameters of about 30-50 nm and readily incorporated hydrophobic guest molecules. Fluorescence correlation spectroscopy (FCS) was used to study nanoparticle stability and triggered release of a model compound in detail. Long-term colloidal stability and model compound retention within the nanoparticles was found when analyzed in cell media at body temperature. In contrast, rapid, complete reduction-triggered disassembly and model compound release was achieved within a physiological reducing environment. The synthesized copolymers revealed no intrinsic cellular toxicity up to 1 mg mL-1. Drug-loaded reduction-sensitive nanoparticles delivered a hydrophobic model anticancer drug (doxorubicin, DOX) to cancer cells (HeLa cells) and an experimental, metabolically unstable antimalarial drug (the serine hydroxymethyltransferase (SHMT) inhibitor (+/-)-1) to Plasmodium falciparum-infected red blood cells (iRBCs), with higher efficacy compared to similar, non-sensitive drug-loaded nanoparticles. These responsive copolymer-based nanoparticles represent a promising candidate as smart nanocarrier platform for various drugs to be applied to different diseases, due to the biocompatibility and biodegradability of the hydrophobic block, and the protein-repellent hydrophilic block.Medical applications of anticancer and antimalarial drugs often suffer from low aqueous

  20. High intensity focused ultrasound responsive metallo-supramolecular block copolymer micelles.

    PubMed

    Liang, Bo; Tong, Rui; Wang, Zhenhua; Guo, Shengwei; Xia, Hesheng

    2014-08-12

    The metal-supramolecular diblock copolymer containing mechano-labile bis(terpyridine)-Cu(II) complex linkage in the junction point was synthesized. These metal-ligand containing amphiphilic copolymers are able to self-assemble in aqueous solution to form spherical micelles with poly(propylene glycol) block forming the hydrophobic core. It is found that high intensity focused ultrasound can open the copolymer micelles and trigger the release of the payload in the micelle. The micellar properties and release kinetics of encapsulated guest molecule in response to ultrasound stimuli were investigated. The weak Cu(II)-terpyridine dynamic bond in the copolymer chain can be cleaved under ultrasound and thus leads to the disruption of the copolymer micelle and the release of loaded cargo. This study will open up a new way for the molecular design of ultrasound modulated drug delivery systems. PMID:25072274

  1. Antimicrobial and antioxidant amphiphilic random copolymers to address medical device-centered infections.

    PubMed

    Taresco, Vincenzo; Crisante, Fernanda; Francolini, Iolanda; Martinelli, Andrea; D'Ilario, Lucio; Ricci-Vitiani, Lucia; Buccarelli, Mariachiara; Pietrelli, Loris; Piozzi, Antonella

    2015-08-01

    Microbial biofilms are known to support a number of human infections, including those related to medical devices. This work is focused on the development of novel dual-function amphiphilic random copolymers to be employed as coatings for medical devices. Particularly, copolymers were obtained by polymerization of an antimicrobial cationic monomer (bearing tertiary amine) and an antioxidant and antimicrobial hydrophobic monomer (containing hydroxytyrosol, HTy). To obtain copolymers with various amphiphilic balance, different molar ratios of the two monomers were used. (1)H NMR and DSC analyses evidenced that HTy aromatic rings are able to interact with each other leading to a supra-macromolecular re-arrangement and decrease the copolymer size in water. All copolymers showed good antioxidant activity and Fe(2+) chelating ability. Cytotoxicity and hemolytic tests evidenced that the amphiphilic balance, cationic charge density and polymer size in solution are key determinants for polymer biocompatibility. As for the antimicrobial properties, the lowest minimal inhibitory concentration (MIC = 40 μg/mL) against Staphylococcus epidermidis was shown by the water-soluble copolymer having the highest HTy molar content (0.3). This copolymer layered onto catheter surfaces was also able to prevent staphylococcal adhesion. This approach permits not only prevention of biofilm infections but also reduction of the risk of emergence of drug-resistant bacteria. Indeed, the combination of two active compounds in the same polymer can provide a synergistic action against biofilms and suppress reactive species oxygen (ROS), known to promote the occurrence of antibiotic resistance.

  2. Antimicrobial and antioxidant amphiphilic random copolymers to address medical device-centered infections.

    PubMed

    Taresco, Vincenzo; Crisante, Fernanda; Francolini, Iolanda; Martinelli, Andrea; D'Ilario, Lucio; Ricci-Vitiani, Lucia; Buccarelli, Mariachiara; Pietrelli, Loris; Piozzi, Antonella

    2015-08-01

    Microbial biofilms are known to support a number of human infections, including those related to medical devices. This work is focused on the development of novel dual-function amphiphilic random copolymers to be employed as coatings for medical devices. Particularly, copolymers were obtained by polymerization of an antimicrobial cationic monomer (bearing tertiary amine) and an antioxidant and antimicrobial hydrophobic monomer (containing hydroxytyrosol, HTy). To obtain copolymers with various amphiphilic balance, different molar ratios of the two monomers were used. (1)H NMR and DSC analyses evidenced that HTy aromatic rings are able to interact with each other leading to a supra-macromolecular re-arrangement and decrease the copolymer size in water. All copolymers showed good antioxidant activity and Fe(2+) chelating ability. Cytotoxicity and hemolytic tests evidenced that the amphiphilic balance, cationic charge density and polymer size in solution are key determinants for polymer biocompatibility. As for the antimicrobial properties, the lowest minimal inhibitory concentration (MIC = 40 μg/mL) against Staphylococcus epidermidis was shown by the water-soluble copolymer having the highest HTy molar content (0.3). This copolymer layered onto catheter surfaces was also able to prevent staphylococcal adhesion. This approach permits not only prevention of biofilm infections but also reduction of the risk of emergence of drug-resistant bacteria. Indeed, the combination of two active compounds in the same polymer can provide a synergistic action against biofilms and suppress reactive species oxygen (ROS), known to promote the occurrence of antibiotic resistance. PMID:25917843

  3. Block and Graft Copolymers of Polyhydroxyalkanoates

    NASA Astrophysics Data System (ADS)

    Marchessault, Robert H.; Ravenelle, François; Kawada, Jumpei

    2004-03-01

    Polyhydroxyalkanoates (PHAs) were modified for diblock copolymer and graft polymer by catalyzed transesterification in the melt and by chemical synthesis to extend the side chains of the PHAs, and the polymers were studied by transmission electron microscopy (TEM) X-ray diffraction, thermal analysis and nuclear magnetic resonance (NMR). Catalyzed transesterification in the melt is used to produce diblock copolymers of poly[3-hydroxybutyrate] (PHB) and monomethoxy poly[ethylene glycol] (mPEG) in a one-step process. The resulting diblock copolymers are amphiphilic and self-assemble into sterically stabilized colloidal suspensions of PHB crystalline lamellae. Graft polymer was synthesized in a two-step chemical synthesis from biosynthesized poly[3-hydroxyoctanoate-co-3-hydroxyundecenoate] (PHOU) containing ca. 25 mol chains. 11-mercaptoundecanoic acid reacts with the side chain alkenes of PHOU by the radical addition creating thioether linkage with terminal carboxyl functionalities. The latter groups were subsequently transformed into the amide or ester linkage by tridecylamine or octadecanol, respectively, producing new graft polymers. The polymers have different physical properties than poly[3-hydroxyoctanoate] (PHO) which is the main component of the PHOU, such as non-stickiness and higher thermal stability. The combination of biosynthesis and chemical synthesis produces a hybrid thermoplastic elastomer with partial biodegradability.

  4. Formation of Anisotropic Block Copolymer Gels

    NASA Astrophysics Data System (ADS)

    Liaw, Chya Yan; Shull, Kenneth; Henderson, Kevin; Joester, Derk

    2011-03-01

    Anisotropic, fibrillar gels are important in a variety of processes. Biomineralization is one example, where the mineralization process often occurs within a matrix of collagen or chitin fibers that trap the mineral precursors and direct the mineralization process. We wish to replicate this type of behavior within block copolymer gels. Particularly, we are interested in employing gels composed of cylindrical micelles, which are anisotropic and closely mimic biological fibers. Micelle geometry is controlled in our system by manipulating the ratio of molecular weights of the two blocks and by controlling the detailed thermal processing history of the copolymer solutions. Small-Angle X-ray Scattering and Dynamic Light Scattering are used to determine the temperature dependence of the gel formation process. Initial experiments are based on a thermally-reversible alcohol-soluble system, that can be subsequently converted to a water soluble system by hydrolysis of a poly(t-butyl methacrylate) block to a poly (methacrylic acid) block. MRSEC.

  5. An amphiphilic graft copolymer-based nanoparticle platform for reduction-responsive anticancer and antimalarial drug delivery.

    PubMed

    Najer, Adrian; Wu, Dalin; Nussbaumer, Martin G; Schwertz, Geoffrey; Schwab, Anatol; Witschel, Matthias C; Schäfer, Anja; Diederich, François; Rottmann, Matthias; Palivan, Cornelia G; Beck, Hans-Peter; Meier, Wolfgang

    2016-08-21

    Medical applications of anticancer and antimalarial drugs often suffer from low aqueous solubility, high systemic toxicity, and metabolic instability. Smart nanocarrier-based drug delivery systems provide means of solving these problems at once. Herein, we present such a smart nanoparticle platform based on self-assembled, reduction-responsive amphiphilic graft copolymers, which were successfully synthesized through thiol-disulfide exchange reaction between thiolated hydrophilic block and pyridyl disulfide functionalized hydrophobic block. These amphiphilic graft copolymers self-assembled into nanoparticles with mean diameters of about 30-50 nm and readily incorporated hydrophobic guest molecules. Fluorescence correlation spectroscopy (FCS) was used to study nanoparticle stability and triggered release of a model compound in detail. Long-term colloidal stability and model compound retention within the nanoparticles was found when analyzed in cell media at body temperature. In contrast, rapid, complete reduction-triggered disassembly and model compound release was achieved within a physiological reducing environment. The synthesized copolymers revealed no intrinsic cellular toxicity up to 1 mg mL(-1). Drug-loaded reduction-sensitive nanoparticles delivered a hydrophobic model anticancer drug (doxorubicin, DOX) to cancer cells (HeLa cells) and an experimental, metabolically unstable antimalarial drug (the serine hydroxymethyltransferase (SHMT) inhibitor (±)-1) to Plasmodium falciparum-infected red blood cells (iRBCs), with higher efficacy compared to similar, non-sensitive drug-loaded nanoparticles. These responsive copolymer-based nanoparticles represent a promising candidate as smart nanocarrier platform for various drugs to be applied to different diseases, due to the biocompatibility and biodegradability of the hydrophobic block, and the protein-repellent hydrophilic block. PMID:27452350

  6. Block copolymer compatibilization of cocontinuous polymer blends.

    SciTech Connect

    Galloway, Jeffrey A.; Macosko, Christopher W.; Bell, Joel R.; Jeon, Hyun K.

    2004-12-01

    The effect of block copolymers on the cocontinuous morphology of 50/50 (w/w) polystyrene (PS)/high density polyethylene (HDPE) blends was investigated using symmetric polystyrene-polyethylene block copolymers (PS-PE) with molecular weights varying from 6 to 200 kg/mol. The coarsening rate during annealing was compared to the Doi-Ohta theory. An intermediate molecular weight PS-PE, 40 kg/mol, showed remarkable results in reducing the phase size and stabilizing the blend morphology during annealing. Mixing small amounts of 6, 100 or 200 kg/mol PS-PE in the blend did not reduce the phase size significantly, but did decrease the coarsening rate during annealing. In stabilizing the morphology, 6 kg/mol PS-PE was inferior to 100 and 200 kg/mol. The existence of an optimal molecular weight block copolymer is due to a balance between the ability of the block copolymer to reach the interface and its relative stabilization effect at the interface.

  7. Microphase separation of block copolymer thin films.

    PubMed

    Zhang, Jilin; Yu, Xinhong; Yang, Ping; Peng, Juan; Luo, Chunxia; Huang, Weihuan; Han, Yanchun

    2010-04-01

    Today, high-ordered micro- and nano-patterned surfaces are widely used in many areas, such as in the preparation of super-thin dielectric films, photonic crystals, antireflective films, super-non-wetting surfaces, bio-compatible surfaces and microelectric devices. Considering the critical fabrication conditions and the irreducible high cost of the photolithography technique in patterning nano-scale structures (<100 nm), the development of other micro- and nano-patterning techniques that can be used to fabricate long-range ordered features - especially nanoscale arrays - is a promising subject in surface science. In contrast to the traditional photolithography patterning technique, block copolymers can spontaneously phase separate into arrays of periodic patterns with length-scales of 10-50 nm, which provides an efficient pathway to pattern nanoscale features. Today, preparing long-range ordered arrays by block copolymer microphase separation is one of the most promising techniques for the fabrication of nanoscale arrays, not only being a simple process but also having a lower cost than traditional methods. In this feature article, we first summarize the many techniques developed to induce ordering in the microphase separation of the block copolymer thin films. Then, evolution, order-order transitions and reversible switching microdomains are considered, since they are very important in the ordered engineering of microphase separation of the block copolymer thin films. Finally, the outlook of this research area will be given.

  8. Aqueous self-assembly of giant bottlebrush block copolymer surfactants as shape-tunable building blocks.

    PubMed

    Fenyves, Ryan; Schmutz, Marc; Horner, Ian J; Bright, Frank V; Rzayev, Javid

    2014-05-28

    Programmed self-assembly of well-defined molecular building blocks enables the fabrication of precisely structured nanomaterials. In this work, we explore a new class of giant polymeric surfactants (Mn = (0.7-4.4) × 10(6) g/mol) with bottlebrush architecture and show that their persistent molecular shape leads to the formation of uniform aggregates in a predictable manner. Amphiphilic bottlebrush block copolymers containing polylactide (PLA) and poly(ethylene oxide) (PEO) side chains were synthesized by a grafting-from method, and their self-assembly in aqueous environment was studied by cryogenic transmission electron microscopy. The produced micelle structures with varying interfacial curvatures and core radii (19-55 nm) boasted rod-like hydrophilic PEO brushes protruding from the hydrophobic PLA cores normal to the interface. Highly uniform spherical micelles with low dispersities were obtained from bottlebrush amphiphiles with packing parameters of ∼0.3, estimated from the polymer structural data. Long cylindrical micelles and other nonspherical aggregates were observed for the first time for compositionally less asymmetric bottlebrush surfactants. Critical micelle concentration values of 1 nM, measured for PEO-rich bottlebrush amphiphiles, indicated an enhanced thermodynamic stability of the produced micelle aggregates. Shape-dependent assembly of bottlebrush surfactants allows for the rational fabrication of a range of micelle structures in narrow morphological windows.

  9. Amphiphilic Surface Active Triblock Copolymers with Mixed Hydrophobic and Hydrophilic Side Chains for Tuned Marine Fouling-Release Properties

    SciTech Connect

    Park, D.; Weinman, C; Finlay, J; Fletcher, B; Paik, M; Sundaram, H; Dimitriou, M; Sohn, K; Callow, M; et al.

    2010-01-01

    Two series of amphiphilic triblock surface active block copolymers (SABCs) were prepared through chemical modification of two polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene ABC triblock copolymer precursors. The methyl ether of poly(ethylene glycol) [M{sub n} {approx} 550 g/mol (PEG550)] and a semifluorinated alcohol (CF{sub 3}(CF{sub 2}){sub 9}(CH{sub 2}){sub 10}OH) [F10H10] were attached at different molar ratios to impart both hydrophobic and hydrophilic groups to the isoprene segment. Coatings on glass slides consisting of a thin layer of the amphiphilic SABC deposited on a thicker layer of an ABA polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene thermoplastic elastomer were prepared for biofouling assays with algae. Dynamic water contact angle analysis, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) measurements were utilized to characterize the surfaces. Clear differences in surface structure were realized as the composition of attached side chains was varied. In biofouling assays, the settlement (attachment) of zoospores of the green alga Ulva was higher for surfaces incorporating a large proportion of the hydrophobic F10H10 side chains, while surfaces with a large proportion of the PEG550 side chains inhibited settlement. The trend in attachment strength of sporelings (young plants) of Ulva did not show such an obvious pattern. However, amphiphilic SABCs incorporating a mixture of PEG550 and F10H10 side chains performed the best. The number of cells of the diatom Navicula attached after exposure to flow decreased as the content of PEG550 to F10H10 side chains increased.

  10. Block copolymers for opto-electronics

    NASA Astrophysics Data System (ADS)

    Sun, Sam-Shajing; Fan, Zhen; Wang, Yiqing; Taft, Charles; Haliburton, James H.; Maaref, Shahin; Ledbetter, Abram J.; Bonner, Carl E.

    2004-05-01

    A D(donor)-B(bridge)-A(acceptor)-B(bridge)-type block copolymer system has been developed and preliminarily examined for potential opto-electronic photovoltaic functions. The unique feature of the device includes a primary DBAB-type block copolymer backbone, where D and A are conjugated donor and acceptor polymer blocks, and B is a non-conjugated and flexible chain, a π orbital stacked and conjugated chain self-assembled and ordered "secondary structure", and a donor/acceptor asymmetric layers sandwiched D/A columnar "tertiary structure". This structure is expected to improve photovoltaic power conversion efficiency significantly in comparison to most existing organic or polymeric donor/acceptor binary photovoltaic systems due to the reduction of "exciton loss", the "carrier loss", as well as the "photon loss" via three-dimensional space and energy level optimizations. Preliminary experimental results revealed better morphology and opto-electronic properties of DBAB vs. D/A blends.

  11. Rapid ordering of block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Majewski, Pawel W.; Yager, Kevin G.

    2016-10-01

    Block-copolymers self-assemble into diverse morphologies, where nanoscale order can be finely tuned via block architecture and processing conditions. However, the ultimate usage of these materials in real-world applications may be hampered by the extremely long thermal annealing times—hours or days—required to achieve good order. Here, we provide an overview of the fundamentals of block-copolymer self-assembly kinetics, and review the techniques that have been demonstrated to influence, and enhance, these ordering kinetics. We discuss the inherent tradeoffs between oven annealing, solvent annealing, microwave annealing, zone annealing, and other directed self-assembly methods; including an assessment of spatial and temporal characteristics. We also review both real-space and reciprocal-space analysis techniques for quantifying order in these systems.

  12. Regulating block copolymer phases via selective homopolymers

    SciTech Connect

    Yang, Shuang E-mail: eqchen@pku.edu.cn; Lei, Zhen; Hu, Nan; Chen, Er-Qiang E-mail: eqchen@pku.edu.cn; Shi, An-Chang

    2015-03-28

    The phase behavior of strongly segregated AB diblock copolymer and selective C homopolymer blends is examined theoretically using a combination of strong stretching theory (SST) and self-consistent field theory (SCFT). The C-homopolymer is immiscible with the B-blocks but strongly attractive with the A-blocks. The effect of homopolymer content on the order-order phase transitions is analyzed. It is observed that, for AB diblock copolymers with majority A-blocks, the addition of the C-homopolymers results in lamellar to cylindrical to spherical phase transitions because of the A/C complexation. For diblock copolymers with minor A-blocks, adding C-homopolymers leads to transitions from spherical or cylindrical morphology with A-rich core to lamellae to inverted cylindrical and spherical morphologies with B-rich core. The results from analytical SST and numerical SCFT are in good agreement within most regions of the phase diagram. But the deviation becomes more obvious when the composition of A-blocks is too small and the content of added C-homopolymers is large enough, where the SCFT predicts a narrow co-existence region between different ordered phases. Furthermore, it is found that the phase behavior of the system is insensitive to the molecular weight of C-homopolymer.

  13. Sulfonated Polymerized Ionic Liquid Block Copolymers.

    PubMed

    Meek, Kelly M; Elabd, Yossef A

    2016-07-01

    The successful synthesis of a new diblock copolymer, referred to as sulfonated polymerized ionic liquid (PIL) block copolymer, poly(SS-Li-b-AEBIm-TFSI), is reported, which contains both sulfonated blocks (sulfonated styrene: SS) and PIL blocks (1-[(2-acryloyloxy)ethyl]-3-butylimidazolium: AEBIm) with both mobile cations (lithium: Li(+) ) and mobile anions (bis(trifluoromethylsulfonyl)imide: TFSI(-) ). Synthesis consists of polymerization via reversible addition-fragmentation chain transfer, followed by post-functionalization reactions to covalently attach the imidazolium cations and sulfonic acid anions to their respective blocks, followed by ion exchange metathesis resulting in mobile Li(+) cations and mobile TFSI(-) anions. Solid-state films containing 1 m Li-TFSI salt dissolved in ionic liquid result in an ion conductivity of >1.5 mS cm(-1) at 70 °C, where small-angle X-ray scattering data indicate a weakly ordered microphase-separated morphology. These results demonstrate a new ion-conducting block copolymer containing both mobile cations and mobile anions. PMID:27125600

  14. Regulating block copolymer phases via selective homopolymers.

    PubMed

    Yang, Shuang; Lei, Zhen; Hu, Nan; Chen, Er-Qiang; Shi, An-Chang

    2015-03-28

    The phase behavior of strongly segregated AB diblock copolymer and selective C homopolymer blends is examined theoretically using a combination of strong stretching theory (SST) and self-consistent field theory (SCFT). The C-homopolymer is immiscible with the B-blocks but strongly attractive with the A-blocks. The effect of homopolymer content on the order-order phase transitions is analyzed. It is observed that, for AB diblock copolymers with majority A-blocks, the addition of the C-homopolymers results in lamellar to cylindrical to spherical phase transitions because of the A/C complexation. For diblock copolymers with minor A-blocks, adding C-homopolymers leads to transitions from spherical or cylindrical morphology with A-rich core to lamellae to inverted cylindrical and spherical morphologies with B-rich core. The results from analytical SST and numerical SCFT are in good agreement within most regions of the phase diagram. But the deviation becomes more obvious when the composition of A-blocks is too small and the content of added C-homopolymers is large enough, where the SCFT predicts a narrow co-existence region between different ordered phases. Furthermore, it is found that the phase behavior of the system is insensitive to the molecular weight of C-homopolymer. PMID:25833605

  15. Transport of Water in Semicrystalline Block Copolymer Membranes

    NASA Astrophysics Data System (ADS)

    Hallinan, Daniel; Oparaji, Onyekachi

    Poly(styrene)-block-poly(ethylene oxide) (PS- b-PEO) is a semicrystalline block copolymer (BCP) with interesting properties. It is mechanically tough, amphiphilic, and has a polar phase. The mechanical toughness is due to the crystallinity of PEO and the high glass transition temperature of PS, as well as the morphological structure of the BCP. The polymer has high CO2, water, and salt solubility that derive from the polar PEO component. Potential applications include CO2 separation, water purification, and lithium air batteries. In all of the aforementioned applications, water transport is an important parameter. The presence of water can also affect thermal and mechanical properties. Water transport and thermal and mechanical properties of a lamellar PS- b-PEO copolymer have been measured as a function of water activity. Water transport can be affected by the heterogeneous nature of a semicrystalline BCP. Therefore, Fourier transform infrared - attenuated total reflectance (FTIR-ATR) spectroscopy has been employed, because water transport and polymer swelling can be measured simultaneously. The effect of BCP structure on transport has been investigated by comparing water transport in PS- b-PEO to a PEO homopolymer. The crystalline content of the PEO and the presence of glassy PS lamellae will be used to explain the transport results.

  16. Influence of Architecture on the Behavior of Microphase Separated Block Copolymers

    NASA Astrophysics Data System (ADS)

    Speetjens, Frank W., II

    chemistry and physics of two other block copolymer systems are explored: (1) the self-assembly, thin film template fabrication, and post fabrication-template modification of reactive poly(styrene-b-vinyl dimethylazalactone) block copolymers, and (2) the synthesis and rheological characteristics of amphiphilic poly(vinyl alcohol)-based ABA triblock copolymer hydrogels.

  17. Real-time monitoring of the penetration of amphiphilic acrylate copolymer in leather using a fluorescent copolymer as tracer.

    PubMed

    Du, Jin-Xia; Shi, Lu; Peng, Bi-Yu

    2015-12-01

    A fluorescent tracer, poly (acrylic-co-stearyl acrylate-co-3-acryloyl fluorescein) [poly (AA-co-SA-co-Ac-Flu)], used for real-time monitoring the penetration of amphiphilic acrylate copolymer, poly (acrylic-co-stearyl acrylate) [poly (AA-co-SA)], in leather was synthesized by radical polymerization of acrylic, stearyl acrylate and fluorescent monomer, 3-acryloyl fluorescein (Ac-Flu). The structure, molecular weight, introduced fluorescent group content and fluorescent characteristics of the fluorescent tracer and target copolymer, amphiphilic acrylate copolymer, were also characterized. The results show that the tracer presents the similar structural characteristics to the target and enough fluorescence intensity with 1.68 wt % of the fluorescent monomer introduced amount. The vertical section of the leather treated with the target copolymer mixing with 7% of the tracer exhibits evident fluorescence, and the change of fluorescence intensity along with the vertical section with treating time increasing can reflect the penetration depth of the target copolymer. The introduction of the fluorescent group in polymer structure through copolymerization with a limited amount of fluorescent monomer, Ac-Flu, is an effective way to make a tracer to monitor the penetration of the target in leather, which provides a new thought for the penetration research of syntans such as vinyl copolymer materials in leather manufacture.

  18. Rod-Coil Block Polyimide Copolymers

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B. (Inventor); Kinder, James D. (Inventor)

    2005-01-01

    This invention is a series of rod-coil block polyimide copolymers that are easy to fabricate into mechanically resilient films with acceptable ionic or protonic conductivity at a variety of temperatures. The copolymers consist of short-rigid polyimide rod segments alternating with polyether coil segments. The rods and coil segments can be linear, branched or mixtures of linear and branched segments. The highly incompatible rods and coil segments phase separate, providing nanoscale channels for ion conduction. The polyimide segments provide dimensional and mechanical stability and can be functionalized in a number of ways to provide specialized functions for a given application. These rod-coil black polyimide copolymers are particularly useful in the preparation of ion conductive membranes for use in the manufacture of fuel cells and lithium based polymer batteries.

  19. Dynamics of Block Copolymer Nanocomposites

    SciTech Connect

    Mochrie, Simon G. J.

    2014-09-09

    A detailed study of the dynamics of cadmium sulfide nanoparticles suspended in polystyrene homopolymer matrices was carried out using X-ray photon correlation spectroscopy for temperatures between 120 and 180 °C. For low molecular weight polystyrene homopolymers, the observed dynamics show a crossover from diffusive to hyper-diffusive behavior with decreasing temperatures. For higher molecular weight polystyrene, the nanoparticle dynamics appear hyper-diffusive at all temperatures studied. The relaxation time and characteristic velocity determined from the measured hyper-diffusive dynamics reveal that the activation energy and underlying forces determined are on the order of 2.14 × 10-19 J and 87 pN, respectively. We also carried out a detailed X-ray scattering study of the static and dynamic behavior of a styrene– isoprene diblock copolymer melt with a styrene volume fraction of 0.3468. At 115 and 120 °C, we observe splitting of the principal Bragg peak, which we attribute to phase coexistence of hexagonal cylindrical and cubic double- gyroid structure. In the disordered phase, above 130 °C, we have characterized the dynamics of composition fluctuations via X-ray photon correlation spectroscopy. Near the peak of the static structure factor, these fluctuations show stretched-exponential relaxations, characterized by a stretching exponent of about 0.36 for a range of temperatures immediately above the MST. The corresponding characteristic relaxation times vary exponentially with temperature, changing by a factor of 2 for each 2 °C change in temperature. At low wavevectors, the measured relaxations are diffusive with relaxation times that change by a factor of 2 for each 8 °C change in temperature.

  20. Synthesis and Characterization of Stimuli Responsive Block Copolymers, Self-Assembly Behavior and Applications

    SciTech Connect

    Determan, Michael Duane

    2005-12-17

    The central theme of this thesis work is to develop new block copolymer materials for biomedical applications. While there are many reports of stimuli-responsive amphiphilic [19-21] and crosslinked hydrogel materials [22], the development of an in situ gel forming, pH responsive pentablock copolymer is a novel contribution to the field, Figure 1.1 is a sketch of an ABCBA pentablock copolymer. The A blocks are cationic tertiary amine methacrylates blocked to a central Pluronic F127 triblock copolymer. In addition to the prerequisite synthetic and macromolecular characterization of these new materials, the self-assembled supramolecular structures formed by the pentablock were experimentally evaluated. This synthesis and characterization process serves to elucidate the important structure property relationships of these novel materials, The pH and temperature responsive behavior of the pentablock copolymer were explored especially with consideration towards injectable drug delivery applications. Future synthesis work will focus on enhancing and tuning the cell specific targeting of DNA/pentablock copolymer polyplexes. The specific goals of this research are: (1) Develop a synthetic route for gel forming pentablock block copolymers with pH and temperature sensitive properties. Synthesis of these novel copolymers is accomplished with ATRP, yielding low polydispersity and control of the block copolymer architecture. Well defined macromolecular characteristics are required to tailor the phase behavior of these materials. (2) Characterize relationship between the size and shape of pentablock copolymer micelles and gel structure and the pH and temperature of the copolymer solutions with SAXS, SANS and CryoTEM. (3) Evaluate the temperature and pH induced phase separation and macroscopic self-assembly phenomenon of the pentablock copolymer. (4) Utilize the knowledge gained from first three goals to design and formulate drug delivery formulations based on the multi

  1. Synthesis of carboxylic block copolymers via reversible addition fragmentation transfer polymerization for tooth erosion prevention.

    PubMed

    Lei, Y; Wang, T; Mitchell, J W; Qiu, J; Kilpatrick-Liverman, L

    2014-12-01

    Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA block copolymers was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Their structures were characterized by gel permeation chromatography (GPC) and (1)H nuclear magnetic resonance (NMR) spectra. The molar fractions of acrylic acid (AA) in the final block copolymer were finely controlled from 0.25 to 0.94, and the molecular weight (Mn) of PMMA-b-PAA was controlled from 10 kDa to 90 kDa. The binding capability of the block copolymer with hydroxyapatite (HAP) was investigated by ultraviolet-visible spectroscopy (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. FTIR spectra confirmed that the PMMA-b-PAA block copolymer could bind to HAP via bridging bidentate bonds. Both UV-Vis and FTIR spectra additionally indicated that a high polymer concentration and low solution pH favored the polymer binding to HAP. The erosion-preventing efficacy of the PMMA-b-PAA block copolymer in inhibiting HAP mineral loss was quantitatively evaluated by atomic absorption spectroscopy (AAS). Based on the results, polymer treatment reduced the amount of calcium released by 27% to 30% in comparison with the unprotected samples. Scanning electron microscope (SEM) observations indicated that PMMA-b-PAA polymer treatment protected enamel from acid erosion. This new amphiphilic block copolymer has significant potential to be integrated into dentifrices or mouthrinses as an alternative non-fluoride ingredient to reduce tooth erosion.

  2. Synthesis of Carboxylic Block Copolymers via Reversible Addition Fragmentation Transfer Polymerization for Tooth Erosion Prevention

    PubMed Central

    Lei, Y.; Wang, T.; Mitchell, J.W.; Qiu, J.; Kilpatrick-Liverman, L.

    2014-01-01

    Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA block copolymers was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Their structures were characterized by gel permeation chromatography (GPC) and 1H nuclear magnetic resonance (NMR) spectra. The molar fractions of acrylic acid (AA) in the final block copolymer were finely controlled from 0.25 to 0.94, and the molecular weight (Mn) of PMMA-b-PAA was controlled from 10 kDa to 90 kDa. The binding capability of the block copolymer with hydroxyapatite (HAP) was investigated by ultraviolet–visible spectroscopy (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. FTIR spectra confirmed that the PMMA-b-PAA block copolymer could bind to HAP via bridging bidentate bonds. Both UV-Vis and FTIR spectra additionally indicated that a high polymer concentration and low solution pH favored the polymer binding to HAP. The erosion-preventing efficacy of the PMMA-b-PAA block copolymer in inhibiting HAP mineral loss was quantitatively evaluated by atomic absorption spectroscopy (AAS). Based on the results, polymer treatment reduced the amount of calcium released by 27% to 30% in comparison with the unprotected samples. Scanning electron microscope (SEM) observations indicated that PMMA-b-PAA polymer treatment protected enamel from acid erosion. This new amphiphilic block copolymer has significant potential to be integrated into dentifrices or mouthrinses as an alternative non-fluoride ingredient to reduce tooth erosion. PMID:25248611

  3. Synthesis, Characterization and Preliminary Biological Evaluation of P(HPMA)-b-P(LLA) Copolymers: A New Type of Functional Biocompatible Block Copolymer.

    PubMed

    Barz, Matthias; Wolf, Florian K; Canal, Fabiana; Koynov, Kaloian; Vicent, Maria J; Frey, Holger; Zentel, Rudolf

    2010-09-01

    We describe a synthetic pathway to functional P(HPMA)-b-P(LLA) block copolymers. The synthesis relies on a combination of ring-opening polymerization of L-lactide, conversion into a chain transfer agent (CTA) for the RAFT polymerization of pentafluorophenyl methacrylate. A series of block copolymers was prepared that exhibited molecular weights $\\overline M _{\\rm n}$ ranging from 7 600 to 34 300 g · mol(-1) , with moderate PDI between 1.3 and 1.45. These reactive precursor polymers have been transformed into biocompatible P(HPMA)-b-P(LLA) copolymers and their fluorescently labeled derivatives by facile replacement of the pentafluorophenyl groups. The fluorescence label attached to this new type of a partially degradable amphiphilic block copolymer was used to study cellular uptake in human cervix adenocarcinoma (HeLa) cells as well as aggregation behavior by fluorescence correlation spectroscopy (FCS).

  4. Cavitation in block copolymer modified epoxy

    NASA Astrophysics Data System (ADS)

    Declet-Perez, Carmelo; Francis, Lorraine; Bates, Frank

    2013-03-01

    Today, brittleness in epoxy networks limits most commercial applications. Significant toughness can be imparted by adding small amounts of micelle forming block copolymers (BCP) without compromising critical properties such as high use temperature and modulus. Curing the network locks in the self-assembled BCP micellar structures formed in the monomer resin providing control of the resulting morphology. Despite significant research over the last decade, a complete description of the parameters influencing toughness in block copolymer modified epoxies is still lacking. In this presentation we compare the ultimate mechanical behavior of epoxies modified with spherical micelle forming BCP's containing rubbery and glassy cores using real-time in-situ small-angle X-ray scattering (SAXS) performed during tensile deformation. Striking differences in the 2D SAXS patterns were documented for epoxies modified with rubbery (PEP) versus glassy (PS) micelle cores. Rubbery cores dilate by 100% in volume upon specimen yielding, while the glassy micelle cores deform at approximately constant volume. These results provide direct evidence of a cavitation mediated mechanism for toughness in block copolymer modified epoxies. We further interpret characteristic butterfly features in the 2D SAXS patterns in terms of epoxy network deformation. Support was provided by the NSF sponsored MRSEC at the University of Minnesota

  5. Engineering topochemical polymerizations using block copolymer templates.

    PubMed

    Zhu, Liangliang; Tran, Helen; Beyer, Frederick L; Walck, Scott D; Li, Xin; Agren, Hans; Killops, Kato L; Campos, Luis M

    2014-09-24

    With the aim to achieve rapid and efficient topochemical polymerizations in the solid state, via solution-based processing of thin films, we report the integration of a diphenyldiacetylene monomer and a poly(styrene-b-acrylic acid) block copolymer template for the generation of supramolecular architectural photopolymerizable materials. This strategy takes advantage of non-covalent interactions to template a topochemical photopolymerization that yields a polydiphenyldiacetylene (PDPDA) derivative. In thin films, it was found that hierarchical self-assembly of the diacetylene monomers by microphase segregation of the block copolymer template enhances the topochemical photopolymerization, which is complete within a 20 s exposure to UV light. Moreover, UV-active cross-linkable groups were incorporated within the block copolymer template to create micropatterns of PDPDA by photolithography, in the same step as the polymerization reaction. The materials design and processing may find potential uses in the microfabrication of sensors and other important areas that benefit from solution-based processing of flexible conjugated materials. PMID:25208609

  6. Effect of Ternary Solutes on the Evolution of Structure and Gel Formation in Amphiphilic Copolymer Solutions

    NASA Astrophysics Data System (ADS)

    Meznarich, Norman Anthony Kang

    Aqueous solutions of polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) amphiphilic triblock copolymers (commercially known as Pluronic surfactants) undergo reversible and temperature-dependent micellization and arrangement into cubic ordered lattices known as "micelle gels". The macroscopic behavior of the ordering is a transition from a liquid to a gel. While the phase behavior and gel structure of pure Pluronic surfactant solutions have been well studied, less is known about the effects of added ternary solutes. In this dissertation, a comprehensive investigation into the effects of the added pharmaceutical methylparaben on solutions of F127 ranging from 10 to 30 wt% was conducted in order to better understand the behavior of F127 in multicomponent pharmaceutical formulations. The viscoelastic properties of F127 gel formation were studied using rheometry, where heating rates of 0.1, 1, and 10 degrees C/min were also used to probe the kinetics of the gel transition. In solutions containing methylparaben, F127 gelation occurred at up to 15 degrees C lower temperatures and was accelerated by a factor of three to four. Small angle x-ray scattering (SAXS) was used to characterize the structure of the ordered domains, and how they were affected by the presence of dissolved pharmaceuticals. It was found that ordered domain formation changed from heterogeneous nucleation and growth to possible homogeneous nucleation and growth. A roughly 2% reduction in the cubic lattice parameter was also observed for solutions containing methylparaben. Differential scanning calorimetry (DSC) experiments were performed on a series of different Pluronic surfactants in order to characterize the micellization behavior as a function of PPO center block length and PEO/PPO ratio. Added methylparaben suppressed the micellization endotherm, the degree of suppression depending linearly on the amount of added methylparaben, as well as the length of the PPO center block and PEO

  7. Phase Transitions in Thin Block Copolymer Films

    SciTech Connect

    Kramer, Edward J.

    2010-10-08

    David Turnbull's experiments and theoretical insights paved the way for much of our modern understanding of phase transitions in materials. In recognition of his contributions, this lecture will concentrate on phase transitions in a material system not considered by Turnbull, thin diblock copolymer films. Well-ordered block copolymer films are attracting increasing interest as we attempt to extend photolithography to smaller dimensions. In the case of diblock copolymer spheres, an ordered monolayer is hexagonal, but the ordered bulk is body-centered cubic (bcc). There is no hexagonal plane in the bcc structure, so a phase transition must occur as n, the number of layers of spheres in the film, increases. How this phase transition occurs with n and how it can be manipulated is the subject of the first part of my presentation. In the second part of the talk, I show that monolayers of diblock copolymer spheres and cylinders undergo order-to-disorder transitions that differ greatly from those of the bulk. These ordered 2D monolayers are susceptible to phonon-generated disorder as well as to thermal generation of defects, such as dislocations, which, while they are line defects in 3D, are point defects in 2D. The results are compared to the theories of melting of 2D crystals (spheres) and of 2D smectic liquid crystals (cylinders), a comparison that will allow us to understand most, but not all, of the features of these order-disorder transitions that occur as the temperature is increased.

  8. Reduction-responsive cholesterol-based block copolymer vesicles for drug delivery.

    PubMed

    Jia, Lin; Cui, Di; Bignon, Jérôme; Di Cicco, Aurelie; Wdzieczak-Bakala, Joanna; Liu, Jianmiao; Li, Min-Hui

    2014-06-01

    We developed a new robust reduction-responsive polymersome based on the amphiphilic block copolymer PEG-SS-PAChol. The stability and robustness were achieved by the smectic physical cross-linking of cholesterol-containing liquid crystal polymer PAChol in the hydrophobic layer. The reduction-sensitivity was introduced by the disulfide bridge (-S-S-) that links the hydrophilic PEG block and the hydrophobic PAChol block. We used a versatile synthetic strategy based on atom transfer radical polymerization (ATRP) to synthesize the reduction-responsive amphiphilic block copolymers. The reductive cleavage of the disulfide bridge in the block copolymers was first evidenced in organic solution. The partial destruction of PEG-SS-PAChol polymersomes in the presence of a reducing agent was then demonstrated by cryo-electron microscopy. Finally, the calcein release from PEG-SS-PAChol polymersomes triggered by glutathione (GSH) was observed both in PBS suspension and in vitro inside the macrophage cells. High GSH concentrations (≥35 mM in PBS or artificially enhanced in macrophage cells by GSH-OEt pretreatment) and long incubation time (in the order of hours) were, however, necessary to get significant calcein release. These polymersomes could be used as drug carriers with very long circulation profiles and slow release kinetics. PMID:24801808

  9. Improved surface property of PVDF membrane with amphiphilic zwitterionic copolymer as membrane additive

    NASA Astrophysics Data System (ADS)

    Li, Jian-Hua; Li, Mi-Zi; Miao, Jing; Wang, Jia-Bin; Shao, Xi-Sheng; Zhang, Qi-Qing

    2012-06-01

    An attempt to improve hydrophilicity and anti-fouling properties of PVDF membranes, a novel amphiphilic zwitterionic copolymer poly(vinylidene fluoride)-graft-poly(sulfobetaine methacrylate) (PVDF-g-PSBMA) was firstly synthesized by atom transfer radical polymerization (ATRP) and used as amphiphilic copolymer additive in the preparation of PVDF membranes. The PVDF-g-PSBMA/PVDF blend membranes were prepared by immersion precipitation process. Fourier transform infrared attenuated reflection spectroscopy (FTIR-ATR) and X-ray photoelectronic spectroscopy (XPS) measurements confirmed that PSBMA brushes from amphiphilic additives were preferentially segregated to membrane-coagulant interface during membrane formation. The morphology of membranes was characterized by scanning electron microscopy (SEM). Water contact angle measurements showed that the surface hydrophilicity of PVDF membranes was improved significantly with the increasing of amphiphilic copolymer PVDF-g-PSBMA in cast solution. Protein static adsorption experiment and dynamic fouling resistance experiment revealed that the surface enrichment of PSBMA brush endowed PVDF blend membrane great improvement of surface anti-fouling ability.

  10. Concentration Dependent Structure of Block Copolymer Solutions

    NASA Astrophysics Data System (ADS)

    Choi, Soohyung; Bates, Frank S.; Lodge, Timothy P.

    2015-03-01

    Addition of solvent molecules into block copolymer can induce additional interactions between the solvent and both blocks, and therefore expands the range of accessible self-assembled morphologies. In particular, the distribution of solvent molecules plays a key role in determining the microstructure and its characteristic domain spacing. In this study, concentration dependent structures formed by poly(styrene-b-ethylene-alt-propylene) (PS-PEP) solution in squalane are investigated using small-angle X-ray scattering. This reveals that squalane is essentially completely segregated into the PEP domains. In addition, the conformation of the PS block changes from stretched to nearly fully relaxed (i.e., Gaussian conformation) as amounts of squalane increases. NRF

  11. Synthesis of zwitterionic polymer-based amphiphilic triblock copolymers by atom transfer radical polymerization for production of extremely stable nanoemlusions

    NASA Astrophysics Data System (ADS)

    Lee, Jin Yong; Kim, Ji Eun; Kim, Jin Woong

    2015-03-01

    In fields of soft matter, there have been growing interests in utilizing amphiphilic block copolymers due to their intriguing properties, such as surface activity as well as self-assembly. In this work, we synthesize a series of poly (2-(methacryloyloxy) ethyl phosphorylcholine)- b-poly (ɛ-caprolactone)- b-poly (2-(methacryloyloxy) ethyl phosphorylcholine) (PMPC- b-PCL- b-PMPC) triblock copolymers by using atom transfer radical polymerization (ATRP). We have a particular interest in using poly (2-(methacryloyloxy) ethyl phosphorylcholine) (PMPC) as a hydrophilic block, since it can have both electrostatic repulsion and steric repulsion in complex fluid systems. Assembling them at the oil-water interface by using the phase inversion method enables production of highly stable nanoemulsions. From the analyses of the crystallography and self-assembly behavior, we have found that the triblock copolymers assemble to form a flexible but tough molecular thin film at the interface, which is essential for the remarkable improvement in the emulsion stability.

  12. Structure and Properties of Block Copolymers of Polystyrene and Polybutadiene

    NASA Astrophysics Data System (ADS)

    Askadskii, Andrei A.; Andryushchenko, T. A.; Zubov, P. I.

    1984-08-01

    Recent studies of the structure and properties of block copolymers of polystyrene and polybutadiene are reviewed, with special emphasis on the effect of the structure and of the formation conditions for the samples on the interrelated physico-mechanical properties. Problems associated with the macro- and micro-layering of block copolymer solutions are examined in detail. Work on the analysis of block copolymer structures from measurements of sorption characteristics is reviewed in the light of an assumed relaxation mechanism for the sorption and swelling processes. The prospects of controlling the structure and properties of block copolymers are shown to be good. The bibliography contains 190 references.

  13. Multi-block copolymers in thin films.

    NASA Astrophysics Data System (ADS)

    Maniadis, Panagiotis; Kober, Edward; Lookman, Turab

    2008-03-01

    We study the behavior of an ABn multi-block copolymer confined to a thin film, using self consistent field theory (SCFT) methods. Due to the breaking of symmetry in the direction of confinement, the propagators do not obey the usual diffusion equation. We derive the diffusion equation which correctly describes the confined polymer system and find that it differs from the original in an area which is approximately 3 times the Kuhn length of the polymer, close to the surface of the film. We use the modified diffusion equation to study the structure of the confined polymer.

  14. Synthesis of hybrid gold/iron oxide nanoparticles in block copolymer micelles for imaging, drug delivery and magnetic hyperthermia.

    SciTech Connect

    Kim, D.-H.; Rozhkova, E. A.; Rajh, T.; Bader, S. D.; Novosad, V.

    2009-10-01

    In our study, hybrid gold/iron oxide loaded thermoresponsive micelles were synthesized for combined hyperthermia and chemotherapy, and optical imaging. Polymeric micelles made of amphiphilic block copolymer of poly(N-isopropylacrylamide-co-acrylamide)-block-poly({var_epsilon}-caprolactone) were conjugated with gold/iron oxide particles which are self-assembled at the hydrophobic polymer core. Thermal sensitivity and magnetic and optical properties of the hybrid gold/iron oxide micelles were investigated for the combined therapy and optical imaging.

  15. "Non-equilibrium" block copolymer micelles with glassy cores: a predictive approach based on theory of equilibrium micelles.

    PubMed

    Nagarajan, Ramanathan

    2015-07-01

    Micelles generated in water from most amphiphilic block copolymers are widely recognized to be non-equilibrium structures. Typically, the micelles are prepared by a kinetic process, first allowing molecular scale dissolution of the block copolymer in a common solvent that likes both the blocks and then gradually replacing the common solvent by water to promote the hydrophobic blocks to aggregate and create the micelles. The non-equilibrium nature of the micelle originates from the fact that dynamic exchange between the block copolymer molecules in the micelle and the singly dispersed block copolymer molecules in water is suppressed, because of the glassy nature of the core forming polymer block and/or its very large hydrophobicity. Although most amphiphilic block copolymers generate such non-equilibrium micelles, no theoretical approach to a priori predict the micelle characteristics currently exists. In this work, we propose a predictive approach for non-equilibrium micelles with glassy cores by applying the equilibrium theory of micelles in two steps. In the first, we calculate the properties of micelles formed in the mixed solvent while true equilibrium prevails, until the micelle core becomes glassy. In the second step, we freeze the micelle aggregation number at this glassy state and calculate the corona dimension from the equilibrium theory of micelles. The condition when the micelle core becomes glassy is independently determined from a statistical thermodynamic treatment of diluent effect on polymer glass transition temperature. The predictions based on this "non-equilibrium" model compare reasonably well with experimental data for polystyrene-polyethylene oxide diblock copolymer, which is the most extensively studied system in the literature. In contrast, the application of the equilibrium model to describe such a system significantly overpredicts the micelle core and corona dimensions and the aggregation number. The non-equilibrium model suggests ways to

  16. Nanophase separation in polystyrene-polyfluorene block copolymers thin films prepared through the breath figure procedure.

    PubMed

    Bolognesi, Alberto; Galeotti, Francesco; Giovanella, Umberto; Bertini, Fabio; Yunus, Sami

    2009-05-01

    The amphiphilic block copolymer formed by a hydrophobic body of polystyrene and a hydrophilic head of poly[9,9-di(2-(2-tetrahydropyranyl-oxy)hexyl)fluorene-alt-9,9-dioctylfluorene] was synthesized, and its solution was used to create thin films with ordered pattern of holes, by means of the breath figure technique. These porous films, after a thermal treatment, were found to show ordered aggregates of the pi-conjugated blocks in the place of the cavities. This is probably due to a preorganization of the two different blocks of the copolymer occurring during the breath figure formation, which is driven by the condensation of water microdroplets on the polymer solution, and to a following phase segregation occurring during the thermal annealing. This approach is a promising tool to be employed for the organization of organic materials at the micro and nanoscale.

  17. Log-rolling block copolymers cylinders

    NASA Astrophysics Data System (ADS)

    Kim, So Youn; Kim, Ye Chan; Kim, Dong Hyup; Kwon, Na Kyung; Register, Richard A.

    Shear has been the most effective method to create long range order of micro- or nano- structures in soft materials. When shear is applied, soft particles or polymers tend to align along the shear direction to minimize the viscous dissipation, thus transverse (so-called ``log-rolling'') alignment is unfavored. In this study, for the first time we report the transverse alignment of cylinder-forming block copolymers. Poly(styrene-b-methyl methacrylate), PS-PMMA, can form a metastable hemicylinder structure when confined in a thin film, and this hemicylinder structure can align either along the shear direction, or transverse to the shear direction (``log-rolling''), depending on the shearing temperature. This unusual ``log-rolling'' behavior is explained by the different chain mobility of the two blocks in PS-PMMA; the rigidity of core cylinder is the critical parameter determining the direction of shear alignment.

  18. Correlated disorder in random block copolymers

    NASA Astrophysics Data System (ADS)

    Westfahl, Harry, Jr.; Schmalian, Jörg

    2005-07-01

    We study the effect of a random Flory-Huggins parameter in a symmetric diblock copolymer melt which is expected to occur in a copolymer where one block is near its structural glass transition. In the clean limit the microphase segregation between the two blocks causes a weak, fluctuation induced first order transition to a lamellar state. Using a renormalization group approach combined with the replica trick to treat the quenched disorder, we show that beyond a critical disorder strength, which depends on the length of the polymer chain, the character of the transition is changed. The system becomes dominated by strong randomness and a glassy rather than an ordered lamellar state occurs. A renormalization of the effective disorder distribution leads to nonlocal disorder correlations that reflect strong compositional fluctuation on the scale of the radius of gyration of the polymer chains. The reason for this behavior is shown to be the chain length dependent role of critical fluctuations, which are less important for shorter chains and become increasingly more relevant as the polymer length increases and the clean first order transition becomes weaker.

  19. Synthesis of non-polar/hydrogen bonding block copolymers

    NASA Astrophysics Data System (ADS)

    Montgomery, Steven J.

    Methods for the synthesis of novel block copolymers consisting of a non-polar segment and a hydrogen bonding segment were developed using a combination of living polymerization techniques. A series of well defined block copolymers was synthesized consisting of polybutadiene-block-poly(t-butyldimethylsilyloxystyrene), polybutadiene-block-poly(p-acetoxystyrene) and polybutadiene-block-poly(methyl methacrylate). The block copolymers containing t-butyldimethylsilyloxystyrene and p-acetoxystyrene may be deprotected to yield polybutadiene-block-poly(4-hydroxystyrene). Specifically, non-polar/hydrogen bonding (NP/HB) block copolymers were synthesized via two routes. The first consisted of anionic polymerization. The second involved a mechanistic transformation technique comprised of anionic and atom transfer radical polymerization techniques. The mechanistic transformation route was determined to be the superior method with regard to the molecular weight of the polymers produced, the abundance of compatible monomers, and the facile nature of the reaction technique.

  20. Piezoelectric Properties of Non-Polar Block Copolymers

    SciTech Connect

    Pester, Christian; Ruppel, Markus A; Schoberth, Heiko; Schmidt, K.; Liedel, Clemens; Van Rijn, Patrick; Littrell, Ken; Schindler, Kerstin; Hiltl, Stephanie; Czubak, Thomas; Mays, Jimmy; Urban, Volker S; Boker, Alexander

    2011-01-01

    Piezoelectric properties in non-polar block copolymers are a novelty in the field of electroactive polymers. The piezoelectric susceptibility of poly(styrene-b-isoprene) block copolymer lamellae is found to be up to an order of magnitude higher when compared to classic piezoelectric materials. The electroactive response increases with temperature and is found to be strongest in the disordered phase.

  1. Solvent enhanced block copolymer ordering in thin films

    NASA Astrophysics Data System (ADS)

    Misner, Matthew J.

    Diblock copolymer self-assembly of materials is emerging as a key element in the fabrication of functional nanostructured materials. By solvent casting or solvent annealing block copolymer thin films, we have demonstrated methods to produce diblock copolymer films with highly oriented, close-packed arrays of nanoscopic cylindrical domains with a high degree of long-range lateral order with few defects. The solvent imparts a high degree of mobility in the microphase-separated copolymer that enables a rapid removal of defects and a high degree of lateral order. Though the use of a selective cosolvent during solvent casting, it was found that the microdomain size and spacing could be increased, leading to a size-tunable system. Additionally, the presence of water also led to the ability to control the microdomain orientation during solvent annealing. Ionic complexation within cylinder-forming PS- b-EO block copolymer thin films was also investigated, where added salts bind PEO block as the minor component. Small amounts of added salts, on the order a few ions per chain, show large effects on the ordering of the copolymer films during solvent annealing. By using gold or cobalt salts, well-organized patterns of nanoparticles can be generated in the copolymer microdomains. Topographically and chemically patterned surfaces were used as a route to sectorizing and controlling the lattice orientation of copolymer films. Topographically patterned surfaces allow well-defined boundaries to confine the copolymer microdomains on a surface and effectively direct the ordering and grain orientation of the copolymer microdomains. Chemically patterned surfaces provide a route to direct the block copolymer ordering on completely flat surface, which may have advantages in applications where adding additional topography may be undesirable. To generate nanoporous templates from PS-b-PEO bases materials several routs were followed. The first route was through the addition and selective

  2. Micelles, Lamellaes and Connected Bilayer Membranes in Block Copolymer Melts, Blends and Solutions

    NASA Astrophysics Data System (ADS)

    Mortensen, Kell

    1997-03-01

    Block copolymers of poly(ethylene oxide), PEO, and poly(propylene oxide), PPO, provide a unique model system for studies of aqueous systems of amphilic macromolecules, as the amphiphilic character can be changed continuously by changing temperature(K Mortensen, W Brown, B. Nordén , Phys. Rev. Letters 13 2340 (1992)) or pressure(K Mortensen, D Schwahn S Janssen Phys. Rev. Letters 71 1728 (1993)). The structural characteristics of aqueous solutions of the PEO-PPO-PEO copolymers and their self-associated assemblies are reviewed(K Mortensen, J. Phys. Cond. Matter 8 A103 (1996)). It is shown by small-angle neutron scattering that at low temperatures and/or concentration the individual copolymers exist in solution as individual unimers. Depending on molecular design, i.e. size of the individual blocks, various aggregates are formed, including spherical, worm-like and disc-shaped micelles. The spherical micelles provide the basis for liquid-crystalline mesophases of cubic structure. The crystallization can be understood as a simple hard-sphere condensation. Worm- or rod-like micelles may form nematic or hexagonally ordered structures, whereas the discs may condense into lamellar phases. While bi-continuous microemulsions frequently appear in ternary phase diagrams of oil, water and low-molecular surfactants, there has only recently been observations of such phases in binary systems of block copolymers and solvent. The first observation was made in an aqueous solution of a low PEO-content PEO-PPO-PEO triblock copolymer(E Hecht, K Mortensen, H Hoffmann, Macromolecules 28 5465, 1995). More recently, the microemulsion sponge phase has been observed in a system of tri-block copolymers dissolved in homopolymers( JH Laurer, JC Fung, JW Sedat, DA Agard, SD Schmit, J Samseth, K Mortensen, RJ Spontak, Langmuir, submitted) and in a ternary systems of diblock copolymer and homopolymers(FS Bates, WW Maurer, PM Lipic MA Hillmyer, KA Almdal, K Mortensen, TP Lodge Science, submitted).

  3. Versatile antifouling polyethersulfone filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive.

    PubMed

    Zhao, Yi-Fan; Zhang, Pei-Bin; Sun, Jian; Liu, Cui-Jing; Yi, Zhuan; Zhu, Li-Ping; Xu, You-Yi

    2015-06-15

    Here we describe the development of versatile antifouling polyethersulfone (PES) filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive. Amphiphilic polyethersulfone-block-poly(2-hydroxyethyl methacrylate) (PES-b-PHEMA) was beforehand designed and used as the blending additive of PES membranes prepared by phase inversion technique. The surface enriched PHEMA blocks on membrane surface acted as an anchor to immobilize the initiating site. Poly(sulfobetaine methacrylate) (PSBMA) were subsequently grafted onto the PES blend membranes by surface-initiated atom transfer radical polymerization (SI-ATRP). The analysis of surface chemistry confirmed the successful grafting of zwitterionic PSBMA brushes on PES membrane surface. The resulted PES-g-PSBMA membranes were capable of separating proteins from protein solution and oil from oil/water emulsion efficiently. Furthermore, the modified membranes showed high hydrophilicity and strongly antifouling properties due to the incorporation of well-defined PSBMA layer. In addition, the PES-g-PSBMA membranes exhibited excellent blood compatibility and durability during the washing process. The developed antifouling PES membranes are versatile and can find their applications in protein filtration, blood purification and oil/water separation, etc. PMID:25752579

  4. Patchy micelles based on coassembly of block copolymer chains and block copolymer brushes on silica particles.

    PubMed

    Zhu, Shuzhe; Li, Zhan-Wei; Zhao, Hanying

    2015-04-14

    Patchy particles are a type of colloidal particles with one or more well-defined patches on the surfaces. The patchy particles with multiple compositions and functionalities have found wide applications from the fundamental studies to practical uses. In this research patchy micelles with thiol groups in the patches were prepared based on coassembly of free block copolymer chains and block copolymer brushes on silica particles. Thiol-terminated and cyanoisopropyl-capped polystyrene-block-poly(N-isopropylacrylamide) block copolymers (PS-b-PNIPAM-SH and PS-b-PNIPAM-CIP) were synthesized by reversible addition-fragmentation chain transfer polymerization and chemical modifications. Pyridyl disulfide-functionalized silica particles (SiO2-SS-Py) were prepared by four-step surface chemical reactions. PS-b-PNIPAM brushes on silica particles were prepared by thiol-disulfide exchange reaction between PS-b-PNIPAM-SH and SiO2-SS-Py. Surface micelles on silica particles were prepared by coassembly of PS-b-PNIPAM-CIP and block copolymer brushes. Upon cleavage of the surface micelles from silica particles, patchy micelles with thiol groups in the patches were obtained. Dynamic light scattering, transmission electron microscopy, and zeta-potential measurements demonstrate the preparation of patchy micelles. Gold nanoparticles can be anchored onto the patchy micelles through S-Au bonds, and asymmetric hybrid structures are formed. The thiol groups can be oxidized to disulfides, which results in directional assembly of the patchy micelles. The self-assembly behavior of the patchy micelles was studied experimentally and by computer simulation. PMID:25811763

  5. Light-emitting block copolymers composition, process and use

    DOEpatents

    Ferraris, John P.; Gutierrez, Jose J.

    2006-11-14

    Generally, and in one form, the present invention is a composition of light-emitting block copolymer. In another form, the present invention is a process producing a light-emitting block copolymers that intends polymerizing a first di(halo-methyl) aromatic monomer compound in the presence of an anionic initiator and a base to form a polymer and contacting a second di(halo-methyl) aromatic monomer compound with the polymer to form a homopolymer or block copolymer wherein the block copolymer is a diblock, triblock, or star polymer. In yet another form, the present invention is an electroluminescent device comprising a light-emitting block copolymer, wherein the electroluminescent device is to be used in the manufacturing of optical and electrical devices.

  6. Block Copolymer Templates for Optical Materials and Devices

    NASA Astrophysics Data System (ADS)

    Urbas, Augustine; Martin, Maldovan; Carter, W. C.; Thomas, E. L.; Fasolka, Michael; Fraser, Cassandra

    2002-03-01

    Block copolymers can act as super-lattices for creating novel optical structures. We have fabricated block copolymer photonic crystals from one, two and three dimensionally periodic systems and have enhanced their dielectric properties towards creating complete 3D band gaps. By using carefully selected blends of linear and star block copolymers, we are able to create hierarchical blends which exhibit precise molecular positioning of fluorescent molecules. We are exploring these unique patterning capabilities of block copolymer systems for the formation of ordered arrays of optically active components within a photonic crystal. Precise location of both fluorescent and nonlinear components within block copolymer photonic crystals affords new opportunities for creating low threshold, upconverting and array lasers as well as optical modulators and other photonic devices.

  7. Electric field induced selective disordering in lamellar block copolymers.

    PubMed

    Ruppel, Markus; Pester, Christian W; Langner, Karol M; Sevink, Geert J A; Schoberth, Heiko G; Schmidt, Kristin; Urban, Volker S; Mays, Jimmy W; Böker, Alexander

    2013-05-28

    External electric fields align nanostructured block copolymers by either rotation of grains or nucleation and growth depending on how strongly the chemically distinct block copolymer components are segregated. In close vicinity to the order-disorder transition, theory and simulations suggest a third mechanism: selective disordering. We present a time-resolved small-angle X-ray scattering study that demonstrates how an electric field can indeed selectively disintegrate ill-aligned lamellae in a lyotropic block copolymer solution, while lamellae with interfaces oriented parallel to the applied field prevail. The present study adds an additional mechanism to the experimentally corroborated suite of mechanistic pathways, by which nanostructured block copolymers can align with an electric field. Our results further unveil the benefit of electric field assisted annealing for mitigating orientational disorder and topological defects in block copolymer mesophases, both in close vicinity to the order-disorder transition and well below it. PMID:23573901

  8. Synthetic cell elements from block copolymers hydrodynamic aspectsÉléments de cellules synthétiques provenant de copolymères enbloc

    NASA Astrophysics Data System (ADS)

    Dalhaimer, Paul; Bates, Frank S.; Aranda-Espinoza, Helim; Discher, Dennis

    2003-03-01

    Amphiphilic block copolymers can self-assemble in water into various stable morphologies which resemble key cell structures, notably filaments and membranes. Filamentous 'worms' of copolymer, microns-long, are briefly introduced, and related dynamics of copolymer vesicle 'polymersomes' are reviewed. Fluorescence visualization of single worms stretched under flow demonstrates their stability as well as a means to control conformation. Polymersome membranes have been more thoroughly studied, especially copolymer molecular weight effects. We summarize results suggestive of a transition from Rouse-like behavior to entangled chains. Viewed together, the results ask the question: what physics are needed next to mimic cell activities such as crawling? To cite this article: P. Dalhaimer et al., C. R. Physique 4 (2003).

  9. Equilibrium and Kinetics of Block Copolymers Micelles

    NASA Astrophysics Data System (ADS)

    Mysona, Joshua; Morse, David

    Both equilibrium properties of micelles, such as the critical micelle concentration (CMC), and dynamical properties such as the micelle lifetime are difficult to study in simulations because of the slow dynamics of the processes by which micelles are created and destroyed. We first discuss a method of precisely identifying the CMC in a simple model of block copolymer micelles in a homopolymer matrix, which makes use of thermodynamic integration to compute the free energy of formation. We then examine the free energy barriers to competing mechanisms for creating and destroying micelles, which could occur predominantly either by a step-wise process involving insertion and extraction of single molecules or by fission and fusion of entire micelles.

  10. Antimicrobial films obtained from latex particles functionalized with quaternized block copolymers.

    PubMed

    Alvarez-Paino, Marta; Juan-Rodríguez, Rafael; Cuervo-Rodríguez, Rocío; Tejero, Rubén; López, Daniel; López-Fabal, Fátima; Gómez-Garcés, José L; Muñoz-Bonilla, Alexandra; Fernández-García, Marta

    2016-04-01

    New amphiphilic block copolymers with antimicrobial properties were obtained by atom transfer radical polymerization (ATRP) and copper catalyzed cycloaddition following two approaches, a simultaneous strategy or a two-step synthesis, which were proven to be very effective methods. These copolymers were subsequently quaternized using two alkyl chains, methyl and butyl, to amplify their antimicrobial properties and to investigate the effect of alkyl length. Antimicrobial experiments in solution were performed with three types of bacteria, two gram-positive and one gram-negative, and a fungus. Those copolymers quaternized with methyl iodide showed better selectivities on gram-positive bacteria, Staphylococcus aureus and Staphylococcus epidermidis, against red blood cells, demonstrating the importance of the quaternizing agent chosen. Once the solution studies were performed, we prepared poly(butyl methacrylate) latex particles functionalized with the antimicrobial copolymers by emulsion polymerization of butyl methacrylate using such copolymers as surfactants. The characterization by various techniques served to test their effectiveness as surfactants. Finally, films were prepared from these emulsions, and their antimicrobial activity was studied against the gram-positive bacteria. The results indicate that the antimicrobial efficiency of the films depends not only on the copolymer activity but also on other factors such as the surface segregation of the antimicrobial agent to the interface. PMID:26741269

  11. Thermodynamic and kinetic control of charged, amphiphilic triblock copolymer assembly via interaction with organic counterions in solvent mixtures

    NASA Astrophysics Data System (ADS)

    Cui, Honggang

    2007-12-01

    Amphiphilic block copolymers, consisting of at least two types of monomers with different affinity to the dissolving solvent(s), have been recognized as a molecular building unit for their chemical tunability and design flexibility. Amphiphilic block copolymers with a chargeable block have structural features of polyelectrolytes, block copolymers and surfactants. The combination of these different features offers great flexibility for developing novel assembled morphologies at the nanoscale and outstanding ability to control and manipulate those morphologies. The nanostructures, formed from the spontaneous association of amphiphilic block copolymer in selective solvents, show promise for applications in nanotechnology and pharmaceuticals, including drug delivery, tissue engineering and bio-imaging. A basic knowledge of their modes of self-assembly and their correspondence to application-related properties is just now being developed and poses a considerable scientific challenge. The goal of this dissertation is to investigate the associative behavior of charged, amphiphilic block copolymers in solvent mixtures while in the presence of organic counterions. Self-assembly of poly (acrylic acid)- block-poly (methyl acrylate)-block-polystyrene (PAA- b-PMA-b-PS) triblock copolymers produces nanodomains in THF/water solution specifically through the interaction with organic counterions (polyamines). These assembled structures can include classic micelles (spheres, cylinders and vesicles), but, more importantly, include non-classic micelles (disks, toroids, branched micelles and segmented micelles). Each micelle structure is stable and reproducible at different assembly conditions. The assembled micellar structures depend on not only solution components (thermodynamics) but also mixing procedure and consequent self-assembly pathway (kinetics). The key factors that determine the thermodynamic interactions that partially define the assembled structures and the kinetic

  12. TOPICAL REVIEW: Multifunctional nanoassemblies of block copolymers for future cancer therapy

    NASA Astrophysics Data System (ADS)

    Cabral, Horacio; Kataoka, Kazunori

    2010-02-01

    Nanoassemblies from amphiphilic block copolymers are promising nanomedicine platforms for cancer diagnosis and therapy due to their relatively small size, high loading capacity of drugs, controlled drug release, in vivo stability and prolonged blood circulation. Recent clinical trials with self-assembled polymeric micelles incorporating anticancer drugs have shown improved antitumor activity and decreased side effects encouraging the further development of nanoassemblies for drug delivery. This review summarizes recent approaches considering stimuli-responsive, multifunctionality and more advanced architectures, such as vesicles or worm-like micelles, for tumor-specific drug and gene delivery.

  13. Block copolymer adhesion promoters via ring-opening metathesis polymerization

    DOEpatents

    Kent, Michael S.; Saunders, Randall

    1997-01-01

    Coupling agents based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization.

  14. Chimeric lipid/block copolymer nanovesicles: Physico-chemical and bio-compatibility evaluation.

    PubMed

    Pippa, Natassa; Stellas, Dimitris; Skandalis, Athanasios; Pispas, Stergios; Demetzos, Costas; Libera, Marcin; Marcinkowski, Andrzej; Trzebicka, Barbara

    2016-10-01

    Chimeric systems are mixed nanovectors composed by different in nature materials and exhibit new functionalities and properties. The particular chimeric nanovectors, formed by the co-assembly of low and high molecular weight amphiphiles, have the potential to be utilized as drug delivery platforms. We have utilized two lipids, l-α-phosphatidylcholine, hydrogenated (Soy)(HSPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), and a poly(oligoethylene glycol acrylate)-b-poly(lauryl acrylate) (POEGA-PLA) block copolymer, at different molar ratios, in aqueous media. Light scattering, differential scanning calorimetry (DSC) and imaging techniques (cryo-TEM, AFM) were employed in order to elucidate the structure and properties of the nanostructures, as well as the cooperativity between the components. DSC experiments showed considerable interaction of the block copolymer with the lipid bilayers and suggested an inhomogeneous distribution of the copolymer chains and lateral phase separation of the components. Vesicle formation was observed in most cases by cryo-TEM with a chimeric membrane exhibiting kinks, in accordance with DSC data. A series of biocompatibility experiments indicated good in vitro biological stability and low cytotoxicity in vivo of the novel nanocarriers. Finally, ibuprofen (IBU) was used as model drug in order to study the loading and the release properties of the prepared chimeric lipid/block copolymer vesicles.

  15. Chimeric lipid/block copolymer nanovesicles: Physico-chemical and bio-compatibility evaluation.

    PubMed

    Pippa, Natassa; Stellas, Dimitris; Skandalis, Athanasios; Pispas, Stergios; Demetzos, Costas; Libera, Marcin; Marcinkowski, Andrzej; Trzebicka, Barbara

    2016-10-01

    Chimeric systems are mixed nanovectors composed by different in nature materials and exhibit new functionalities and properties. The particular chimeric nanovectors, formed by the co-assembly of low and high molecular weight amphiphiles, have the potential to be utilized as drug delivery platforms. We have utilized two lipids, l-α-phosphatidylcholine, hydrogenated (Soy)(HSPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), and a poly(oligoethylene glycol acrylate)-b-poly(lauryl acrylate) (POEGA-PLA) block copolymer, at different molar ratios, in aqueous media. Light scattering, differential scanning calorimetry (DSC) and imaging techniques (cryo-TEM, AFM) were employed in order to elucidate the structure and properties of the nanostructures, as well as the cooperativity between the components. DSC experiments showed considerable interaction of the block copolymer with the lipid bilayers and suggested an inhomogeneous distribution of the copolymer chains and lateral phase separation of the components. Vesicle formation was observed in most cases by cryo-TEM with a chimeric membrane exhibiting kinks, in accordance with DSC data. A series of biocompatibility experiments indicated good in vitro biological stability and low cytotoxicity in vivo of the novel nanocarriers. Finally, ibuprofen (IBU) was used as model drug in order to study the loading and the release properties of the prepared chimeric lipid/block copolymer vesicles. PMID:27519828

  16. Impact of starch content on protein adsorption characteristics in amphiphilic hybrid graft copolymers.

    PubMed

    Sengupta, Arijit; Linehan, Allison R; Iovine, Peter M

    2016-01-01

    Amphiphilic hybrid graft copolymers were synthesized using a graft-to methodology and their protein adsorption profiles studied. Three different hydrophilic side chains were studied: hydroxypropylated high amylose starch, maltodextrin, and polyethylene glycol (PEG). In the high amylose starch compositions, there was a pronounced decrease in protein adsorption with increasing polysaccharide content. As the starch content in the graft copolymers increased from 10 wt% to 53 wt%, BSA protein adsorption decreased by 83% whereas fibrinogen adsorption was reduced by 40%. Comparisons between the starch-containing hybrid polymers and their respective hydrophobic urethane-linked polyesters were also made. Hybrid 53, containing 53 wt% starch, showed a 85% reduction in BSA adsorption and 51% reduction in fibrinogen relative to their urethane-linked polyester backbone controls. Grafting branched high amylopectin-derived maltodextrin to the synthetic polymer backbones also conferred modest protein resistance to the hydrophobic backbone polymer. Lastly, it was found that a high amylose graft structure provided comparable, if not slightly more effective, protein resistance compared to a similarly constructed PEG-containing amphiphilic copolymer.

  17. Morphological studies on block copolymer modified PA 6 blends

    NASA Astrophysics Data System (ADS)

    Poindl, M.; Bonten, C.

    2014-05-01

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  18. Morphological studies on block copolymer modified PA 6 blends

    SciTech Connect

    Poindl, M. E-mail: christian.bonten@ikt.uni-stuttgart.de; Bonten, C. E-mail: christian.bonten@ikt.uni-stuttgart.de

    2014-05-15

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  19. Crystallization induced block copolymer assembly at curved liquid-liquid interface

    NASA Astrophysics Data System (ADS)

    Qi, Hao; Zhou, Tian; Zhou, Hao; Li, Christopher; Soft Materials Lab Team

    In a selected solvent, amphiphilic block copolymers can self-assemble into various micelle structures which find widespread applications in nanomedicine. Herein we report a directed assembly of poly (l-lactide acid)-b-poly (ethylene glycol) (PLLA-b-PEG) at curved oil/water interfaces. Oil droplets were dispersed in water phase upon sonication with amphiphilic PLLA-b-PEG as the surfactant. Subsequent crystallization of PLLA segments resulted in the formation of lamellasomes consisting of crystalline PLLA shell and densely-grafted (approx.1chain/nm2) PEG layer. The structure, morphology, and mechanical properties of these unique polymer ensembles were investigated using transmission electron microscopy and atomic force microscopy. Detailed formation mechanism will be discussed in detail.

  20. Nanopatterning of recombinant proteins and viruses using block copolymer templates

    NASA Astrophysics Data System (ADS)

    Cresce, Arthur Von Wald

    The study of interfaces is important in understanding biological interactions, including cellular signaling and virus infection. This thesis is an original effort to examine the interaction between a block copolymer and both a protein and a virus. Block copolymers intrinsically form nanometer-scale structures over large areas without expensive processing, making them ideal for the synthesis of the nanopatterned surfaces used in this study. The geometry of these nanostructures can be easily tuned for different applications by altering the block ratio and composition of the block copolymer. Block copolymers can be used for controlled uptake of metal ions, where one block selectively binds metal ions while the other does not. 5-norbornene-2,3-dicarboxylic acid is synthesized through ring-opening metathesis polymerization. It formed spherical domains with spheres approximately 30 nm in diameter, and these spheres were then subsequently loaded with nickel ion. This norbornene block copolymer was tested for its ability to bind histidine-tagged green fluorescent protein (hisGFP), and it was found that the nickel-loaded copolymer was able to retain hisGFP through chelation between the histidine tag and the metal-containing portions of the copolymer surface. Poly(styrene-b-4-vinylpyridine) (PS/P4VP) was also loaded with nickel, forming a cylindrical microstructure. The binding of Tobacco mosaic virus and Tobacco necrosis virus was tested through Tween 20 detergent washes. Electron microscopy allowed for observation of both block copolymer nanostructures and virus particles. Results showed that Tween washes could not remove bound Tobacco mosaic virus from the surface of PS/P4VP. It was also seen that the size and tunability of block copolymers and the lack of processing needed to attain different structures makes them attractive for many applications, including microfluidic devices, surfaces to influence cellular signaling and growth, and as a nanopatterning surface for

  1. Modification of nanofibrillated cellulose using amphiphilic block-structured galactoglucomannans.

    PubMed

    Lozhechnikova, Alina; Dax, Daniel; Vartiainen, Jari; Willför, Stefan; Xu, Chunlin; Österberg, Monika

    2014-09-22

    Nanofibrillated cellulose (NFC) and hemicelluloses have shown to be highly promising renewable components both as barrier materials and in novel biocomposites. However, the hydrophilic nature of these materials restricts their use in some applications. In this work, the usability of modified O-acetyl galactoglucomannan (GGM) for modification of NFC surface properties was studied. Four GGM-block-structured, amphiphilic derivatives were synthesized using either fatty acids or polydimethylsiloxane as hydrophobic tails. The adsorption of these GGM derivatives was consecutively examined in aqueous solution using a quartz crystal microbalance with dissipation monitoring (QCM-D). It was found that the hydrophobic tails did not hinder adsorption of the GGM derivatives to cellulose, which was concluded to be due to the presence of the native GGM-block with high affinity to cellulose. The layer properties of the adsorbed block-co-polymers were discussed and evaluated. Self-standing NFC films were further prepared and coated with the GGM derivatives and the effect of the surface modification on wetting properties and oxygen permeability (OP) of the modified films was assessed. PMID:24906743

  2. Poly(trimethylene carbonate)/Poly(malic acid) Amphiphilic Diblock Copolymers as Biocompatible Nanoparticles.

    PubMed

    Barouti, Ghislaine; Khalil, Ali; Orione, Clement; Jarnouen, Kathleen; Cammas-Marion, Sandrine; Loyer, Pascal; Guillaume, Sophie M

    2016-02-18

    Amphiphilic polycarbonate-poly(hydroxyalkanoate) diblock copolymers, namely, poly(trimethylene carbonate) (PTMC)-b-poly(β-malic acid) (PMLA), are reported for the first time. The synthetic strategy relies on commercially available catalysts and initiator. The controlled ring-opening polymerization (ROP) of trimethylene carbonate (TMC) catalyzed by the organic guanidine base 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), associated with iPrOH as an initiator, provided iPrO-PTMC-OH, which served as a macroinitiator in the controlled ROP of benzyl β-malolactonate (MLABe) catalyzed by the neodymium triflate salt (Nd(OTf)3). The resulting hydrophobic iPrO-PTMC-b-PMLABe-OH copolymers were then hydrogenolyzed into the parent iPrO-PTMC-b-PMLA-OH copolymers. A range of well-defined copolymers, featuring different sizes of segments (Mn,NMR up to 9300 g mol(-1) ; ÐM =1.28-1.40), were thus isolated in gram quantities, as evidenced by NMR spectroscopy, size exclusion chromatography, thermogravimetric analysis, differential scanning calorimetry, and contact angle analyses. Subsequently, PTMC-b-PMLA copolymers with different hydrophilic weight fractions (11-75 %) self-assembled in phosphate-buffered saline upon nanoprecipitation into well-defined nano-objects with Dh =61-176 nm, a polydispersity index <0.25, and a negative surface charge, as characterized by dynamic light scattering and zeta-potential analyses. In addition, these nanoparticles demonstrated no significant effect on cell viability at low concentrations, and a very low cytotoxicity at high concentrations only for PTMC-b-PMLA copolymers exhibiting hydrophilic fractions over 47 %, thus illustrating the potential of these copolymers as promising nanoparticles.

  3. Amphiphilic copolymer coated upconversion nanoparticles for near-infrared light-triggered dual anticancer treatment

    NASA Astrophysics Data System (ADS)

    Yang, Shun; Li, Najun; Liu, Zhuang; Sha, Wenwei; Chen, Dongyun; Xu, Qingfeng; Lu, Jianmei

    2014-11-01

    The light-triggered controlled release of anticancer drugs accompanied with NIR-responsive photodynamic therapy was prepared via a self-assembly process. Firstly, Mn2+-doped upconversion nanoparticles (UCNPs) were coated with a mesoporous silica shell and modified with photosensitizer (Chlorin e6) and long alkyl chains. And then the NIR light-responsive amphiphilic copolymer containing 9,10-dialkoxyanthracene groups was synthesized and then coated as the outermost layer. Upon irradiation with a 980 nm laser, the CCUCNPs@PM would absorb and then convert the NIR light to higher-energy visible red light (660 nm) via the UCNPs-based core, which could excite Chlorin e6 (Ce-6) to produce singlet oxygen (1O2). Then the 1O2-sensitive dialkoxyanthracene group in the amphiphilic copolymer would be degraded and detach from the surface of the CCUCNPs@PM, followed by the controlled release of the pre-loaded drugs and the photodynamic therapy for cancer cells caused by the excess 1O2. In vitro and in vivo experiments also demonstrated that the drug-loaded CCUCNPs@PM possessed better therapeutic efficacy compared with vacant ones. Therefore, the NIR light-controlled chemotherapy and photodynamic therapy could be realized simultaneously by CCUCNPs@PM.The light-triggered controlled release of anticancer drugs accompanied with NIR-responsive photodynamic therapy was prepared via a self-assembly process. Firstly, Mn2+-doped upconversion nanoparticles (UCNPs) were coated with a mesoporous silica shell and modified with photosensitizer (Chlorin e6) and long alkyl chains. And then the NIR light-responsive amphiphilic copolymer containing 9,10-dialkoxyanthracene groups was synthesized and then coated as the outermost layer. Upon irradiation with a 980 nm laser, the CCUCNPs@PM would absorb and then convert the NIR light to higher-energy visible red light (660 nm) via the UCNPs-based core, which could excite Chlorin e6 (Ce-6) to produce singlet oxygen (1O2). Then the 1O2-sensitive

  4. Hydrophilic Monodisperse Magnetic Nanoparticles Protected by an Amphiphilic Alternating Copolymer

    PubMed Central

    Shtykova, Eleonora V.; Huang, Xinlei; Gao, Xinfeng; Dyke, Jason C.; Schmucker, Abrin L.; Dragnea, Bogdan; Remmes, Nicholas; Baxter, David V.; Stein, Barry; Konarev, Peter V.; Svergun, Dmitri I.; Bronstein, Lyudmila M.

    2009-01-01

    Iron oxide nanoparticles (NPs) with diameters of 16.1, 20.5, and 20.8 nm prepared from iron oleate precursors were coated with poly(maleic acid-alt-1-octadecene) (PMAcOD). The coating procedure exploited hydrophobic interactions of octadecene and oleic acid tails while hydrolysis of maleic anhydride moieties allowed the NP hydrophilicity. The PMAcOD nanostructure in water and the PMAcOD-coated NPs were studied using transmission electron microscopy, ζ-potential measurements, small-angle X-ray scattering, and fluorescence measurements. The combination of several techniques suggests that independently of the iron oxide core and oleic acid shell structures, PMAcOD encapsulates NPs, forming stable hydrophilic shells which withstand absorption of hydrophobic molecules, such as pyrene, without shell disintegration. Moreover, the PMAcOD molecules are predominantly attached to a single NP instead of self-assembling into the PMAcOD disklike nanostructures or attachment to several NPs. This leads to highly monodisperse aqueous samples with only a small fraction of NPs forming large aggregates due to cross-linking by the copolymer macromolecules. PMID:19194520

  5. Structure of Block Copolymer Hydrogel Formed by Complex Coacervate Process

    NASA Astrophysics Data System (ADS)

    Choi, Soohyung; Ortony, Julia; Krogstad, Daniel; Spruell, Jason; Lynd, Nathaniel; Han, Songi; Kramer, Edward

    2012-02-01

    Complex coacervation occurs when oppositely charged polyelectrolytes associate in solution, forming dense micron-sized droplets. Hydrogels with coacervate block domains were formed by mixing two ABA and A'BA' triblock copolymer solutions in water where the A and A' blocks are oppositely charged. Small-angle neutron scattering (SANS) was used to investigate the structure of hydrogels formed by ABA triblock copolymers (A block: poly(allyl glycidyl ether) functionalized with guanidinium (A) or sulfonate (A'), B block: poly(ethylene oxide)). By using an appropriate fitting model, structural information such as coacervate core block radius and water volume fraction w can be extracted from SANS data. The results reveal that w in the coacervate core block was significantly higher than in conventional triblock copolymer hydrogels where microphase separation is driven by the hydrophobicity of the core-forming blocks.

  6. Manipulating Ordering Transitions in Interfacially Modified Block Copolymers

    SciTech Connect

    Singh, N.; Tureau, M; Epps, T

    2009-01-01

    We report a synthetic strategy that allows us to manipulate the interfacial region between blocks and control ordering transitions in poly(isoprene-b-styrene) [P(I-S)] block copolymers. This interfacial modification is accomplished by combining a semi-batch feed with anionic polymerization techniques. Using this approach, we are able to control the segmental composition and molecular interactions in our phase-separated block copolymers, independent of molecular weight and block constituents. A library of copolymers is prepared with various interfacial modifications to examine the effect of interfacial composition on copolymer self-assembly. The morphological characteristics of the self-assembled structures are investigated using small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and dynamic mechanical analysis (DMA). Normal and inverse tapered block copolymers, containing approximately 15-35 vol% tapered material, show a measurable decrease in the order-disorder transition temperature (TODT) relative to the corresponding non-tapered diblock copolymers, with the inverse tapered materials showing the greatest deviation in TODT. Additionally, TODT was inversely related to the volume fraction of the tapered region in both normal and inverse tapered copolymer materials.

  7. Colloidal inverse bicontinuous cubic membranes of block copolymers with tunable surface functional groups.

    PubMed

    La, Yunju; Park, Chiyoung; Shin, Tae Joo; Joo, Sang Hoon; Kang, Sebyung; Kim, Kyoung Taek

    2014-06-01

    Analogous to the complex membranes found in cellular organelles, such as the endoplasmic reticulum, the inverse cubic mesophases of lipids and their colloidal forms (cubosomes) possess internal networks of water channels arranged in crystalline order, which provide a unique nanospace for membrane-protein crystallization and guest encapsulation. Polymeric analogues of cubosomes formed by the direct self-assembly of block copolymers in solution could provide new polymeric mesoporous materials with a three-dimensionally organized internal maze of large water channels. Here we report the self-assembly of amphiphilic dendritic-linear block copolymers into polymer cubosomes in aqueous solution. The presence of precisely defined bulky dendritic blocks drives the block copolymers to form spontaneously highly curved bilayers in aqueous solution. This results in the formation of colloidal inverse bicontinuous cubic mesophases. The internal networks of water channels provide a high surface area with tunable surface functional groups that can serve as anchoring points for large guests such as proteins and enzymes. PMID:24848240

  8. Molecular Exchange Dynamics in Block Copolymer Micelles

    NASA Astrophysics Data System (ADS)

    Bates, Frank; Lu, Jie; Choi, Soohyung; Lodge, Timothy

    2012-02-01

    Poly(styrene-b-ethylene propylene) (PS-PEP) diblock copolymers were mixed with squalane (C30H62) at 1% by weight resulting in the formation of spherical micelles. The structure and dynamics of molecular exchange were characterized by synchrotron small-angle x-ray scattering (SAXS) and time resolved small-angle neutron scattering (TR-SANS), respectively, between 100 C and 160 C. TR-SANS measurements were performed with solutions initially containing deuterium labeled micelle cores and normal cores dispersed in a contrast matched squalane. Monitoring the reduction in scattering intensity as a function of time at various temperatures revealed molecular exchange dynamics highly sensitive to the core molecular weight and molecular weight distribution. Time-temperature superposition of data acquired at different temperatures produced a single master curve for all the mixtures. Experiments conducted with isotopically labeled micelle cores, each formed from two different but relatively mondisperse PS blocks, confirmed a simple dynamical model based on first order kinetics and core Rouse single chain relaxation. These findings demonstrate a dramatic transition to nonergodicity with increasing micelle core molecular weight and confirm the origins of the logarithmic exchange kinetics in such systems.

  9. Preparation of shell cross-linked nano-objects from hybrid-peptide block copolymers.

    PubMed

    Rodríguez-Hernández, Juan; Babin, Jérôme; Zappone, Bruno; Lecommandoux, Sébastien

    2005-01-01

    Supramolecular structures formed by self-assembly of diblock copolymers in solution are stable over restricted environmental conditions: concentration, temperature, pH, or ion strength among others. To enlarge their domain of application, it appears necessary to develop stabilization strategies. We report here different strategies to stabilize the shell of micelles formed by self-assembly of amphiphilic polydiene-b-polypeptide diblock copolymers. For this purpose, covalent bonds can be formed between either amine or carboxylic acid groups distributed along the soluble peptide block and a cross-linking agent that contains respectively aldehyde or amine functions. Shell stabilization affords systems with unique properties that combine three main advantages: shape persistence, control of the porosity, and stimuli-responsive behavior. The covalent capture of such macromolecular objects has been studied by light scattering, AFM, and conductimetry measurements.

  10. Synthesis and Characterization of Smart Block Copolymers for Biomineralization and Biomedical Applications

    SciTech Connect

    Kanapathipillai, Mathumai

    2008-01-01

    Self-assembly is a powerful tool in forming structures with nanoscale dimensions. Self-assembly of macromolecules provides an efficient and rapid pathway for the formation of structures from the nanometer to micrometer range that are difficult, if not impossible to obtain by conventional lithographic techniques [1]. Depending on the morphologies obtained (size, shape, periodicity, etc.) these self-assembled systems have already been applied or shown to be useful for a number of applications in nanotechnology [2], biomineralization [3, 4], drug delivery [5, 6] and gene therapy [7]. In this respect, amphiphilic block copolymers that self-organize in solution have been found to be very versatile [1]. In recent years, polymer-micellar systems have been designed that are adaptable to their environment and able to respond in a controlled manner to external stimuli. In short, synthesis of 'nanoscale objects' that exhibit 'stimulus-responsive' properties is a topic gathering momentum, because their behavior is reminiscent of that exhibited by proteins [8]. By integrating environmentally sensitive homopolymers into amphiphilic block copolymers, smart block copolymers with self assembled supramolecular structures that exhibit stimuli or environmentally responsive properties can be obtained [1]. Several synthetic polymers are known to have environmentally responsive properties. Changes in the physical, chemical or biochemical environment of these polymers results in modulation of the solubility or chain conformation of the polymer [9]. There are many common schemes of engineering stimuli responsive properties into materials [8, 9]. Polymers exhibiting lower critical solution temperature (LCST) are soluble in solvent below a specific temperature and phase separate from solvent above that temperature while polymers exhibiting upper critical solution temperatures (UCST) phase separate below a certain temperature. The solubility of polymers with ionizable moieties depends on the

  11. New adhesive systems based on functionalized block copolymers

    SciTech Connect

    Kent, M.; Saunders, R.; Hurst, M.; Small, J.; Emerson, J.; Zamora, D.

    1997-05-01

    The goal of this work was to evaluate chemically-functionalized block copolymers as adhesion promoters for metal/thermoset resin interfaces. Novel block copolymers were synthesized which contain pendant functional groups reactive toward copper and epoxy resins. In particular, imidazole and triazole functionalities that chelate with copper were incorporated onto one block, while secondary amines were incorporated onto the second block. These copolymers were found to self-assemble from solution onto copper surfaces to form monolayers. The structure of the adsorbed monolayers were studied in detail by neutron reflection and time-of-flight secondary ion mass spectrometry. The monolayer structure was found to vary markedly with the solution conditions and adsorption protocol. Appropriate conditions were found for which the two blocks form separate layers on the surface with the amine functionalized block exposed at the air surface. Adhesion testing of block copolymer-coated copper with epoxy resins was performed in both lap shear and peel modes. Modest enhancements in bond strengths were observed with the block copolymer applied to the native oxide. However, it was discovered that the native oxide is the weak link, and that by simply removing the native oxide, and then applying an epoxy resin before the native oxide can reform, excellent bond strength in the as-prepared state as well as excellent retention of bond strength after exposure to solder in ambient conditions are obtained. It is recommended that long term aging studies be performed with and without the block copolymer. In addition, the functionalized block copolymer method should be evaluated for another system that has inherently poor bonding, such as the nickel/silicone interface, and for systems involving metals and alloys which form oxides very rapidly, such as aluminum and stainless steel, where bonding strategies involve stabilizing the native oxide.

  12. Self-doped microphase separated block copolymer electrolyte

    DOEpatents

    Mayes, Anne M.; Sadoway, Donald R.; Banerjee, Pallab; Soo, Philip; Huang, Biying

    2002-01-01

    A polymer electrolyte includes a self-doped microphase separated block copolymer including at least one ionically conductive block and at least one second block that is immiscible in the ionically conductive block, an anion immobilized on the polymer electrolyte and a cationic species. The ionically conductive block provides a continuous ionically conductive pathway through the electrolyte. The electrolyte may be used as an electrolyte in an electrochemical cell.

  13. Preparation and Morphology of ABn Mictoarm Block Copolymers

    NASA Astrophysics Data System (ADS)

    Takano, Atsushi; Watanabe, Momoka; Asai, Yusuke; Suzuki, Jiro; Matsushita, Yushu

    A series of ABn mictoarm block copolymers (bottle brush copolymers) consisting of polystyrene (S) as a backbone and polyisoprenes (I) as grafts were precisely synthesized by an anionic polymerization, and their microphase-separated structures were investigated by transmission electron microscopy (TEM) and small-angle X-ray scattering(SAXS). A copolymer with composition of φS =0.57 and number of grafts(n) of 10 shows characteristic cylindrical structure, where microdomains of S reveals hexagonal cross section with non-constant mean curvature interface. While a sample with composition of φS =0.37 and number of grafts(n) of 40 shows spherical structure with rather large S isolated domains and characteristic domain packing manner was found. Furthermore composition dependence of microphase-separated structures for SIn mictoarm block copolymers were investigated and compared to SI diblock copolymer system.

  14. Oligoaniline-containing supramolecular block copolymer nanodielectric materials.

    PubMed

    Hardy, Christopher G; Islam, Md Sayful; Gonzalez-Delozier, Dioni; Ploehn, Harry J; Tang, Chuanbing

    2012-05-14

    We report a new generation of nanodielectric energy storage materials based on supramolecular block copolymers. In our approach, highly polarizable, conducting nanodomains are embedded within an insulating matrix through block copolymer microphase separation. An applied electric field leads to electronic polarization of the conducting domains. The high interfacial area of microphase-separated domains amplifies the polarization, leading to high dielectric permittivity. Specifically, reversible addition fragmentation transfer (RAFT) polymerization was used to prepare block copolymers with poly(methyl acrylate) (PMA) as the insulating segment and a strongly acidic dopant moiety, poly-(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA), as the basis for the conducting segment. The PAMPSA block was complexed with an oligoaniline trimer to form a dopant-conjugated moiety complex that is electronically conductive after oxidation. For the undoped neat block copolymers, the increase of the PMA block length leads to a transition in dielectric properties from ionic conductor to dielectric capacitor with polarization resulting from migration of protons within the isolated PAMPSA domains. The oligoaniline-doped copolymers show remarkably different dielectric properties. At frequencies above 200 kHz, they exhibit characteristics of dielectric capacitors with much higher permittivity and lower dielectric loss than the corresponding undoped copolymers. PMID:22331602

  15. Oligoaniline-containing supramolecular block copolymer nanodielectric materials.

    PubMed

    Hardy, Christopher G; Islam, Md Sayful; Gonzalez-Delozier, Dioni; Ploehn, Harry J; Tang, Chuanbing

    2012-05-14

    We report a new generation of nanodielectric energy storage materials based on supramolecular block copolymers. In our approach, highly polarizable, conducting nanodomains are embedded within an insulating matrix through block copolymer microphase separation. An applied electric field leads to electronic polarization of the conducting domains. The high interfacial area of microphase-separated domains amplifies the polarization, leading to high dielectric permittivity. Specifically, reversible addition fragmentation transfer (RAFT) polymerization was used to prepare block copolymers with poly(methyl acrylate) (PMA) as the insulating segment and a strongly acidic dopant moiety, poly-(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA), as the basis for the conducting segment. The PAMPSA block was complexed with an oligoaniline trimer to form a dopant-conjugated moiety complex that is electronically conductive after oxidation. For the undoped neat block copolymers, the increase of the PMA block length leads to a transition in dielectric properties from ionic conductor to dielectric capacitor with polarization resulting from migration of protons within the isolated PAMPSA domains. The oligoaniline-doped copolymers show remarkably different dielectric properties. At frequencies above 200 kHz, they exhibit characteristics of dielectric capacitors with much higher permittivity and lower dielectric loss than the corresponding undoped copolymers.

  16. Electrically conductive doped block copolymer of polyacetylene and polyisoprene

    DOEpatents

    Aldissi, Mahmoud

    1985-01-01

    An electrically conductive block copolymer of polyisoprene and polyacetyl and a method of making the same are disclosed. The polymer is prepared by first polymerizing isoprene with n-butyllithium in a toluene solution to form an active isoprenyllithium polymer. The active polymer is reacted with an equimolar amount of titanium butoxide and subsequently exposed to gaseous acetylene. A block copolymer of polyisoprene and polyacetylene is formed. The copolymer is soluble in common solvents and may be doped with I.sub.2 to give it an electrical conductivity in the metallic regime.

  17. Using Tapered Block Copolymers to Create Conducting Nanomaterials

    NASA Astrophysics Data System (ADS)

    Epps, Thomas, III

    2014-03-01

    Soft materials, such as polymers, colloids, surfactants, and liquid crystals, are a technologically important class of matter employed in a variety of applications. One sub-class of soft material, block copolymers, provides the opportunity to design materials with attractive chemical and mechanical properties based on the ability to assemble into periodic structures with nanoscale domain spacings. Several applications for block copolymers currently under investigation in my group include battery and fuel cell membranes, analytical separations membranes, nano-tool templates, precursors to electronic arrays, and drug delivery vehicles. One area of recent progress in the group focuses on the behavior of conventional block copolymer and tapered block copolymer systems for lithium battery membrane applications. We find that we can tune poly(styrene- b-ethylene oxide) diblock copolymer nanostructures by adjusting the lithium counterion and lithium salt concentration, as well as the taper volume fraction and composition. Additionally, we can estimate the effective interaction parameters (χeff) for the salt-doped copolymers to determine the overall influence of tapering on the energetics of copolymer assembly. These tapered materials allow us to design nanostructured membrane systems with increased conductivity and improved mechanical properties in ion transport devices. We gratefully acknowledge AFOSR-PECASE (FA9550-09-1-0706) and NSF-CAREER (DMR-0645586) for financial support.

  18. Self-Assembly of Amphiphilic Block Copolypeptoids – Micelles, Worms and Polymersomes

    NASA Astrophysics Data System (ADS)

    Fetsch, Corinna; Gaitzsch, Jens; Messager, Lea; Battaglia, Giuseppe; Luxenhofer, Robert

    2016-09-01

    Polypeptoids are an old but recently rediscovered polymer class with interesting synthetic, physico-chemical and biological characteristics. Here, we introduce new aromatic monomers, N-benzyl glycine N-carboxyanhydride and N-phenethyl glycine N-carboxyanhydride and their block copolymers with the hydrophilic polysarcosine. We compare their self-assembly in water and aqueous buffer with the self-assembly of amphiphilic block copolypeptoids with aliphatic side chains. The aggregates in water were investigated by dynamic light scattering and electron microscopy. We found a variety of morphologies, which were influenced by the polymer structure as well as by the preparation method. Overall, we found polymersomes, worm-like micelles and oligo-lamellar morphologies as well as some less defined aggregates of interconnected worms and vesicles. Such, this contribution may serve as a starting point for a more detailed investigation of the self-assembly behavior of the rich class of polypeptoids and for a better understanding between the differences in the aggregation behavior of non-uniform polypeptoids and uniform peptoids.

  19. Self-Assembly of Amphiphilic Block Copolypeptoids – Micelles, Worms and Polymersomes

    PubMed Central

    Fetsch, Corinna; Gaitzsch, Jens; Messager, Lea; Battaglia, Giuseppe; Luxenhofer, Robert

    2016-01-01

    Polypeptoids are an old but recently rediscovered polymer class with interesting synthetic, physico-chemical and biological characteristics. Here, we introduce new aromatic monomers, N-benzyl glycine N-carboxyanhydride and N-phenethyl glycine N-carboxyanhydride and their block copolymers with the hydrophilic polysarcosine. We compare their self-assembly in water and aqueous buffer with the self-assembly of amphiphilic block copolypeptoids with aliphatic side chains. The aggregates in water were investigated by dynamic light scattering and electron microscopy. We found a variety of morphologies, which were influenced by the polymer structure as well as by the preparation method. Overall, we found polymersomes, worm-like micelles and oligo-lamellar morphologies as well as some less defined aggregates of interconnected worms and vesicles. Such, this contribution may serve as a starting point for a more detailed investigation of the self-assembly behavior of the rich class of polypeptoids and for a better understanding between the differences in the aggregation behavior of non-uniform polypeptoids and uniform peptoids. PMID:27666081

  20. Self-assembly of a series of random copolymers bearing amphiphilic side chains.

    PubMed

    Wu, Xu; Qiao, Yingjie; Yang, Hui; Wang, Jinben

    2010-09-15

    A novel series of comb-like random copolymers were prepared by polymerization of amphiphilic macromonomers, 2-(acrylamido)-octane sulfonic acid (AMC(8)S), 2-(acrylamido)-dodecane sulfonic acid (AMC(12)S), and 2-(acrylamido)-hexadecane sulfonic acid (AMC(16)S), with 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS) respectively. The synthesis of the polymers with the same contents of amphiphilic units as side chains, but different chain length, enabled us to study the chain length dependence of their association in salt solution. Steady-state fluorescence measurements with pyrene as a polarity probe, quasielastic light scattering techniques (QELS) and transmission electron micrograph (TEM) were employed to investigate the associative properties of the system. The above investigations showed that all kinds of side chains begin to assemble at certain polymer concentrations and the critical aggregation concentration (CAC) decrease dramatically with the increase in the length and content of alkyl. An interesting phenomenon is that the assembly tends more favorably to occur among different molecules rather than within single molecule when the number of carbon atoms in the alkyl groups or the polymer concentration increases, leading to the formation of larger multimolecular micelle-like aggregate. The aim of the present work is to establish the fundamental preconditions of intramolecular and intermolecular association fashions for the polymers, which is useful for the exploitation of functional groups and contributes to the development of amphiphilic random polymers. PMID:20576273

  1. Mechano-responsive hydrogels crosslinked by reactive block copolymer micelles

    NASA Astrophysics Data System (ADS)

    Xiao, Longxi

    Hydrogels are crosslinked polymeric networks that can swell in water without dissolution. Owing to their structural similarity to the native extracelluar matrices, hydrogels have been widely used in biomedical applications. Synthetic hydrogels have been designed to respond to various stimuli, but mechanical signals have not incorporated into hydrogel matrices. Because most tissues in the body are subjected to various types of mechanical forces, and cells within these tissues have sophisticated mechano-transduction machinery, this thesis is focused on developing hydrogel materials with built-in mechano-sensing mechanisms for use as tissue engineering scaffolds or drug release devices. Self-assembled block copolymer micelles (BCMs) with reactive handles were employed as the nanoscopic crosslinkers for the construction of covalently crosslinked networks. BCMs were assembled from amphiphilic diblock copolymers of poly(n-butyl acrylate) and poly(acrylic acid) partially modified with acrylate. Radical polymerization of acrylamide in the presence of micellar crosslinkers gave rise to elastomeric hydrogels whose mechanical properties can be tuned by varying the BCM composition and concentration. TEM imaging revealed that the covalently integrated BCMs underwent strain-dependent reversible deformation. A model hydrophobic drug, pyrene, loaded into the core of BCMs prior to the hydrogel formation, was dynamically released in response to externally applied mechanical forces, through force-induced reversible micelle deformation and the penetration of water molecules into the micelle core. The mechano-responsive hydrogel has been studied for tissue repair and regeneration purposes. Glycidyl methacrylate (GMA)-modified hyaluronic acid (HA) was photochemically crosslinked in the presence of dexamethasone (DEX)-loaded crosslinkable BCMs. The resultant HA gels (HAxBCM) contain covalently integrated micellar compartments with DEX being sequestered in the hydrophobic core. Compared

  2. Defects in a Noncentrosymmetric Lemellar Block Copolymer Blend

    SciTech Connect

    Chen, Shujun; Gido, Samuel; Tsoukatos, Thodoris; Avgeropoulos, Apostolos; Hadjichristidis, Nikos; Hong, Kunlun; Mays, Jimmy

    2005-01-01

    Here we report results from a defect study on the noncentrosymmetric (NCS) lamellar blend of an ABCD tetrablock copolymer and an AD diblock copolymer. The block copolymers used were polystyrene-block-polybutadiene-block-polyisoprene-block-polycyclohexadiene and polystyrene-block-polycyclohexadiene. Coexisting tetrablock-rich mixed centrosymmetric (CS) and NCS lamellar morphologies were seen in TEM, as predicted by the mean-field theory. NCS grain boundary defects similar to those in CS lamellar systems were observed as well as new defects unique to NCS layered systems, such as chain polarity reversals and kink bands with dilation or compression of the layers. In addition to morphology observations, geometrical and energetic calculations were performed on several new NCS defects, which are in good agreement with experimental results.

  3. Patterned silica films using microphase separation of a block copolymer

    NASA Astrophysics Data System (ADS)

    Kataoka, Sho; Takeuchi, Yasutaka; Endo, Akira

    2014-11-01

    Block copolymers exhibit various nanoscale ordered morphologies induced by microphase separation. Here, we present a method for providing two types of patterned silica films on Si wafer substrates simply by shifting the phase equilibrium of a block copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-P4VP). In this method, siloxane is adsorbed onto poly(4-vinylpyridine) blocks of PS-P4VP whose structure varies with solvent polarity and is calcined to remove the block copolymer. Siloxane is in a dispersed phase with toluene as a solvent resulting in silica nanoparticle arrays, while siloxane is in a continuous phase with N, N-dimethylformamide (DMF) resulting in silica films with ordered mesopores. Since the pore size of silica films prepared in DMF is approximately 20 nm, the film has the ability to serve as a support for enzymes such as laccase.

  4. Synthesis of Electroneutralized Amphiphilic Copolymers with Peptide Dendrons for Intramuscular Gene Delivery.

    PubMed

    Pu, Linyu; Wang, Jiali; Li, Na; Chai, Qiuxia; Irache, Juan M; Wang, Gang; Tang, James Zhenggui; Gu, Zhongwei

    2016-06-01

    Intramuscular gene delivery materials are of great importance in plasmid-based gene therapy system, but there is limited information so far on how to design and synthesize them. A previous study showed that the peptide dendron-based triblock copolymer with its components arranged in a reversed biomembrane architecture could significantly increase intramuscular gene delivery and expression. Herein, we wonder whether copolymers with biomembrane-mimicking arrangement may have similar function on intramuscular gene delivery. Meanwhile, it is of great significance to uncover the influence of electric charge and molecular structure on the function of the copolymers. To address the issues, amphiphilic triblock copolymers arranged in hydrophilic-hydrophobic-hydrophilic structure were constructed despite the paradoxical characteristics and difficulties in synthesizing such hydrophilic but electroneutral molecules. The as-prepared two copolymers, dendronG2(l-lysine-OH)-poly propylene glycol2k(PPG2k)-dendronG2(l-lysine-OH) (rL2PL2) and dendronG3(l-lysine-OH)-PPG2k-dendronG3(l-lysine-OH) (rL3PL3), were in similar structure but had different hydrophilic components and surface charges, thus leading to different capabilities in gene delivery and expression in skeletal muscle. rL2PL2 was more efficient than Pluronic L64 and rL3PL3 when mediating luciferase, β-galactosidase, and fluorescent protein expressions. Furthermore, rL2PL2-mediated growth-hormone-releasing hormone expression could significantly induce mouse body weight increase in the first 21 days after injection. In addition, both rL2PL2 and rL3PL3 showed good in vivo biosafety in local and systemic administration. Altogether, rL2PL2-mediated gene expression in skeletal muscle exhibited applicable potential for gene therapy. The study revealed that the molecular structure and electric charge were critical factors governing the function of the copolymers for intramuscular gene delivery. It can be concluded that, combined

  5. Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan Lane

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there

  6. Block Copolymer Bottlebrushes: New Routes to Ever Smaller Microdomain Sizes

    NASA Astrophysics Data System (ADS)

    Mahanthappa, Mahesh; Speetjens, Frank

    Block copolymer self-assembly presents exciting opportunities for the development of nanotemplates for advanced lithography applications, wherein the microdomain sizes (~10-100 nm) are governed by the total copolymer degree of polymerization, N. However, this methodology is limited in its smallest achievable length scale, since AB diblock copolymers self-assemble only above a critical N that depends on the magnitude of the effective segmental interaction parameter χAB. Numerous recent reports have focused on developing ``high χAB'' AB diblocks that self-assemble at low values of N. In this talk we explore the ability of non-linear polymer architectures to induce block copolymer ordering at reduced length scales. Thus, we describe the melt and thin-film self-assembly behavior of block copolymer bottlebrushes derived from linking the block junctions of low molecular weight AB diblocks. We quantitatively demonstrate that increasing the bottlebrush backbone degree of polymerization (Nbackbone) results in a larger reduction in the critical copolymer arm degree of polymerization (Narm) required for self-assembly, thus reducing the length scales at which these materials self-assemble.

  7. Block Copolymer Nanocomposites in Electric Fields: Kinetics of Alignment

    SciTech Connect

    Liedel, Clemens; Pester, Christian; Ruppel, Markus A; Lewin, Christian; Pavan, Mariela J.; Urban, Volker S; Shenhar, Roy; Bosecke, Peter; Boker, Alexander

    2013-01-01

    We investigate the kinetics of block copolymer/nanoparticle composite alignment in an electric field using in situ transmission small-angle X-ray scattering. As a model system, we employ a lamellae forming polystyrene-block-poly(2-vinyl pyridine) block copolymer with different contents of gold nanoparticles in thick films under solvent vapor annealing. While the alignment improves with increasing nanoparticle fraction, the kinetics slows down. This is explained by changes in the degree of phase separation and viscosity. Our findings provide extended insights into the basics of nanocomposite alignment.

  8. Block copolymer adhesion promoters via ring-opening metathesis polymerization

    DOEpatents

    Kent, M.S.; Saunders, R.

    1997-02-18

    Coupling agents are disclosed based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization. 18 figs.

  9. Reordering transitions during annealing of block copolymer cylinder phases

    SciTech Connect

    Majewski, Pawel W.; Yager, Kevin G.

    2015-10-06

    While equilibrium block-copolymer morphologies are dictated by energy-minimization effects, the semi-ordered states observed experimentally often depend on the details of ordering pathways and kinetics. In this study, we explore reordering transitions in thin films of block-copolymer cylinder-forming polystyrene-block-poly(methyl methacrylate). We observe several transient states as films order towards horizontally-aligned cylinders. In particular, there is an early-stage reorganization from randomly-packed cylinders into hexagonally-packed vertically-aligned cylinders; followed by a reorientation transition from vertical to horizontal cylinder states. These transitions are thermally activated. The growth of horizontal grains within an otherwise vertical morphology proceeds anisotropically, resulting in anisotropic grains in the final horizontal state. The size, shape, and anisotropy of grains are influenced by ordering history; for instance, faster heating rates reduce grain anisotropy. These results help elucidate aspects of pathway-dependent ordering in block-copolymer thin films.

  10. Orienting Nanostructured Block Copolymer Thin Films via Entropy

    NASA Astrophysics Data System (ADS)

    Lo, Ting-Ya; Dehghan, Ashkan; Georgopanos, Prokopios; Avgeropoulos, Apostolos; Shi, An-Chang; Ho, Rong-Ming

    2015-03-01

    Controlling the orientation of nanostructured thin films of block copolymers (BCPs) is essential for next generation lithography using BCPs. According to conventional wisdom, the orientation of BCPs is mainly determined by molecular interactions (enthalpy-driven orientation). Here, we demonstrate that entropic effect can be used to control the orientation of BCP thin films. Specifically, the architecture of star-block copolymers consisting polystyrene (PS) and poly(dimethylsiloxane) (PDMS) blocks is used to regulate the entropic contribution to the self-assembled nanostructures. Our experimental and theoretical results unequivocally demonstrate that entropy-driven perpendicular orientation of BCP nanostructures can be induced by increasing the arm number of the star-block copolymers with the same volume fractions of PS and PDMS.

  11. Graphene oxide-enhanced sol-gel transition sensitivity and drug release performance of an amphiphilic copolymer-based nanocomposite

    PubMed Central

    Hu, Huawen; Wang, Xiaowen; Lee, Ka I; Ma, Kaikai; Hu, Hong; Xin, John H.

    2016-01-01

    We report the fabrication of a highly sensitive amphiphilic copolymer-based nanocomposite incorporating with graphene oxide (GO), which exhibited a low-intensity UV light-triggered sol-gel transition. Non-cytotoxicity was observed for the composite gels after the GO incorporation. Of particular interest were the microchannels that were formed spontaneously within the GO-incorporated UV-gel, which expedited sustained drug release. Therefore, the present highly UV-sensitive, non-cytotoxic amphiphilic copolymer-based composites is expected to provide enhanced photothermal therapy and chemotherapy by means of GO’s unique photothermal properties, as well as through efficient passive targeting resulting from the sol-gel transition characteristic of the copolymer-based system with improved sensitivity, which thus promises the enhanced treatment of patients with cancer and other diseases. PMID:27539298

  12. Graphene oxide-enhanced sol-gel transition sensitivity and drug release performance of an amphiphilic copolymer-based nanocomposite

    NASA Astrophysics Data System (ADS)

    Hu, Huawen; Wang, Xiaowen; Lee, Ka I.; Ma, Kaikai; Hu, Hong; Xin, John H.

    2016-08-01

    We report the fabrication of a highly sensitive amphiphilic copolymer-based nanocomposite incorporating with graphene oxide (GO), which exhibited a low-intensity UV light-triggered sol-gel transition. Non-cytotoxicity was observed for the composite gels after the GO incorporation. Of particular interest were the microchannels that were formed spontaneously within the GO-incorporated UV-gel, which expedited sustained drug release. Therefore, the present highly UV-sensitive, non-cytotoxic amphiphilic copolymer-based composites is expected to provide enhanced photothermal therapy and chemotherapy by means of GO’s unique photothermal properties, as well as through efficient passive targeting resulting from the sol-gel transition characteristic of the copolymer-based system with improved sensitivity, which thus promises the enhanced treatment of patients with cancer and other diseases.

  13. Hierarchical multiscale hyperporous block copolymer membranes via tunable dual-phase separation

    PubMed Central

    Yoo, Seungmin; Kim, Jung-Hwan; Shin, Myoungsoo; Park, Hyungmin; Kim, Jeong-Hoon; Lee, Sang-Young; Park, Soojin

    2015-01-01

    The rational design and realization of revolutionary porous structures have been long-standing challenges in membrane science. We demonstrate a new class of amphiphilic polystyrene-block-poly(4-vinylpyridine) block copolymer (BCP)–based porous membranes featuring hierarchical multiscale hyperporous structures. The introduction of surface energy–modifying agents and the control of major phase separation parameters (such as nonsolvent polarity and solvent drying time) enable tunable dual-phase separation of BCPs, eventually leading to macro/nanoscale porous structures and chemical functionalities far beyond those accessible with conventional approaches. Application of this BCP membrane to a lithium-ion battery separator affords exceptional improvement in electrochemical performance. The dual-phase separation–driven macro/nanopore construction strategy, owing to its simplicity and tunability, is expected to be readily applicable to a rich variety of membrane fields including molecular separation, water purification, and energy-related devices. PMID:26601212

  14. Desalination membranes from functional block copolymer via non-solvent induced phase inversion

    NASA Astrophysics Data System (ADS)

    Sung, Hyemin; Poelma, Justin; Leibfarth, Frank; Hawker, Craig; Bang, Joona

    2012-02-01

    Commercially available reverse osmosis (RO) and forward osmosis (FO) membranes are most commonly derived from materials such as polysulfone, polyimide, and cellulose acetate. While these membranes have improved the efficiency of the desalination process, they suffer from mechanical and chemical stability, fouling issues, and low fluxes. In this study, we combine a well-established membrane formation method, non-solvent-induced phase separation, with the self-assembly of a functional amphiphilic block copolymersAn amine and acid functional polystyrene-block-poly(ethylene oxide-co-allyl glycidyl ether) were chosen for the membranes. Membranes were formed by casting a concentrated polymer solution (12 to 25 wt% polymer) on PET fabric followed by immersion in a non-solvent bath. Scanning electron microscopy revealed an asymmetric porous structure consisting of a dense skin layer on top of a highly porous layer. Membrane performance was investigating using an FO test cell under the seawater condition.

  15. Aqueous Self-Assembly of Non-Ionic Bottlebrush Block Copolymer Surfactants with Tunable Molecular Shapes

    NASA Astrophysics Data System (ADS)

    Rzayev, Javid

    2015-03-01

    Polymer amphiphiles provide a robust and versatile platform for the fabrication of nanostructured soft matter. In this research, we explore a new class of polymer surfactants based on comb-like bottlebrush architecture as highly tunable molecular building blocks for aqueous self-assembly. Excluded volume interactions between densely grafted polymer side chains in the bottlebrush architecture are alleviated by backbone stretching, which leads to the formation of shape-persistent cylindrical macromolecules whose molecular dimensions can be precisely tailored during chemical synthesis. Amphiphilic bottlebrush block copolymers containing hydrophobic polylactide (PLA) and hydrophilic poly(oligoethylene oxide methacrylate) (PEO) side chains of various lengths were synthesized by a combination of controlled radical and ring-opening polymerizations. In dilute aqueous solutions, bottlebrush surfactants rapidly assembled into spherical, cylindrical and bilayer aggregates, as visualized by cryogenic transmission electron microscopy (cryo-TEM). Depending on the compositional side chain asymmetry, the formation of spherical micelles with different sizes and dispersities was observed. The molecular shape-dependent assembly was analyzed with help of a packing parameter (p) computed from the molecular composition data akin to small molecule surfactants, with most uniform spherical aggregates observed for bottlebrush amphiphiles with p close to 0.3. The formation of highly uniform micelles and the presence of a rich morphological diagram with relatively narrow compositional windows were attributed to the lack of conformational freedom in bottlebrush surfactants. Similarly, the unusual formation of cylindrical micelles with long aspect ratios for such high molecular weight amphiphiles was attributed to their inability to stabilize morphological defects, such as Y-junctions, with large deviations from mean curvature. Financial support for this work was provided by the National

  16. The plumber's nightmare: a new morphology in block copolymer-ceramic nanocomposites and mesoporous aluminosilicates.

    PubMed

    Finnefrock, Adam C; Ulrich, Ralph; Toombes, Gilman E S; Gruner, Sol M; Wiesner, Ulrich

    2003-10-29

    A novel cubic bicontinuous morphology is found in polymer-ceramic nanocomposites and mesoporous aluminosilicates that are derived by an amphiphilic diblock copolymer, poly(isoprene-b-ethylene oxide) (PI-b-PEO), used as a structure-directing agent for an inorganic aluminosilicate. Small-angle X-ray scattering (SAXS) was employed to unambiguously identify the Im(-)3m crystallographic symmetry of the materials by fitting individual Bragg peak positions in the two-dimensional X-ray images. Structure factor calculations, in conjunction with results from transmission electron microscopy, were used to narrow the range of possible structures consistent with the symmetry and showed the plumber's nightmare morphology to be consistent with the data. The samples are made by deposition onto a substrate that imposes a strain field, generating a lattice distortion. This distortion is quantitatively analyzed and shown to have resulted in shrinkage of the crystallites by approximately one-third in a direction perpendicular to the substrate, in both as-made composites and calcined ceramic materials. Finally, the observation of the bicontinuous block-copolymer-derived hybrid morphology is discussed in the context of a pseudo-ternary morphology diagram and compared to existing studies of ternary phase diagrams of amphiphiles in a mixture of two solvents. The calcined mesoporous materials have potential applications in the fields of catalysis, separation technology, and microelectronics.

  17. Method of forming oriented block copolymer line patterns, block copolymer line patterns formed thereby, and their use to form patterned articles

    SciTech Connect

    Russell, Thomas P.; Hong, Sung Woo; Lee, Doug Hyun; Park, Soojin; Xu, Ting

    2015-10-13

    A block copolymer film having a line pattern with a high degree of long-range order is formed by a method that includes forming a block copolymer film on a substrate surface with parallel facets, and annealing the block copolymer film to form an annealed block copolymer film having linear microdomains parallel to the substrate surface and orthogonal to the parallel facets of the substrate. The line-patterned block copolymer films are useful for the fabrication of magnetic storage media, polarizing devices, and arrays of nanowires.

  18. Influencing the structure of block copolymer micelles with small molecule additives

    NASA Astrophysics Data System (ADS)

    Robertson, Megan; Singh, Avantika; Cooksey, Tyler; Kidd, Bryce; Piemonte, Rachele; Wang, Shu; Mai Le, Kim; Madsen, Louis

    Amphiphilic block copolymer micelles in water are under broad exploration for drug delivery applications due to their high loading capacity and targeted drug delivery. We aim to understand the kinetic and thermodynamic processes that underlie the self-assembly of diblock copolymer micelle systems. The present work focuses on diblock copolymers containing poly(ethylene oxide) (a hydrophilic polymer) and polycaprolactone (a hydrophobic polymer), which spontaneously self-assemble into spherical micelles in water. Addition of a common good solvent (a co-solvent) for both of the constituting blocks, such as tetrahydrofuran (THF), reduces the interfacial tension at the core-corona interface. We are currently investigating the effect of this phenomenon on the micelle structural properties, using small-angle scattering and nuclear magnetic resonance. We have characterized the hydrodynamic radius, core radius, corona thickness, aggregation number, degree of swelling of the micelle core with the co-solvent, and unimer (free chain) concentration, as a function of the co-solvent concentration. Fundamental knowledge from these studies will inform design of drug delivery systems by allowing us to tailor micelle properties for optimal cargo loading.

  19. Radical-cured block copolymer-modified thermosets

    SciTech Connect

    Redline, Erica M.; Francis, Lorraine F.; Bates, Frank S.

    2013-01-10

    Poly(ethylene-alt-propylene)-b-poly(ethylene oxide) (PEP-PEO) diblock copolymers were synthesized and added at 4 wt % to 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (BisGMA), a monomer that cures using free radical chemistry. In separate experiments, poly(ethylene glycol) dimethacrylate (PEGDMA) was combined as a secondary monomer with BisGMA and the monomers were loaded with 4 wt % PEP-PEO. The diblock copolymers self-assembled into well-dispersed spherical micelles with PEP cores and PEO coronas. No appreciable change in the final extent of cure of the thermosets was caused by the addition of diblock copolymer, except in the case of BisGMA, where the addition of the block copolymer increased extent of cure by 12%. Furthermore, the extent of cure was increased by 29% and 37% with the addition of 25 and 50 wt % PEGDMA, respectively. Elastic modulus and fracture resistance were also determined, and the values indicate that the addition of block copolymers does not significantly toughen the thermoset materials. This finding is surprising when compared with the large increase in fracture resistance seen in block copolymer-modified epoxies, and an explanation is proposed.

  20. Nanopatterning of Viruses and Proteins Using Microphase Separated Block Copolymers

    NASA Astrophysics Data System (ADS)

    Cresce, Arthur; Lewandowski, Angela; Bentley, William; Kofinas, Peter

    2006-03-01

    Diblock copolymers containing nickel ions have been prepared that are capable of selectively adsorbing histidine-tagged green fluorescent protein (hisGFP), and also binding tobacco mosaic virus (TMV). A block copolymer of norbornene and norbornene dicarboxylic acid was synthesized using ring-opening metathesis polymerization. A 400/50 block ratio achieved a spherical microphase-separated morphology with roughly 20 nm diameter dicarboxylic acid spheres. The spherical phase was exposed to nickel ions in solution, templating the formation of nickel nanoparticles. This process gave a nickel-loaded diblock copolymer film whose surface was used to chelate hisGFP. Fluorescence spectroscopy and TEM confirmed the presence of the protein on the polymer surface. A sulfonated triblock copolymer was loaded with nickel ions using a similar solution-doping procedure. The morphology of this copolymer was lamellar, and its sulfonated block was loaded with nickel ions. TEM studies revealed the presence of the virus on the surface of the copolymer and showed that the bond between the TMV and the polymer surface can withstand severe detergent washes.

  1. Liquid-crystalline ordering helps block copolymer self-assembly.

    PubMed

    Yu, Haifeng; Kobayashi, Takaomi; Yang, Huai

    2011-08-01

    Interaction between liquid-crystalline elastic deformation and microphase separation in liquid-crystalline block copolymers enables them to supramolecularly assemble into ordered nanostructures with high regularity. With the help of liquid-crystalline alignment, parallel and perpendicular patterning of nanostructures is fabricated with excellent reproducibility and mass production, which provides nanotemplates and nanofabrication processes for preparing varieties of nanomaterials. Furthermore, nanoscale microphase separation improves the optical performance of block-copolymer fi lms by eliminating the scattering of visible light, leading to advanced applications in optical devices and actuators. Recent progress in liquid-crystalline block copolymers, including their phase diagram, structure-property relationship, nanostructure control and nanotemplate applications, is reviewed. PMID:21910267

  2. Smectic block copolymer thin films on corrugated substrates.

    PubMed

    Pezzutti, Aldo D; Gómez, Leopoldo R; Vega, Daniel A

    2015-04-14

    In this work we study equilibrium and non-equilibrium structures of smectic block copolymer thin films deposited on a topographically patterned substrate. A Brazovskii free energy model is employed to analyze the coupling between the smectic texture and the local mean curvature of the substrate. The substrate's curvature produces out-of-plane deformations of the block copolymer such that equilibrium textures are modified and dictated by the underlying geometry. For weak curvatures it is shown that the free energy of the block copolymer film follows a Helfrich form, scaling with the square of the mean curvature, with a bending constant dependent on the local pattern orientation. On substrates of varying mean curvature simulations show that topological defects are rapidly expelled from regions with large curvature. These results compare well with available experimental data of poly(styrene)-co-poly(ethylene-alt-propylene) smectic thin films.

  3. Characterization of Lithium Polysulfide Salts in Homopolymers and Block Copolymers

    NASA Astrophysics Data System (ADS)

    Wang, Dunyang; Wujcik, Kevin; Balsara, Nitash

    Ion-conducting polymers are important for solid-state batteries due to the promise of better safety and the potential to produce higher energy density batteries. Nanostructured block copolymer electrolytes can provide high ionic conductivity and mechanical strength through microphase separation. One of the potential use of block copolymer electrolytes is in lithium-sulfur batteries, a system that has high theoretical energy density wherein the reduction of sulfur leads to the formation of lithium polysulfide intermediates. In this study we investigate the effect of block copolymer morphology on the speciation and transport properties of the polysulfides. The morphology and conductivities of polystyrene-b-poly(ethylene oxide) (SEO) containing lithium polysulfides were studies using small-angle X-ray scattering and ac impedance spectroscopy. UV-vis spectroscopy is being used to determine nature of the polysulfide species in poly(ethylene oxide) and SEO. Department of Energy, Soft Matter Electron Microscopy Program and Battery Materials Research Program.

  4. Controlling block copolymer phase behavior using ionic surfactant

    NASA Astrophysics Data System (ADS)

    Ray, D.; Aswal, V. K.

    2016-05-01

    The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO26PO39EO26)] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle-surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at higher temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.

  5. Synthesis and morphology characterization of polydimethylsiloxane-containing block copolymers

    NASA Astrophysics Data System (ADS)

    Wadley, Maurice

    The thin film morphology characteristics of polydimethylsiloxane-containing block copolymers have been investigated. For this investigation, a commercially available hydroxyl terminated PDMS was purchased from Gelest and attached to a carboxylic acid functional reversible addition-fragmentation chain transfer (RAFT) agent by Steglich esterification. This produced macro-RAFT agents to which styrene monomer was polymerized. By using this approach the generation of low polydispersity polystyrene-block-polydimethylsiloxane (PS-block-PDMS) copolymers of various molecular weights spanning a wide volume fraction range in which the PDMS block remained the same in each polymerization. Synthesized block copolymers were characterized by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. Bulk and thin film characterization of PS-block-PDMS copolymers was done by small-angle x-ray scattering (SAXS), transmission electron microscopy (TEM), contact angle measurements, scanning force microscopy (SFM), and grazing incidence small-angle X-ray scattering (GISAXS). The following observations have been made. For PS-rich PS-block -PDMS copolymer thin films the low surface tension of PDMS caused it to migrate to the film surface regardless of solvent choice. The surface morphology was found to depend strongly on the solubility parameter of the solvent and exhibited SFM images consistent with parallel cylinder, perforated lamellar, and lamellar surface layers with increasing solvent solubility parameter. This behavior was due to the selective swelling of the individual blocks under slightly selective, good solvent conditions. A custom solvent annealing apparatus provided similar results in which order-order transitions in the thin films were observed with increasing solvent solubility parameter. Additionally improvements in the long-range order were observed after 1 h of solvent annealing. PS-rich PS-block-PDMS copolymer thin films also displayed PDMS

  6. Association behaviors of dodecyltrimethylammonium bromide with double hydrophilic block co-polymer poly(ethylene glycol)-block-poly(glutamate sodium).

    PubMed

    Han, Yuchun; Xia, Lin; Zhu, Linyi; Zhang, Shusheng; Li, Zhibo; Wang, Yilin

    2012-10-30

    The association behaviors of single-chain surfactant dodecyltrimethylammonium bromide (DTAB) with double hydrophilic block co-polymers poly(ethylene glycol)-b-poly(sodium glutamate) (PEG(113)-PGlu(50) or PEG(113)-PGlu(100)) were investigated using isothermal titration microcalorimetry, cryogenic transmission electron microscopy, circular dichroism, ζ potential, and particle size measurements. The electrostatic interaction between DTAB and the oppositely charged carboxylate groups of PEG-PGlu induces the formation of super-amphiphiles, which further self-assemble into ordered aggregates. Dependent upon the charge ratios between DTAB and the glutamic acid residue of the co-polymer, the mixture solutions can change from transparent to opalescent without precipitation. Dependent upon the chain length of the PGlu block, the mixture of DTAB and PEG-PGlu diblocks can form two different aggregates at their corresponding electroneutral point. Spherical and rod-like aggregates are formed in the PEG(113)-PGlu(50)/DTAB mixture, while the vesicular aggregates are observed in the PEG(113)-PGlu(100)/DTAB mixture solution. Because the PEG(113)-PGlu(100)/DTAB super-amphiphile has more hydrophobic components than that of the PEG(113)-PGlu(50)/DTAB super-amphiphile, the former prefers forming the ordered aggregates with higher curvature, such as spherical and rod aggregates, but the latter prefers forming vesicular aggregates with lower curvature.

  7. Molecular origin of photovoltaic performance in donor-block-acceptor all-conjugated block copolymers

    DOE PAGES

    Smith, Kendall A.; Lin, Yen -Hao; Mok, Jorge W.; Yager, Kevin G.; Strzalka, Joseph; Nie, Wanyi; Mohite, Aditya D.; Verduzco, Rafael

    2015-11-03

    All-conjugated block copolymers may be an effective route to self-assembled photovoltaic devices, but we lack basic information on the relationship between molecular characteristics and photovoltaic performance. Here, we synthesize a library of poly(3-hexylthiophene) (P3HT) block poly((9,9-dialkylfluorene)-2,7-diyl-alt-[4,7-bis(alkylthiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT) donor-block-acceptor all-conjugated block copolymers and carry out a comprehensive study of processing conditions, crystallinity, domain sizes, and side-chain structure on photovoltaic device performance. We find that all block copolymers studied exhibit an out-of-plane crystal orientation after deposition, and on thermal annealing at high temperatures the crystal orientation flips to an in-plane orientation. By varying processing conditions on polymer photovoltaic devices, we show thatmore » the crystal orientation has only a modest effect (15-20%) on photovoltaic performance. The addition of side-chains to the PFTBT block is found to decrease photovoltaic power conversion efficiencies by at least an order of magnitude. Through grazing-incidence X-ray measurements we find that the addition of side-chains to the PFTBT acceptor block results in weak segregation and small (< 10 nm) block copolymer self-assembled donor and acceptor domains. This work is the most comprehensive to date on all-conjugated block copolymer systems and suggests that photovoltaic performance of block copolymers depends strongly on the miscibility of donor and acceptor blocks, which impacts donor and acceptor domain sizes and purity. Lastly, strategies for improving the device performance of block copolymer photovoltaics should seek to increase segregation between donor and acceptor polymer domains.« less

  8. Self-assembled micelles of novel amphiphilic copolymer cholesterol-coupled F68 containing cabazitaxel as a drug delivery system.

    PubMed

    Song, Yanzhi; Tian, Qingjing; Huang, Zhenjun; Fan, Di; She, Zhennan; Liu, Xinrong; Cheng, Xiaobo; Yu, Bin; Deng, Yihui

    2014-01-01

    Despite being one of the most promising amphiphilic block copolymers, use of Pluronic F68 in drug delivery is limited due to its high critical micelle concentration (CMC). In this study, we developed a novel F68 derivative, cholesterol-coupled F68 (F68-CHMC). This new derivative has a CMC of 10 μg/mL, which is 400-fold lower than that of F68. The drug-loading capacity of F68-CHMC was investigated by encapsulating cabazitaxel, a novel antitumor drug. Drug-loaded micelles were fabricated by a self-assembly method with simple dilution. The optimum particle size of the micelles was 17.5±2.1 nm, with an entrapment efficiency of 98.1% and a drug loading efficiency of 3.16%. In vitro release studies demonstrated that cabazitaxel-loaded F68-CHMC micelles had delayed and sustained-release properties. A cytotoxicity assay of S180 cells showed that blank F68-CHMC was noncytotoxic with a cell viability of nearly 100%, even at a concentration of 1,000 μg/mL. The IC50 revealed that cabazitaxel-loaded F68-CHMC micelles were more cytotoxic than Tween 80-based cabazitaxel solution and free cabazitaxel. In vivo antitumor activity against S180 cells also indicated better tumor inhibition by the micelles (79.2%) than by Tween 80 solution (56.2%, P<0.05). Based on these results, we conclude that the F68-CHMC copolymer may be a potential nanocarrier to improve the solubility and biological activity of cabazitaxel and other hydrophobic drugs.

  9. Structure-directing star-shaped block copolymers: supramolecular vesicles for the delivery of anticancer drugs.

    PubMed

    Yang, Chuan; Liu, Shao Qiong; Venkataraman, Shrinivas; Gao, Shu Jun; Ke, Xiyu; Chia, Xin Tian; Hedrick, James L; Yang, Yi Yan

    2015-06-28

    Amphiphilic polycarbonate/PEG copolymer with a star-like architecture was designed to facilitate a unique supramolecular transformation of micelles to vesicles in aqueous solution for the efficient delivery of anticancer drugs. The star-shaped amphipilic block copolymer was synthesized by initiating the ring-opening polymerization of trimethylene carbonate (TMC) from methyl cholate through a combination of metal-free organo-catalytic living ring-opening polymerization and post-polymerization chain-end derivatization strategies. Subsequently, the self-assembly of the star-like polymer in aqueous solution into nanosized vesicles for anti-cancer drug delivery was studied. DOX was physically encapsulated into vesicles by dialysis and drug loading level was significant (22.5% in weight) for DOX. Importantly, DOX-loaded nanoparticles self-assembled from the star-like copolymer exhibited greater kinetic stability and higher DOX loading capacity than micelles prepared from cholesterol-initiated diblock analogue. The advantageous disparity is believed to be due to the transformation of micelles (diblock copolymer) to vesicles (star-like block copolymer) that possess greater core space for drug loading as well as the ability of such supramolecular structures to encapsulate DOX. DOX-loaded vesicles effectively inhibited the proliferation of 4T1, MDA-MB-231 and BT-474 cells, with IC50 values of 10, 1.5 and 1.0mg/L, respectively. DOX-loaded vesicles injected into 4T1 tumor-bearing mice exhibited enhanced accumulation in tumor tissue due to the enhanced permeation and retention (EPR) effect. Importantly, DOX-loaded vesicles demonstrated greater tumor growth inhibition than free DOX without causing significant body weight loss or cardiotoxicity. The unique ability of the star-like copolymer emanating from the methyl cholate core provided the requisite modification in the block copolymer interfacial curvature to generate vesicles of high loading capacity for DOX with significant

  10. Structure-directing star-shaped block copolymers: supramolecular vesicles for the delivery of anticancer drugs.

    PubMed

    Yang, Chuan; Liu, Shao Qiong; Venkataraman, Shrinivas; Gao, Shu Jun; Ke, Xiyu; Chia, Xin Tian; Hedrick, James L; Yang, Yi Yan

    2015-06-28

    Amphiphilic polycarbonate/PEG copolymer with a star-like architecture was designed to facilitate a unique supramolecular transformation of micelles to vesicles in aqueous solution for the efficient delivery of anticancer drugs. The star-shaped amphipilic block copolymer was synthesized by initiating the ring-opening polymerization of trimethylene carbonate (TMC) from methyl cholate through a combination of metal-free organo-catalytic living ring-opening polymerization and post-polymerization chain-end derivatization strategies. Subsequently, the self-assembly of the star-like polymer in aqueous solution into nanosized vesicles for anti-cancer drug delivery was studied. DOX was physically encapsulated into vesicles by dialysis and drug loading level was significant (22.5% in weight) for DOX. Importantly, DOX-loaded nanoparticles self-assembled from the star-like copolymer exhibited greater kinetic stability and higher DOX loading capacity than micelles prepared from cholesterol-initiated diblock analogue. The advantageous disparity is believed to be due to the transformation of micelles (diblock copolymer) to vesicles (star-like block copolymer) that possess greater core space for drug loading as well as the ability of such supramolecular structures to encapsulate DOX. DOX-loaded vesicles effectively inhibited the proliferation of 4T1, MDA-MB-231 and BT-474 cells, with IC50 values of 10, 1.5 and 1.0mg/L, respectively. DOX-loaded vesicles injected into 4T1 tumor-bearing mice exhibited enhanced accumulation in tumor tissue due to the enhanced permeation and retention (EPR) effect. Importantly, DOX-loaded vesicles demonstrated greater tumor growth inhibition than free DOX without causing significant body weight loss or cardiotoxicity. The unique ability of the star-like copolymer emanating from the methyl cholate core provided the requisite modification in the block copolymer interfacial curvature to generate vesicles of high loading capacity for DOX with significant

  11. Regular and Irregular Mixing in Hydrocarbon Block Copolymers

    NASA Astrophysics Data System (ADS)

    Register, Richard; Beckingham, Bryan

    2014-03-01

    Since hydrocarbon polymers interact through relatively simple (dispersive) interactions, one might expect them to be described by simple models of mixing energetics, such as regular mixing. However, the pioneering work of Graessley on saturated hydrocarbon polymer blends showed that while regular mixing is obeyed in some cases, both positive and negative deviations (in the magnitude of the mixing enthalpy) from regular mixing are observed in other cases. Here, we describe the mixing energetics for two series of hydrocarbon polymers wherein the interaction strengths may be continuously tuned, and which can be readily incorporated into block copolymers. Random copolymers of styrene and medium-vinyl isoprene, in which either the isoprene or both the isoprene and styrene units have been saturated, obey regular mixing over the entire composition range and for both hydrogenated derivatives. Well-defined block copolymers with arbitrarily small interblock interaction strengths can be constructed from these units, permitting the interdomain spacing to be made arbitrarily large while holding the order-disorder transition temperature constant. However, block copolymers of hydrogenated polybutadiene with such random copolymers show very strong positive deviations from regular mixing when the styrene aromaticity is preserved, and sizable negative deviations when the styrene units are saturated to vinylcyclohexane. Both of these cases can be quantitatively described by a ternary mixing model.

  12. Yield Stress Enhancement in Glassy-Polyethylene Block Copolymers

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    Polyethylene (PE) has the highest annual production volume of all synthetic polymers worldwide, and is valuable across many applications due to its low cost, toughness, processability, and chemical resistance. However, PE is not well suited to certain applications due to its modest yield stress and Young's modulus (approximately 30 MPa and 1 GPa, respectively for linear, high-density PE). Irreversible deformation of PE results from dislocation of crystal stems and eventual crystal fragmentation under applied stress. The liquid-like amorphous fraction provides no useful mechanical support to the crystal fold surface in a PE homopolymer, so the only method to enhance the force required for crystal slip, and hence the yield stress, is crystal thickening via thermal treatment. An alternative route towards modifying the mechanical properties of PE involves copolymerization of a minority high-glass transition temperature block into a majority-PE block copolymer. In this work, we investigate a system of glassy/linear-PE block copolymers prepared via ring-opening metathesis polymerization of cyclopentene and substituted norbornene monomers followed by hydrogenation. We demonstrate that a large change in mechanical properties can be achieved with the addition of a short glassy block (e.g. a doubling of the yield stress and Young's modulus versus PE homopolymer with the addition of 25 percent glassy block). Furthermore, owing to the low interaction energy between PE and the substituted polynorbornene blocks employed, these high-yield PE block copolymers can exhibit single-phase melts for ease of processability.

  13. Protective effects of nonionic tri-block copolymers on bile acid-mediated epithelial barrier disruption.

    SciTech Connect

    Edelstein, A.; Fink, D.; Musch, M.; Valuckaite, V.; Zabornia, O.; Grubjesic, S.; Firestone, M. A.; Matthews, J. B.; Alverdy, J. C.

    2011-11-01

    Translocation of bacteria and other luminal factors from the intestine following surgical injury can be a major driver of critical illness. Bile acids have been shown to play a key role in the loss of intestinal epithelial barrier function during states of host stress. Experiments to study the ability of nonionic block copolymers to abrogate barrier failure in response to bile acid exposure are described. In vitro experiments were performed with the bile salt sodium deoxycholate on Caco-2 enterocyte monolayers using transepithelial electrical resistance to assay barrier function. A bisphenol A coupled triblock polyethylene glycol (PEG), PEG 15-20, was shown to prevent sodium deoxycholate-induced barrier failure. Enzyme-linked immunosorbent assay, lactate dehydrogenase, and caspase 3-based cell death detection assays demonstrated that bile acid-induced apoptosis and necrosis were prevented with PEG 15-20. Immunofluorescence microscopic visualization of the tight junctional protein zonula occludens 1 (ZO-1) demonstrated that PEG 15-20 prevented significant changes in tight junction organization induced by bile acid exposure. Preliminary transepithelial electrical resistance-based studies examining structure-function correlates of polymer protection against bile acid damage were performed with a small library of PEG-based copolymers. Polymer properties associated with optimal protection against bile acid-induced barrier disruption were PEG-based compounds with a molecular weight greater than 10 kd and amphiphilicity. The data demonstrate that PEG-based copolymer architecture is an important determinant that confers protection against bile acid injury of intestinal epithelia.

  14. Block Copolymer Membranes for Efficient Capture of a Chemotherapy Drug

    PubMed Central

    2016-01-01

    We introduce the use of block copolymer membranes for an emerging application, “drug capture”. The polymer is incorporated in a new class of biomedical devices, referred to as ChemoFilter, which is an image-guided temporarily deployable endovascular device designed to increase the efficacy of chemotherapy-based cancer treatment. We show that block copolymer membranes consisting of functional sulfonated polystyrene end blocks and a structural polyethylene middle block (S-SES) are capable of capturing doxorubicin, a chemotherapy drug. We focus on the relationship between morphology of the membrane in the ChemoFilter device and efficacy of doxorubicin capture measured in vitro. Using small-angle X-ray scattering and cryogenic scanning transmission electron microscopy, we discovered that rapid doxorubicin capture is associated with the presence of water-rich channels in the lamellar-forming S-SES membranes in aqueous environment. PMID:27547493

  15. Fluctuation Dynamics of Block Copolymer Vesicles

    SciTech Connect

    Falus, P.; Borthwick, M.A.; Mochrie, S.G.J.

    2010-07-13

    X-ray photon correlation spectroscopy was used to characterize the wave-vector- and temperature-dependent dynamics of spontaneous thermal fluctuations in a vesicle (L4) phase that occurs in a blend of a symmetric poly(styrene-ethylene/butylene-styrene) triblock copolymer with a polystyrene homopolymer. Measurements of the intermediate scattering function reveal stretched-exponential behavior versus time, with a stretching exponent slightly larger than 2/3. The corresponding relaxation rates show an approximate q{sup 3} dependence versus wave vector. Overall, the experimental measurements are well described by theories that treat the dynamics of independent membrane plaquettes.

  16. Flash NanoPrecipitation of organic actives via confined micromixing and block copolymer stabilization

    NASA Astrophysics Data System (ADS)

    Johnson, Brian K.

    This dissertation provides a method and the understanding required to produce nanoparticles of organic actives using Flash NanoPrecipitation . The process comprises mixing a solvent phase containing molecularly dissolved amphiphilic block copolymer and an organic active with an anti-solvent. One block of the copolymer precipitates to alter the nucleation and growth of the organic active while the other remains in solution for particle stabilization. A custom built confined impinging jets (CIJ) mixer provides optimum micromixing at the laboratory or full scale within milliseconds. Comparison to other reactor designs is provided. The resulting nanoparticles have functional surfaces tailored to meet the needs of pharmaceutical or specialty chemical formulations. Example beta-carotene nanoparticles with a polyethylene oxide surface are produced at high concentration, high yield, low stabilizer content, and a size suitable for sterile filtration or larger. The technical challenges in nanoparticle production are explained via the characteristic times for mixing, copolymer aggregation, and organic active particle formation. The time for Flash NanoPrecipitation is shown to depend strongly on the time for copolymer aggregation, and control of the organic nucleation versus growth is critical to achieve nanoparticles. Mixing operating lines explain the impact of solubility differences between the colloidal stabilizer and the organic active as function of mixing rate. Techniques to measure the solubility of the copolymer and DeltaG° , DeltaH°, and DeltaS° of micellization are demonstrated. An analytical CIJ mixer is developed by quantifying the characteristic time and physical mechanism of mixing. The methodology described to find an absolute mixing lifetime is also applied to a vortex mixer at a spectrum of flow ratios away from one. Dimensional analysis using the process Damkohler number, defined as the ratio of the mixing to the process time, is applied to precipitation

  17. High-Density Reconstitution of Functional Water Channels into Vesicular and Planar Block Copolymer Membranes

    PubMed Central

    2012-01-01

    The exquisite selectivity and unique transport properties of membrane proteins can be harnessed for a variety of engineering and biomedical applications if suitable membranes can be produced. Amphiphilic block copolymers (BCPs), developed as stable lipid analogs, form membranes that functionally incorporate membrane proteins and are ideal for such applications. While high protein density and planar membrane morphology are most desirable, BCP–membrane protein aggregates have so far been limited to low protein densities in either vesicular or bilayer morphologies. Here, we used dialysis to reproducibly form planar and vesicular BCP membranes with a high density of reconstituted aquaporin-0 (AQP0) water channels. We show that AQP0 retains its biological activity when incorporated at high density in BCP membranes, and that the morphology of the BCP–protein aggregates can be controlled by adjusting the amount of incorporated AQP0. We also show that BCPs can be used to form two-dimensional crystals of AQP0. PMID:23082933

  18. Comb-like amphiphilic polypeptide-based copolymer nanomicelles for co-delivery of doxorubicin and P-gp siRNA into MCF-7 cells.

    PubMed

    Suo, Aili; Qian, Junmin; Zhang, Yaping; Liu, Rongrong; Xu, Weijun; Wang, Hejing

    2016-05-01

    A comb-like amphiphilic copolymer methoxypolyethylene glycol-graft-poly(L-lysine)-block-poly(L-phenylalanine) (mPEG-g-PLL-b-Phe) was successfully synthesized. To synthesize mPEG-g-PLL-b-Phe, diblock copolymer PLL-b-Phe was first synthesized by successive ring-opening polymerization of α-amino acid N-carboxyanhydrides followed by the removal of benzyloxycarbonyl protecting groups, and then mPEG was grafted onto PLL-b-Phe by reductive amination via Schiff's base formation. The chemical structures of the copolymers were identified by (1)H NMR. mPEG-g-PLL-b-Phe copolymer had a critical micelle concentration of 6.0mg/L and could self-assemble in an aqueous solution into multicompartment nanomicelles with a mean diameter of approximately 78 nm. The nanomicelles could encapsulate doxorubicin (DOX) through hydrophobic and π-π stacking interactions between DOX molecules and Phe blocks and simultaneously complex P-gp siRNA with cationic PLL blocks via electrostatic interactions. The DOX/P-gp siRNA-loaded nanomicelles showed spherical morphology, possessed narrow particle size distribution and had a mean particle size of 120 nm. The DOX/P-gp siRNA-loaded nanomicelles exhibited pH-responsive release behaviors and displayed accelerated release under acidic conditions. The DOX/P-gp siRNA-loaded nanomicelles were efficiently internalized into MCF-7 cells, and DOX released could successfully reach nuclei. In vitro cytotoxicity assay demonstrated that the DOX/P-gp siRNA-loaded nanomicelles showed a much higher cytotoxicity in MCF-7 cells than DOX-loaded nanomicelles due to their synergistic killing effect and that the blank nanomicelles had good biocompatibility. Thus, the novel comb-like mPEG-g-PLL-b-Phe nanomicelles could be a promising vehicle for co-delivery of chemotherapeutic drug and genetic material.

  19. Synthesis and Characterization of Silicate Ester Prodrugs and Poly(ethylene glycol)-b-poly(lactic-co-glycolic acid) Block Copolymers for Formulation into Prodrug-Loaded Nanoparticles

    NASA Astrophysics Data System (ADS)

    Wohl, Adam Richard

    Fine control of the physical and chemical properties of customized materials is a field that is rapidly advancing. This is especially critical in pursuits to develop and optimize novel nanoparticle drug delivery. Specifically, I aim to apply chemistry concepts to test the hypothesis "Silicate ester prodrugs of paclitaxel, customized to have the proper hydrophobicity and hydrolytic lability, can be formulated with well-defined, biocompatible, amphiphilic block copolymers into nanoparticles that are effective drugs." Chapter 1 briefly describes the context and motivation of the scientific pursuits described in this thesis. In Chapter 2, a family of model silicate esters is synthesized, the hydrolysis rate of each compound is benchmarked, and trends are established based upon the steric bulk and leaving group ability of the silicate substituents. These trends are then applied to the synthesis of labile silicate ester prodrugs in Chapter 3. The bulk of this chapter focuses on the synthesis, hydrolysis, and cytotoxicity of prodrugs based on paclitaxel, a widely used chemotherapeutic agent. In Chapter 4, a new methodology for the synthesis of narrowly dispersed, "random" poly(lactic-co-glycolic acid) polymers by a constant infusion of the glycolide monomer is detailed. Using poly(ethylene glycol) as a macroinitiator, amphiphilic block copolymers were synthesized. Co-formulating a paclitaxel silicate and an amphiphilic block copolymer via flash nanoprecipitation led to highly prodrug-loaded, kinetically trapped nanoparticles. Studies to determine the structure, morphology, behavior, and efficacy of these nanoparticles are described in Chapter 5. Efforts to develop a general strategy for the selective end-functionalization of the polyether block of these amphiphilic block copolymers are discussed in Chapter 6. Examples of this strategy include functionalization of the polyether with an azide or a maleimide. Finally, Chapter 7 provides an outlook for future development of

  20. Amphiphilic peptides and their cross-disciplinary role as building blocks for nanoscience.

    PubMed

    Cavalli, Silvia; Albericio, Fernando; Kros, Alexander

    2010-01-01

    Peptides are particularly attractive as molecular building blocks in the bottom-up fabrication of supramolecular structures based on self-assembly and have potential in many important applications in the fields of biotechnology and bioengineering. In the first part of this critical review the main categories of peptide-based amphiphiles will be discussed by showing some relevant examples, which demonstrate the importance of amphiphilic peptides as molecular building blocks for nanostructures. In the second part of this review we will review the cross-disciplinary role of peptide-based supramolecular nanoarchitectures ranging from chemistry to biology, medicine, materials science, and engineering through discussing several examples of applied nanomaterials (216 references).

  1. Block copolymer-mediated synthesis of size-tunable gold nanospheres and nanoplates.

    PubMed

    Goy-López, Sonia; Castro, Emilio; Taboada, Pablo; Mosquera, Víctor

    2008-11-18

    We have successfully controlled the size and shape of isotropic and anisotropic gold nanocrystals through a one-step reaction by using amphiphilic polyethylene oxide-polystyrene oxide block copolymers as both reductant and stabilizing agents in water solution. Spherical or quasispherical nanoparticles were obtained at room temperature with tunable mean sizes and polydispersities depending on reaction conditions, that is, on copolymer block length, and copolymer and gold salt concentrations. By moderate increases of reaction temperature up to 65 degrees C, progressive formation of single-crystalline gold nanoplates in good yields takes place (up to 70%) without the necessity of additional reactants or growing solutions. These nanoplates are characterized by lateral mean sizes between 0.1-1.2 microm depending on copolymer concentration and reaction temperature, with mainly truncated or rounded triangular shapes with {111} planes as two basal surfaces. This allows us to tune the surface plasmon band of the nanoplates from ca. 850 nm to more than 1100 nm, well inside the near-infrared region (NIR), which enables the use of these type of nanostructures as a very promsing materials in applications such as optical coatings, SERS, and cancer cell hyperthermia. We proposed that the growth of these nanostructures can stem from a decrease in the reaction rate as temperature increases due to an enhanced copolymer hydrophobicity, which gives rise to a structure of interacting micelles formed from the fluid via a percolation transition (known as "soft gel") at elevated temperatures. In this way, reduction becomes slow enough to allow kinetic control of the reaction, and preferential adsorption of the copolymer molecules/micelles on certain crystallographic planes can favor the growth of certain nanocrystal facets to give the final structure. This alternative water-based system provides a more convenient and environmentally benign route to the synthesis of shape-controlled noble

  2. Chemically enhancing block copolymers for block-selective synthesis of self-assembled metal oxide nanostructures.

    PubMed

    Kamcev, Jovan; Germack, David S; Nykypanchuk, Dmytro; Grubbs, Robert B; Nam, Chang-Yong; Black, Charles T

    2013-01-22

    We report chemical modification of self-assembled block copolymer thin films by ultraviolet light that enhances the block-selective affinity of organometallic precursors otherwise lacking preference for either copolymer block. Sequential precursor loading and reaction facilitate formation of zinc oxide, titanium dioxide, and aluminum oxide nanostructures within the polystyrene domains of both lamellar- and cylindrical-phase modified polystyrene-block-poly(methyl methacrylate) thin film templates. Near-edge X-ray absorption fine structure measurements and Fourier transform infrared spectroscopy show that photo-oxidation by ultraviolet light creates Lewis basic groups within polystyrene, resulting in an increased Lewis base-acid interaction with the organometallic precursors. The approach provides a method for generating both aluminum oxide patterns and their corresponding inverses using the same block copolymer template.

  3. Amphiphilic graft copolymers with ethyl cellulose backbone: Synthesis, self-assembly and tunable temperature-CO2 response.

    PubMed

    Yuan, Weizhong; Zou, Hui; Shen, Jin

    2016-01-20

    Amphiphilic ethyl cellulose-graft-poly(N,N-dimethylaminoethyl methacrylate) (EC-g-PDMAEMA) and ethyl cellulose-graft-poly(2-(2-methoxyethoxy)ethyl methacrylate-co-N,N-dimethylaminoethyl methacrylate) (EC-g-P(MEO2MA-co-DMAEMA)) graft copolymers were easily synthesized by atom transfer radical polymerization (ATRP). The micelles self-assembled from the copolymer presented switchable temperature-CO2 dually responsive properties. The value of lower critical solution temperature (LCST) for the copolymer micelle solutions could be adjusted by CO2/Ar. Moreover, due to the alteration of the ratio of DMAEMA to MEO2MA, the LCST values of the micelle solutions decreased with the increase of MEO2MA in copolymer. The temperature-CO2 dually responsive properties of the copolymer were reversible and could be accomplished through altering the temperature and bubbling CO2/Ar. The hydrodynamic radius (Rh) of the copolymer micelles was also influenced by the ratio of DMAEMA to MEO2MA and the stimuli of temperature and CO2/Ar. As a drug release system, the copolymer micelles could achieve the control release of doxorubicin (DOX) by changing the temperature and alternatively bubbling CO2/Ar.

  4. Block-copolymer-induced structure formation in microemulsions

    SciTech Connect

    Hilfiker, R.; Eicke, H.F.; Steeb, C.; Hofmeier, U. )

    1991-02-07

    Transient electric birefringence measurements were performed on water/AOT (sodium bis(2-ethylhexyl) sulfosuccinate)/isooctane microemulsions with various amounts of block-copoly(oxyethylene/isoprene/oxyethylene) added. The authors could show that addition of the copolymer leads to a formation of nanodroplet (ND)-copolymer-aggregates. The contributions of NDs and aggregates to the induced birefringence could easily be separated because the NDs exhibited a negative and the aggregates a positive induced birefringence and because the time scales corresponding to the two processes were different.

  5. Nanostructured anion conducting block copolymer electrolyte thin films

    NASA Astrophysics Data System (ADS)

    Arges, Christopher; Kambe, Yu; Nealey, Paul

    Lamellae forming block copolymer electrolyte (BCE) thin-films with perpendicular aligned orientation were registered with high fidelity over large areas via a self-assembly process followed by a novel chemical vapor infiltration reaction (CVIR) technique. In this scheme, poly(styrene- b-2-vinyl pyridine) (PS bP2VP) block copolymers were self-assembled with perpendicular orientations on neutral chemical brushes using solvent vapor annealing. The ionic groups were selectively introduced into the P2VP block via a Menshutkin reaction that converted the nitrogen in the pyridine to n-methylpyridinium - anion carrier groups. FTIR-ATR and XPS tools confirmed the formation of the aforementioned ionic moieties post CVIR process and structure imaging tools (e.g., SEM and AFM imaging, GI-SAXS and RSOXs) established that incorporation of the ionic groups did not alter the self-assembled nanostructured films nor did subsequent ion-exchange processes. Electrochemical impedance spectroscopy determined the in-plane ion conductivity of different counteranions in the BCE thin films and alteration to the symmetry of the block copolymer film substantially improved (or hindered) BCE ion conductivity if the P2VP block's volume fraction was slightly greater than (or less than) 0.5. U.S. Department of Energy, Office of Science under Contract No. DE-AC02-06CH11357.

  6. Formation and Characterization of Anisotropic Block Copolymer Gels

    NASA Astrophysics Data System (ADS)

    Liaw, Chya Yan; Joester, Derk; Burghardt, Wesley; Shull, Kenneth

    2012-02-01

    Cylindrical micelles formed from block copolymer solutions closely mimic biological fibers that are presumed to guide mineral formation during biosynthesis of hard tissues like bone. The goal of our work is to use acrylic block copolymers as oriented templates for studying mineral formation reactions in model systems where the structure of the underlying template is well characterized and reproducible. Self-consistent mean field theory is first applied to investigate the thermodynamically stable micellar morphologies as a function of temperature and block copolymer composition. Small-angle x-ray scattering, optical birefringence and shear rheometry are used to study the morphology development during thermal processing. Initial experiments are based on a thermally-reversible alcohol-soluble system that can be converted to an aqueous gel by hydrolysis of a poly(t-butyl methacrylate) block to a poly(methacrylic acid) block. Aligned cylindrical domains are formed in the alcohol-based system when shear is applied in an appropriate temperature regime, which is below the critical micelle temperature but above the temperature at which the relaxation time of the gels becomes too large. Processing strategies for producing the desired cylindrical morphologies are being developed that account for both thermodynamic and kinetic effects.

  7. Preparation of biocompatible zwitterionic block copolymer vesicles by direct dissolution in water and subsequent silicification within their membranes.

    PubMed

    Du, Jianzhong; Armes, Steven P

    2009-08-18

    The facile preparation of block copolymer vesicles in pure water and their subsequent stabilization by sol-gel chemistry within the vesicle membrane is described. An amphiphilic biocompatible zwitterionic diblock copolymer, poly(epsilon-caprolactone)-block-poly[2-(methacryloyloxy)ethyl phosphorylcholine], PCL-b-PMPC, was synthesized by (i) ring-opening polymerization of epsilon-caprolactone, (ii) end-group modification by esterification, and (iii) atom transfer radical polymerization (ATRP) of 2-(methacryloyloxy)ethyl phosphorylcholine (MPC). Unusually, block copolymer vesicles were formed instantly upon adding dried copolymer powder into hot water without using organic cosolvents, pH adjustment, or even stirring. This protocol is much more convenient than previously reported methods such as solvent-switching and film rehydration. The PCL vesicle membrane is moderately hydrophobic and fully biodegradable. The highly biocompatible PMPC chains are expressed on both the exterior and interior surface of the membrane. These vesicles can be stabilized by aqueous sol-gel chemistry within the hydrophobic PCL vesicle membrane by using tetramethyl orthosilicate (TMOS) as the silica precursor in the absence of any external catalyst. The water-immiscible TMOS precursor is initially solubilized within the hydrophobic membrane prior to its in situ transformation into silica. The vesicles were characterized by 1H NMR spectroscopy, atomic force microscopy, transmission electron microscopy, and dynamic light scattering.

  8. Amphiphilic, cross-linkable diblock copolymers for multifunctionalized nanoparticles as biological probes

    NASA Astrophysics Data System (ADS)

    Schmidtke, Christian; Pöselt, Elmar; Ostermann, Johannes; Pietsch, Andrea; Kloust, Hauke; Tran, Huong; Schotten, Theo; Bastús, Neus G.; Eggers, Robin; Weller, Horst

    2013-07-01

    Nanoparticles (NPs) play an increasingly important role in biological labeling and imaging applications. However, preserving their useful properties in an aqueous biological environment remains challenging, even more as NPs therein have to be long-time stable, biocompatible and nontoxic. For in vivo applications, size control is crucial in order to route excretion pathways, e.g. renal clearance vs. hepato-biliary accumulation. Equally necessary, cellular and tissue specific targeting demands suitable linker chemistry for surface functionalization with affinity molecules, like peptides, proteins, carbohydrates and nucleotides. Herein, we report a three stage encapsulation process for NPs comprised of (1) a partial ligand exchange by a multidentate polyolefinic amine ligand, PI-N3, (2) micellar encapsulation with a precisely tuned amphiphilic diblock PI-b-PEG copolymer, in which the PI chains intercalate to the PI-N3 prepolymer and (3) radical cross-linking of the adjacent alkenyl bonds. As a result, water-soluble NPs were obtained, which virtually maintained their primal physical properties and were exceptionally stable in biological media. PEG-terminal functionalization of the diblock PI-b-PEG copolymer with numerous functional groups was mostly straightforward by chain termination of the living anionic polymerization (LAP) with the respective reagents. More complex affinity ligands, e.g. carbohydrates or biotin, were introduced in a two-step process, prior to micellar encapsulation. Advantageously, this pre-assembly approach opens up rapid access to precisely tuned multifunctional NPs, just by using mixtures of diverse functional PI-b-PEG polymers in a combinatorial manner. All constructs showed no toxicity from 0.001 to 1 μM (particle concentration) in standard WST and LDH assays on A549 cells, as well as only marginal unspecific cellular uptake, even in serum-free medium.Nanoparticles (NPs) play an increasingly important role in biological labeling and imaging

  9. Nanopatterned barium titanate on block copolymers

    NASA Astrophysics Data System (ADS)

    Lee, Tu

    This dissertation describes the synthesis, the characterization and the modeling of a triblock copolymer of polystyrene(PS)-polybutadiene(PB)-polystyrene(PS) monolayer thin film patterned with nanometer sized cubic BaTiO3 crystals, with a focus on the influence of length scales and the hierarchical structure on the ferroelectric properties of BaTiO3. BaTiO3, a dielectric and a ferroelectric, is used extensively in multilayer capacitors, thermistors and electrooptic devices. Its ferroelectric properties are known to be size dependent in the nanometer scale. To gain further insight into the fundamental characteristics of BaTiO3 in the nanometer scale, BaTiO3 is crystallized, for the first time, in a confined environment hosted by a PS-PB-PS triblock copolymer monolayer thin film with nanodomains of tunable geometry and size. The engineering of the PS-PB-PS triblock copolymer monolayer thin film includes fractionation, elimination of interfacial interaction, control of film thickness and minimization of pinholes. The resulting monolayer contains cylindrical PS nanodomains embedded in a PB matrix. The film thickness, the diameter of the PS domain and the domain center-to-domain center distance are 31 nm, 15 nm and 31 nm respectively. Cubic BaTiO3 nanoparticles having a narrow size distribution of 10 nm are formed and located predominantly within the PB matrices by three steps: epoxidation-hydroxylation, barium titanation and vapor-phase hydrothermal process. The volume fraction of BaTiO3 phase is 0.0113. The effective dielectric constant of the BaTiO3/PS-PB-PS composite monolayer is 5.5 +/- 2.5. With the assistance of dielectric mixing rules, the dielectric constant of the cubic BaTiO3 phase is determined to be 160. The relative low dielectric constant of the BaTiO3 phase is usually explained by the critical size above which BaTiO3 particles are tetragonal and ferroelectric and below which particles are cubic and non-ferroelectric. But, the inconsistency of the

  10. Nonionic block copolymers assemble on the surface of protein bionanoparticle.

    PubMed

    Liu, Zhi; Gu, Jingxia; Wu, Man; Jiang, Shidong; Wu, Dayong; Wang, Qian; Niu, Zhongwei; Huang, Yong

    2012-08-21

    Efficient delivery of therapeutic proteins to a target site remains a challenge due to rapid clearance from the body. Here, we selected tobacco mosaic virus (TMV) as a model protein system to investigate the interactions between the protein and a nonionic block copolymer as a possible protecting agent for the protein. By varying the temperature, we were able to obtain core-shell structures based on hydrophobic interactions among PO blocks and noncovalent interactions between TMV and EO blocks. The protein-polymer interactions were characterized by dynamic light scattering and isothermal titration calorimetry. This study establishes principles for the possible design of clinically useful protein delivery systems.

  11. Oil industry wastewater treatment with fouling resistant membranes containing amphiphilic comb copolymers.

    PubMed

    Asatekin, Ayse; Mayes, Anne M

    2009-06-15

    The oil industry produces large volumes of wastewater, including oil well produced water brought to the surface during oil drilling, and refinery wastewater. These streams are difficult to treat due to large concentrations of oil. Ultrafiltration (UF) is very promising for their treatment to remove oil, but has been limited by economic obstacles due to severe membrane fouling. In a recent study, novel UF membranes incorporating the amphiphilic comb copolymer additive polyacrylonitrile-graft-poly(ethylene oxide), PAN-g-PEO, were found to exhibit complete resistance to irreversible fouling by several classes of organic foulants (J. Membr. Sci. 2007, 298, 136-146). The current work focuses on application of these novel UF membranes to the treatment of oily wastewater feed streams, employing three industrial samples of oil well produced water and refinery wastewater. UF membranes cast with 20 wt % PAN-g-PEO in PAN achieved removals of dispersed and free oils of over 96% based on chemical oxygen demand (COD) for produced water samples, comparable to a PAN UF commercial membrane control. For refinery wastewater treatment the COD removal values were substantially lower, between 41 and 44%, due to higher contents of dissolved organics. Comb copolymer modified membranes showed significantly better fouling resistance than controls, recovering fully their initial fluxes after a simulated backwash for each of the three wastewater samples tested. The results indicate that UF membranes incorporating PAN-g-PEO can be cleaned completely by physical methods alone, which should extend membrane lifetimes substantially and improve the process economics for treatment of oil-contaminated waters.

  12. Oil industry wastewater treatment with fouling resistant membranes containing amphiphilic comb copolymers.

    PubMed

    Asatekin, Ayse; Mayes, Anne M

    2009-06-15

    The oil industry produces large volumes of wastewater, including oil well produced water brought to the surface during oil drilling, and refinery wastewater. These streams are difficult to treat due to large concentrations of oil. Ultrafiltration (UF) is very promising for their treatment to remove oil, but has been limited by economic obstacles due to severe membrane fouling. In a recent study, novel UF membranes incorporating the amphiphilic comb copolymer additive polyacrylonitrile-graft-poly(ethylene oxide), PAN-g-PEO, were found to exhibit complete resistance to irreversible fouling by several classes of organic foulants (J. Membr. Sci. 2007, 298, 136-146). The current work focuses on application of these novel UF membranes to the treatment of oily wastewater feed streams, employing three industrial samples of oil well produced water and refinery wastewater. UF membranes cast with 20 wt % PAN-g-PEO in PAN achieved removals of dispersed and free oils of over 96% based on chemical oxygen demand (COD) for produced water samples, comparable to a PAN UF commercial membrane control. For refinery wastewater treatment the COD removal values were substantially lower, between 41 and 44%, due to higher contents of dissolved organics. Comb copolymer modified membranes showed significantly better fouling resistance than controls, recovering fully their initial fluxes after a simulated backwash for each of the three wastewater samples tested. The results indicate that UF membranes incorporating PAN-g-PEO can be cleaned completely by physical methods alone, which should extend membrane lifetimes substantially and improve the process economics for treatment of oil-contaminated waters. PMID:19603666

  13. One-pot glovebox-free synthesis, characterization, and self-assembly of novel amphiphilic poly(sarcosine-b-caprolactone) diblock copolymers.

    PubMed

    Cui, Saide; Wang, Xin; Li, Zhenjiang; Zhang, Qiguo; Wu, Wenzhuo; Liu, Jingjing; Wu, Hao; Chen, Cheng; Guo, Kai

    2014-11-01

    Novel amphiphilic polypeptoid-polyester diblock copolymers based on poly(sarcosine) (PSar) and poly(ε-caprolactone) (PCL) are synthesized by a one-pot glovebox-free approach. In this method, sarcosine N-carboxy anhydride (Sar-NCA) is firstly polymerized in the presence of benzylamine under N(2) flow, then the resulting poly(sarcosine) is used in situ as the macro-initiator for the ring-opening polymerization (ROP) of ε-caprolactone using tin(II) octanoate as a catalyst. The degree of poly-merization of each block is controlled by various feed ratios of monomer/initiator. The diblock copolymers with controlled molecular weight and narrow molecular weight distributions (Đ(M) < 1.2) are characterized by (1)H NMR, (13)C NMR, and size-exclusion chromatography. The self-assembly behavior of PSar-b-PCL in water is investigated by dynamic light scattering (DLS) and transmission electron microscopy. DLS results reveal that the diblock copolymers associate into nanoparticles with average hydrodynamic diameters (D(H)) around 100 nm in water, which may be used as drug delivery carriers.

  14. One-pot glovebox-free synthesis, characterization, and self-assembly of novel amphiphilic poly(sarcosine-b-caprolactone) diblock copolymers.

    PubMed

    Cui, Saide; Wang, Xin; Li, Zhenjiang; Zhang, Qiguo; Wu, Wenzhuo; Liu, Jingjing; Wu, Hao; Chen, Cheng; Guo, Kai

    2014-11-01

    Novel amphiphilic polypeptoid-polyester diblock copolymers based on poly(sarcosine) (PSar) and poly(ε-caprolactone) (PCL) are synthesized by a one-pot glovebox-free approach. In this method, sarcosine N-carboxy anhydride (Sar-NCA) is firstly polymerized in the presence of benzylamine under N(2) flow, then the resulting poly(sarcosine) is used in situ as the macro-initiator for the ring-opening polymerization (ROP) of ε-caprolactone using tin(II) octanoate as a catalyst. The degree of poly-merization of each block is controlled by various feed ratios of monomer/initiator. The diblock copolymers with controlled molecular weight and narrow molecular weight distributions (Đ(M) < 1.2) are characterized by (1)H NMR, (13)C NMR, and size-exclusion chromatography. The self-assembly behavior of PSar-b-PCL in water is investigated by dynamic light scattering (DLS) and transmission electron microscopy. DLS results reveal that the diblock copolymers associate into nanoparticles with average hydrodynamic diameters (D(H)) around 100 nm in water, which may be used as drug delivery carriers. PMID:25283643

  15. Simple, generalizable route to highly aligned block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Qiang, Zhe; Cavicchi, Kevin; Vogt, Bryan; University of Akron Team

    Macroscopic alignment of block copolymer domains in thin films is desired for many applications, such as cell responsive surfaces or optical polarizers. Alignment generally requires specialized tools that apply external fields, shear force gradient, or produce topological patterned substrates. This requirement limits the broad academic application of aligned BCPs. Here, we describe a simple modification of commonly utilized solvent vapor annealing (SVA) process for macroscopic alignment of BCPs. Adhering a flat, crosslinked elastomer pad to the BCP film leads to differential swelling between the elastomer pad and BCP to produce a shear force that aligns the ordered BCP domains. The role of elastomer properties, solvent quality, drying rate and degree of segregation of the block copolymer will be discussed to provide generalized rules for alignment with this technique. Cylindrical nanostructures formed in polystyrene-block-polydimethylsiloxane can be transformed into arrays of silica lines and increasing the thickness from a monolayer to bilayer can effectively halve the spacing of the lines. These results illustrate a generalized method for BCP alignment and a potential route for the generation of complex hierarchical assembled structures. A generalized method for block copolymer thin film alignment: solvent vapor annealing with shear.

  16. Design of block copolymer templated solid state batteries

    NASA Astrophysics Data System (ADS)

    Bullock, Steven Edward

    The advent of portable electronics has placed a great demand on the power requirements of battery systems. High power batteries for small devices, such as cell phones, laptop computers, and personal data assistants (PDA's) have focused primarily on lithium ion batteries. With the introduction of large flexible panel displays, the need for a flexible battery system is apparent. Ring Opening Metathesis Polymerization (ROMP) is a facile method for synthesizing block copolymers with polar functional groups. These functional groups allow the formation of metal oxide clusters via a template of the microphase separated block copolymer domains. In this thesis, the synthesis of a flexible polymer battery system is described. Diblock copolymers of an ionically conductive unsaturated polyethylene oxide block with a carboxylic acid functionalized block were synthesized and characterized with NMR, IR and Gel Permeation Chromatography (GPC). Characterization of polymer templated LiMn2O 4 clusters and nanocomposites synthesized for the study have a distributed cluster morphology within the polymer matrix. The nanocomposites were analyzed with transmission electron microscopy to determine the morphology of the nanocomposites. Battery performance was characterized with cyclic voltammetry and galvanostatic charge/discharge cycling for power capacity. The ionic conductivity was measured with impedance spectroscopy. The novel room temperature templating strategy used for the synthesis of these ionically conductive nanocomposites requires no thermal cycling steps. This makes it attractive for processing of sheet structures to power flexible displays.

  17. Reordering transitions during annealing of block copolymer cylinder phases

    DOE PAGES

    Majewski, Pawel W.; Yager, Kevin G.

    2015-10-06

    While equilibrium block-copolymer morphologies are dictated by energy-minimization effects, the semi-ordered states observed experimentally often depend on the details of ordering pathways and kinetics. In this study, we explore reordering transitions in thin films of block-copolymer cylinder-forming polystyrene-block-poly(methyl methacrylate). We observe several transient states as films order towards horizontally-aligned cylinders. In particular, there is an early-stage reorganization from randomly-packed cylinders into hexagonally-packed vertically-aligned cylinders; followed by a reorientation transition from vertical to horizontal cylinder states. These transitions are thermally activated. The growth of horizontal grains within an otherwise vertical morphology proceeds anisotropically, resulting in anisotropic grains in the final horizontalmore » state. The size, shape, and anisotropy of grains are influenced by ordering history; for instance, faster heating rates reduce grain anisotropy. These results help elucidate aspects of pathway-dependent ordering in block-copolymer thin films.« less

  18. Synthesis of amphiphilic copolymers containing zwitterionic sulfobetaine as pH and redox responsive drug carriers.

    PubMed

    Cai, Mengtan; Leng, Mengtian; Lu, Aijing; He, Liu; Xie, Xiaoxiong; Huang, Lei; Ma, Yuhao; Cao, Jun; Chen, Yuanwei; Luo, Xianglin

    2015-02-01

    Amphiphilic poly(ɛ-caprolactone)-SS-poly(N,N-diethylaminoethyl methacrylate)-r-poly(N-(3-sulfopropyl)-N-methacrylate-N,N-diethylammonium-betaine) (PCL-SS-PDEASB) was designed and synthesized successfully. pH and redox dually responsive micelles were prepared based on the obtained copolymers, with zwitterionic sulfobetaines as hydrophilic shell, DEA as pH sensitive content and disulfide as redox responsive linkage. The micelle diameters were all less than 200 nm and the micelle diameter distributions were narrow. These micelles could be triggered by pH and redox condition. The drug release from the drug-loaded micelles displayed fastest under simultaneously acidic and reductive conditions. Results of in vitro cell toxicity evaluation showed that introduction of sulfobetaines could greatly decrease the toxicity of poly(ɛ-caprolactone)-SS-poly(N,N-diethylaminoethyl methacrylate) (PCL-SS-PDEA) micelles. DOX-loaded PCL-SS-PDEASB micelles showed higher efficiency to kill HeLa cells than DOX-loaded PCL-PDEASB micelles. Half inhibitory concentration (IC50) of DOX-loaded PCL-SS-PDEASB micelles decreased with the content of sulfobetaines increasing and was even closer to that of DOX·HCl. Thus, the pH and redox dually responsive biodegradable micelles generated by PCL-SS-PDEASB may be potential smart drug carriers for tumor targeted delivery. PMID:25531063

  19. Dissipative particle dynamics simulation study on vesicles self-assembled from amphiphilic hyperbranched multiarm copolymers.

    PubMed

    Wang, Yuling; Li, Bin; Jin, Haibao; Zhou, Yongfeng; Lu, Zhongyuan; Yan, Deyue

    2014-08-01

    Hyperbranched multiarm copolymers (HMCs) have been shown to hold great potential as precursors in self-assembly, and many impressive supramolecular structures have been prepared through the self-assembly of HMCs in solution. However, theoretical studies on the corresponding self-assembly mechanism have been greatly lagging behind. Herein, we report the self-assembly of normal or reverse vesicles from amphiphilic HMCs by dissipative particle dynamics (DPD) simulation. The simulation disclosed both the self-assembly mechanisms and dynamics of vesicles. It indicates that the self-assembly of HMCs involves several steps, from randomly distributed unimolecular micelles to small spherical micelles, to membrane-like micelles, to finally small vesicles. The membranes are formed through the direct aggregation and lateral fusion of small micelles, and the bending and closing of the membranes give rise to small vesicles. Finally, large and steady vesicles are formed through the fusion of small vesicles. In addition, the bilayer or monolayer molecular packing modes as well as the mircrophase separation behaviors of HMCs in normal or reverse vesicles have also been studied. These simulation results explore details that cannot be observed in the experiments to a certain degree, and have extended the understanding of the vesicular self-assembly process of HMCs.

  20. Iron nanoparticles coated with amphiphilic polysiloxane graft copolymers: dispersibility and contaminant treatability.

    PubMed

    Krajangpan, Sita; Kalita, Harjyoti; Chisholm, Bret J; Bezbaruah, Achintya N

    2012-09-18

    Amphiphilic polysiloxane graft copolymers (APGCs) were used as a delivery vehicle for nanoscale zerovalent iron (NZVI). The APGCs were designed to enable adsorption onto NZVI surfaces via carboxylic acid anchoring groups and polyethylene glycol (PEG) grafts were used to provide dispersibility in water. Degradation studies were conducted with trichloroethylene (TCE) as the model contaminant. TCE degradation rate with APGC-coated NZVI (CNZVI) was determined to be higher as compared to bare NZVI. The surface normalized degradation rate constants, k(SA) (Lm(2-) h(-1)), for TCE removal by CNZVI and bare NZVI ranged from 0.008 to 0.0760 to 007-0.016, respectively. Shelf life studies conducted over 12 months to access colloidal stability and 6 months to access TCE degradation indicated that colloidal stability and chemical reactivity of CNZVI remained more or less unchanged. The sedimentation characteristics of CNZVI under different ionic strength conditions (0-10 mM) did not change significantly. The steric nature of particle stabilization is expected to improve aquifer injection efficiency of the coated NZVI for groundwater remediation.

  1. Periodic nanostructures from self assembled wedge-type block-copolymers

    DOEpatents

    Xia, Yan; Sveinbjornsson, Benjamin R.; Grubbs, Robert H.; Weitekamp, Raymond; Miyake, Garret M.; Piunova, Victoria; Daeffler, Christopher Scot

    2015-06-02

    The invention provides a class of wedge-type block copolymers having a plurality of chemically different blocks, at least a portion of which incorporates a wedge group-containing block providing useful properties. For example, use of one or more wedge group-containing blocks in some block copolymers of the invention significantly inhibits chain entanglement and, thus, the present block copolymers materials provide a class of polymer materials capable of efficient molecular self-assembly to generate a range of structures, such as periodic nanostructures and microstructures. Materials of the present invention include copolymers having one or more wedge group-containing blocks, and optionally for some applications copolymers also incorporating one or more polymer side group-containing blocks. The present invention also provides useful methods of making and using wedge-type block copolymers.

  2. The influence of block copolymers on silica-filled polyisoprene

    NASA Astrophysics Data System (ADS)

    Gurovich, Daniel

    2001-10-01

    In the present work, precipitated silica, liquid polyisoprene, and poly(dimethyl siloxane-co-isoprene) block copolymer (PDMS-PI) are mixed in different formulations. The dynamic rheological properties of the resulting uncured materials are measured and used to assess filler-filler networking. In small-amplitude tests, composites containing PDMS-PI exhibit lower values of the dynamic storage modulus (G') than those observed in control samples prepared without copolymer additives. The control samples remain stable during several months of storage, while most of the samples containing low molecular weight block copolymers show evidence of an aging process. The only sample that showed no evidence of aging contained PDMS-PI of the highest molecular weight used in the study (42 kg/mol). The rheological manifestations of the aging process include a pronounced decrease in small-amplitude G' with time, accompanied by weakening amplitude dependence of both G' and G ″. These suggest a progressive reduction of filler-filler interactions, presumably caused by the development of a block copolymer layer at the filler-polymer interface. The make-up of that interfacial region is investigated by means of magic-angle spinning solid-state proton NMR experiments carried out on bound polymer fractions that survive extraction in a good solvent. Spin-spin relaxation times and the intensities of the relaxation modes associated with these characteristic times are used to identify the proportion of both PDMS and polyisoprene among the segments strongly immobilized by close contact with the silica surface and among the rest of the bound (un-extracted) interfacial layer. The changes in mechanical properties are correlated not with the overall composition of the bound polymer fraction, but with the increase in PDMS segments in close contact with the filler surface. At low block copolymer concentrations the rate of segregation of PDMS segments towards the silica surface is determined by the

  3. In vitro controlled release of clove essential oil in self-assembly of amphiphilic polyethylene glycol-block-polycaprolactone.

    PubMed

    Thonggoom, O; Punrattanasin, N; Srisawang, N; Promawan, N; Thonggoom, R

    2016-05-01

    In this study, a micellar delivery system with an amphiphilic diblock copolymer of poly (ethylene glycol) and poly (ɛ-caprolactone) was synthesised and used to incorporate hydrophobic clove essential oil (CEO). To determine an optimal delivery system, the effects of the copolymer's hydrophobic block length and the CEO-loading content on the encapsulation of CEO were investigated. Percentages of entrapment efficiency (%EE), CEO loading (%CEO), and in vitro release profiles were determined. The size, size distribution, zeta potential, and morphology of the obtained micelles were determined by DLS, FE-SEM, and TEM. The %EE, %CEO, and in vitro release profiles of CEO incorporated in micelles were analysed by HPLC. The study revealed a sustained release profile of CEO from CEO-loaded micelles. The results indicate the successful formulation of CEO-loaded PEG-b-PCL micelle nanoparticles. It is suggested that this micelle system has considerably potential applications in the sustained release of CEO in intravascular drug delivery. PMID:26988617

  4. Magnetic alignment of block copolymer microdomains by intrinsic chain anisotropy

    SciTech Connect

    Rokhlenko, Yekaterina; Yager, Kevin G.; Gopinadhan, Manesh; Osuji, Chinedum O.; Zhang, Kai; O'Hern, Corey S.; Larson, Steven R.; Gopalan, Padma; Majewski, Pawel W.

    2015-12-18

    We examine the role of intrinsic chain susceptibility anisotropy in magnetic field directed self-assembly of a block copolymer using in situ x-ray scattering. Alignment of a lamellar mesophase is observed on cooling across the disorder-order transition with the resulting orientational order inversely proportional to the cooling rate. We discuss the origin of the susceptibility anisotropy, Δχ, that drives alignment and calculate its magnitude using coarse-grained molecular dynamics to sample conformations of surface-tethered chains, finding Δχ ≈ 2×10–8. From field-dependent scattering data, we estimate that grains of ≈ 1.2 μm are present during alignment. Furthermore, these results demonstrate that intrinsic anisotropy is sufficient to support strong field-induced mesophase alignment and suggest a versatile strategy for field control of orientational order in block copolymers.

  5. Magnetic alignment of block copolymer microdomains by intrinsic chain anisotropy

    DOE PAGES

    Rokhlenko, Yekaterina; Yager, Kevin G.; Gopinadhan, Manesh; Osuji, Chinedum O.; Zhang, Kai; O'Hern, Corey S.; Larson, Steven R.; Gopalan, Padma; Majewski, Pawel W.

    2015-12-18

    We examine the role of intrinsic chain susceptibility anisotropy in magnetic field directed self-assembly of a block copolymer using in situ x-ray scattering. Alignment of a lamellar mesophase is observed on cooling across the disorder-order transition with the resulting orientational order inversely proportional to the cooling rate. We discuss the origin of the susceptibility anisotropy, Δχ, that drives alignment and calculate its magnitude using coarse-grained molecular dynamics to sample conformations of surface-tethered chains, finding Δχ ≈ 2×10–8. From field-dependent scattering data, we estimate that grains of ≈ 1.2 μm are present during alignment. Furthermore, these results demonstrate that intrinsic anisotropymore » is sufficient to support strong field-induced mesophase alignment and suggest a versatile strategy for field control of orientational order in block copolymers.« less

  6. Self-assembled phases of block copolymer blend thin films.

    PubMed

    Yager, Kevin G; Lai, Erica; Black, Charles T

    2014-10-28

    The patterns formed by self-assembled thin films of blended cylindrical and lamellar polystyrene-b-poly(methyl methacrylate) block copolymers can be either a spatially uniform, single type of nanostructure or separate, coexisting regions of cylinders and lamellae, depending on fractional composition and molecular weight ratio of the blend constituents. In blends of block copolymers with different molecular weights, the morphology of the smaller molecular weight component more strongly dictates the resulting pattern. Although molecular scale chain mixing distorts microdomain characteristic length scales from those of the pure components, even coexisting morphologies exhibit the same domain spacing. We quantitatively account for the phase behavior of thin-film blends of cylinders and lamellae using a physical, thermodynamic model balancing the energy of chain distortions with the entropy of mixing. PMID:25285733

  7. Magnetic Alignment of Block Copolymer Microdomains by Intrinsic Chain Anisotropy

    NASA Astrophysics Data System (ADS)

    Rokhlenko, Yekaterina; Gopinadhan, Manesh; Osuji, Chinedum O.; Zhang, Kai; O'Hern, Corey S.; Larson, Steven R.; Gopalan, Padma; Majewski, Paweł W.; Yager, Kevin G.

    2015-12-01

    We examine the role of intrinsic chain susceptibility anisotropy in magnetic field directed self-assembly of a block copolymer using in situ x-ray scattering. Alignment of a lamellar mesophase is observed on cooling across the disorder-order transition with the resulting orientational order inversely proportional to the cooling rate. We discuss the origin of the susceptibility anisotropy, Δ χ , that drives alignment and calculate its magnitude using coarse-grained molecular dynamics to sample conformations of surface-tethered chains, finding Δ χ ≈2 ×1 0-8. From field-dependent scattering data, we estimate that grains of ≈1.2 μ m are present during alignment. These results demonstrate that intrinsic anisotropy is sufficient to support strong field-induced mesophase alignment and suggest a versatile strategy for field control of orientational order in block copolymers.

  8. Beyond Orientation: The Impact of Electric Fields on Block Copolymers

    SciTech Connect

    Liedel, Clemens; Boker, A.; Pester, Christian; Ruppel, Markus A; Urban, Volker S

    2012-01-01

    Since the first report on electric field-induced alignment of block copolymers (BCPs) in 1991, electric fields have been shown not only to direct the orientation of BCP nanostructures in bulk, solution, and thin films, but also to reversibly induce order-order transitions, affect the order-disorder transition temperature, and control morphologies' dimensions with nanometer precision. Theoretical and experimental results of the past years in this very interesting field of research are summarized and future perspectives are outlined.

  9. Dispersion characteristics of nanocomposites based on functionalized block copolymers

    NASA Astrophysics Data System (ADS)

    Ke, Linping

    The dispersion characteristics of organoclay nanocomposites based on functionalized block copolymers have been investigated. For the investigation, polystyrene-block-polybutadiene (SB diblock) copolymers synthesized via anionic polymerization were first hydroxylated via hydroboration/oxidation to obtain polystyrene-block-hydroxylated polybutadiene (SBOH diblock) copolymers. Then, the SBOH diblock copolymer was attached with pyridine, pyrimidine, terpyridine, or terpyridine-Ruthenium (Ru) complex functional groups to obtain SB-pyridine, SB-pyrimidine, SB-terpyridine (SB-Terpy), and SB-Terpy-Ru complex diblock copolymers. Subsequently, each of these functionalized block copolymers was used to prepare, via solution blending, organoclay nanocomposites, for which natural clay (montmorillonite, MMT) and two commercial organoclays (Cloisite 30B and Cloisite 15A) were employed. The dispersion characteristics of the organoclay nanocomposites were investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM), and oscillatory rheometry (OR). We have made the following observations. The SBOH/Cloisite 30B nanocomposite had a very high degree of dispersion of Cloisite 30B aggregates, whereas the SBOH/Cloisite 15A and SBOH/MMT nanocomposites had a very low degree of dispersion of the aggregates of Cloisite 15A or MMT. In situ Fourier transform infrared (FTIR) spectroscopy has revealed that hydrogen bonds were formed between the hydroxyl groups in the SBOH diblock copolymer and the surfactant residing at the surface of Cloisite 30B in the former nanocomposite, yielding a very high degree of dispersion of Cloisite 30B aggregates, while no hydrogen bonds were formed in the latter two nanocomposites. The (SB-pyridine)/Cloisite 30B nanocomposite had intercalation of aggregates of Cloisite 30B, while the (SB-pyridine)/Cloisite 15A and (SB-pyridine)/MMT nanocomposites had a very low degree of dispersion of the aggregates of Cloisite 15A or MMT in the SB

  10. Proton Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan; Tyagi, Madhu; Reimer, Jeffrey; Segalman, Rachel

    2011-03-01

    Nanostructured block copolymer/ionic liquid mixtures are of interest for creating membranes having high proton conductivity coupled with high thermal stability. In these mixtures, it is anticipated that nanoconfinement to block copolymer domains will affect ionic liquid proton transport properties. Using pulsed-field gradient NMR and quasi-elastic neutron scattering, this relationship has been investigated for mixtures of poly(styrene-b- 2-vinylpyridine) (S2VP) with ionic liquids composed of imidazole and bis(trifluoromethane)sulfonimide (HTFSI), where the ionic liquids selectively reside in the P2VP domains of the block copolymer. Proton mobility is highest in the neat ionic liquids when there is an excess of imidazole compared to HTFSI due to proton hopping between hydrogen-bonded imidazoles. As predicted, the amount of proton hopping can be tuned by nanoconfinement, as evidenced by the finding that a lamellar mixture of an imidazole- excess ionic liquid with S2VP has greater proton mobility than a corresponding disordered mixture of the ionic liquid with P2VP homopolymer.

  11. Stereocomplex Formation in Incompatible Racemic Chiral Polylactide Block Copolymers

    NASA Astrophysics Data System (ADS)

    Sun, Lu; Zhu, Lei

    2006-03-01

    Stereocomplexes in incompatible racemic chiral polylactide (PLA) block copolymers have not been widely studied. In this work, we synthesized PLLA and PDLA containing block copolymers by ring opening polymerization of L- and D-lactides from hydroxyl-terminated hydrophilic [poly(ethylene oxide) (PEO)] and hydrophobic [poly(ethylene-co-1,2-butylene) (PEB)] oligomers, respectively. Two samples PEO-b-PLLA (2,000-5,400) and PEB-b-PDLA (4,200-5,400) were chosen. The stereocomplexes were cast from equal molar blends of above two block copolymers in chloroform solution, followed by two different thermal treatments before stereocomplex formation; The blend was either heated to 250 C and quickly quench to 160 C or heated to 250 C for 15 min and quench to 160 C for stereocomplex crystal growth. Before the formation of stereocomplexes, lamellar and cylindrical morphologies were observed in blends for the first and second thermal treatments, respectively, as evidenced by small-angle X-ray scattering (SAXS). After complete crystal growth, the 100% stereocomplexes was confirmed by differential scanning calorimetry and wide-angle X-ray diffraction (WAXD). The morphologies of stereocomplexes grown from these two pre-existing microphases (lamellar vs. cylindrical) were studied by time-resolved SAXS and transmission electron microscopy (TEM).

  12. Electrically Tunable Soft-Solid Block Copolymer Structural Color.

    PubMed

    Park, Tae Joon; Hwang, Sun Kak; Park, Sungmin; Cho, Sung Hwan; Park, Tae Hyun; Jeong, Beomjin; Kang, Han Sol; Ryu, Du Yeol; Huh, June; Thomas, Edwin L; Park, Cheolmin

    2015-12-22

    One-dimensional photonic crystals based on the periodic stacking of two different dielectric layers have been widely studied, but the fabrication of mechanically flexible polymer structural color (SC) films, with electro-active color switching, remains challenging. Here, we demonstrate free-standing electric field tunable ionic liquid (IL) swollen block copolymer (BCP) films. Placement of a polymer/ionic liquid film-reservoir adjacent to a self-assembled poly(styrene-block-quaternized 2-vinylpyridine) (PS-b-QP2VP) copolymer SC film allowed the development of red (R), green (G), and blue (B) full-color SC block copolymer films by swelling of the QP2VP domains by the ionic liquid associated with water molecules. The IL-polymer/BCP SC film is mechanically flexible with excellent color stability over several days at ambient conditions. The selective swelling of the QP2VP domains could be controlled by both the ratio of the IL to a polymer in the gel-like IL reservoir layer and by an applied voltage in the range of -3 to +6 V using a metal/IL reservoir/SC film/IL reservoir/metal capacitor type device.

  13. Ultralow Oil-Fouling Heterogeneous Poly(ether sulfone) Ultrafiltration Membrane via Blending with Novel Amphiphilic Fluorinated Gradient Copolymers.

    PubMed

    Zhang, Guangfa; Jiang, Jingxian; Zhang, Qinghua; Gao, Fan; Zhan, Xiaoli; Chen, Fengqiu

    2016-02-01

    A novel amphiphilic fluorinated gradient copolymer was prepared by semibatch reversible addition-fragmentation chain transfer (RAFT) method using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate (TFOA) as monomers. The resultant amphiphilic copolymers were then incorporated into the poly(ether sulfone) (PES) to fabricate PES blend membranes via the non-solvent-induced phase separation method (NIPS). During the phase inversion process, both hydrophilic (PEGMA) and low surface energy (TFOA) segments significantly enriched on the membrane surface by surface segregation to form an amphiphilic surface, which was demonstrated by surface wetting properties and X-ray photoelectron spectroscopy (XPS) measurements. According to the filtration experiments of oil-in-water emulsion, the heterogeneous membranes exhibited superior oil-fouling resistant properties, that is, low flux decay (as low as 15.4%) and high flux recovery (almost 100%), compared to the pure PES membrane. The synergistic effect of fouling-resistant and fouling-release mechanisms was found to be responsible for the excellent antifouling capacities. The findings of this study offer a facile and robust strategy for fabricating ultralow oil-fouling membranes that might be used for effective oil/water separation.

  14. Responsive block copolymer photonics triggered by protein-polyelectrolyte coacervation.

    PubMed

    Fan, Yin; Tang, Shengchang; Thomas, Edwin L; Olsen, Bradley D

    2014-11-25

    Ionic interactions between proteins and polyelectrolytes are demonstrated as a method to trigger responsive transitions in block copolymer (BCP) photonic gels containing one neutral hydrophobic block and one cationic hydrophilic block. Poly(2-vinylpyridine) (P2VP) blocks in lamellar poly(styrene-b-2-vinylpyridine) block copolymer thin films are quaternized with primary bromides to yield swollen gels that show strong reflectivity peaks in the visible range; exposure to aqueous solutions of various proteins alters the swelling ratios of the quaternized P2VP (QP2VP) gel layers in the PS-QP2VP materials due to the ionic interactions between proteins and the polyelectrolyte. Parameters such as charge density, hydrophobicity, and cross-link density of the QP2VP gel layers as well as the charge and size of the proteins play significant roles on the photonic responses of the BCP gels. Differences in the size and pH-dependent charge of proteins provide a basis for fingerprinting proteins based on their temporal and equilibrium photonic response. The results demonstrate that the BCP gels and their photonic effect provide a robust and visually interpretable method to differentiate different proteins.

  15. Effect of water uptake on morphology of polymerized ionic liquid block copolymers and random copolymers

    NASA Astrophysics Data System (ADS)

    Wang, Tsen-Shan; Ye, Yuesheng; Elabd, Yossef; Winey, Karen

    2012-02-01

    Dynamic studies of polymer morphology probe how the physical properties of polymerized ionic liquids are affected by the environment, such as temperature or moisture. For a series of poly(methyl methacrylate-b-1-[2-(methacryloyloxy)ethyl]-3-Butylimidazolium X^-) block and random copolymers with hydrophilic counterions (X^- = Br^-, HCO3^-, OH^-), the introduction of water vapor to the system can swell the ionic liquid block, causing enlarged hydrophilic domains and swollen channels for ion conduction. This expected expansion of ionic liquid domains in humid environments can be used to intelligently design these copolymers for use in technological applications. The effect of water vapor exposure in these imidazolium-based acrylate polymers is studied by small-angle X-ray scattering. These morphology results will be discussed alongside complementary studies of water uptake and ion conductivity.

  16. High χ block copolymers based on chemical modification of poly(t-butyl acrylate) containing block copolymers

    NASA Astrophysics Data System (ADS)

    Park, Sungmin; Jo, Seongjun; Lee, Yonghoon; Ryu, Chang Y.; Ryu, Du Yeol; Chun, Jun Sung

    2016-03-01

    We report the synthesis and characterization of novel block copolymer (BCP) materials for the directed self-assembly (DSA) nanolithography applications. Specifically, the poly(t-butyl acrylate) (PtBA) block in the styrenic block copolymers have been chemically modified to a fluorinated block for the enhancement of the BCP χ-parameters. dPSb- PtBA had been first synthesized by anionic polymerization to prepare a well-defined BCP precursor with narrow polydispersity for the fluorination of PtBA block. Then, the precursor BCP was chemically modified by transalcoholysis of the PtBA-block with 2,2,2-trifluoroethanol. This strategy offers the advantage of flexibility and controllability to tailor the χ-parameter, while maintaining the narrow molecular weight distribution of the BCP materials for the advanced lithography applications. The transmission electron microscopy/small angle x-ray scattering (TEM/SAXS) characterization results of the modified BCP consisting of poly(fluoroalkylate) and PS supported the development of highly ordered lamellar domains in bulk.

  17. Block copolymers for alkaline fuel cell membrane materials

    NASA Astrophysics Data System (ADS)

    Li, Yifan

    Alkaline fuel cells (AFCs) using anion exchange membranes (AEMs) as electrolyte have recently received considerable attention. AFCs offer some advantages over proton exchange membrane fuel cells, including the potential of non-noble metal (e.g. nickel, silver) catalyst on the cathode, which can dramatically lower the fuel cell cost. The main drawback of traditional AFCs is the use of liquid electrolyte (e.g. aqueous potassium hydroxide), which can result in the formation of carbonate precipitates by reaction with carbon dioxide. AEMs with tethered cations can overcome the precipitates formed in traditional AFCs. Our current research focuses on developing different polymer systems (blend, block, grafted, and crosslinked polymers) in order to understand alkaline fuel cell membrane in many aspects and design optimized anion exchange membranes with better alkaline stability, mechanical integrity and ionic conductivity. A number of distinct materials have been produced and characterized. A polymer blend system comprised of poly(vinylbenzyl chloride)-b-polystyrene (PVBC-b-PS) diblock copolymer, prepared by nitroxide mediated polymerization (NMP), with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) or brominated PPO was studied for conversion into a blend membrane for AEM. The formation of a miscible blend matrix improved mechanical properties while maintaining high ionic conductivity through formation of phase separated ionic domains. Using anionic polymerization, a polyethylene based block copolymer was designed where the polyethylene-based block copolymer formed bicontinuous morphological structures to enhance the hydroxide conductivity (up to 94 mS/cm at 80 °C) while excellent mechanical properties (strain up to 205%) of the polyethylene block copolymer membrane was observed. A polymer system was designed and characterized with monomethoxy polyethylene glycol (mPEG) as a hydrophilic polymer grafted through substitution of pendent benzyl chloride groups of a PVBC

  18. The effects of ethylene oxide containing lipopolymers and tri-block copolymers on lipid bilayers of dipalmitoylphosphatidylcholine.

    PubMed Central

    Baekmark, T R; Pedersen, S; Jørgensen, K; Mouritsen, O G

    1997-01-01

    A comparative study is conducted on the influence of two types of polymeric compounds on the phase behavior of 1,2-dihexadecanoyl-s,n-glycero-3-phosphotidylcholine (DC16PC) lipid bilayers. The first polymeric compound is a lipopolymer, with two different lengths of a hydrophilic polyethylene oxide moity, anchored to the bilayer by a 1,2-dioctadecanoyl-s,n-glycero-3-phosphoethanolamine (DC18PE) lipid. The second type, which is a novel type of membrane-spanning object, is an amphiphilic tri-block copolymer composed of two hydrophilic stretches of polyethylene oxide separated by a hydrophobic stretch of polystyrene. Hence the tri-block copolymer may act as a membrane-spanning macromolecule mimicking an amphiphilic protein or polypeptide. Differential scanning calorimetry is used to determine a partial phase diagram for the lipopolymer systems and to assess the amount of lipopolymer that can be loaded into DC16PC lipid bilayers before micellization takes place. Unilamellar and micellar phase structures are investigated by fluorescence quenching using bilayer permeating dithionite. The chain length-dependent critical lipopolymer concentration, denoting the lamellar-to-micellar phase transition, compares favorably with a theoretical prediction based on free-energy considerations involving bilayer cohesion and lateral pressure exerted by the polymer chains. Images FIGURE 10 PMID:9284315

  19. Biodegradable PELA block copolymers: in vitro degradation and tissue reaction.

    PubMed

    Younes, H; Nataf, P R; Cohn, D; Appelbaum, Y J; Pizov, G; Uretzky, G

    1988-01-01

    Degradation of, and tissue reaction elicited by a series of polyethylene oxide (PEO)/polylactic acid (PLA) PELA block copolymers were studied in vitro and in vivo. In particular, the effect of pH, temperature and enzymatic activity was addressed. The mass loss was faster, the more basic the media, while, expectedly, PELA copolymers degraded faster with the higher temperature. The addition of an enzyme (carboxylic ester hydrolase) had no effect. The degradation process strongly affected the mechanical properties of the materials under investigation, the elongation at break dropping drastically after two days of degradation. After seven days, only gross observation of the extensively degraded samples was possible. The in vivo studies compared the tissue reaction elicited by various PELA copolymers to that evoked by PLA. Evaluation of tissue reaction observed with a PELA sample after sterilization with gamma radiation showed acute inflammation with considerable dispersion of the material, 12 days after implantation. The granulomatous reaction observed with PELA copolymers after ethylene oxide sterilization was identical to the reaction observed with PLA. PMID:3064826

  20. Complex self-assembly of reverse poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) triblock copolymers with long hydrophobic and extremely lengthy hydrophilic blocks.

    PubMed

    Cambón, Adriana; Figueroa-Ochoa, Edgar; Juárez, Josué; Villar-Álvarez, Eva; Pardo, Alberto; Barbosa, Silvia; Soltero, J F Armando; Taboada, Pablo; Mosquera, Víctor

    2014-05-15

    Amphiphilic block copolymers have emerged during last years as a fascinating substrate material to develop micellar nanocontainers able to solubilize, protect, transport, and release under external or internal stimuli different classes of cargos to diseased cells or tissues. However, this class of materials can also induce biologically relevant actions, which complement the therapeutic activity of their cargo molecules through their mutual interactions with biologically relevant entities (cellular membranes, proteins, organelles...); these interactions at the same time, are regulated by the nature, conformation, and state of the copolymeric chains. For these reasons, in this paper we investigated the self-assembly process and physico-chemcial properties of two reverse triblock poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) block copolymers, BO14EO378BO14 and BO21EO385BO21, which have been recently found to be very useful as drug delivery nanovehicles and biological response modifiers under certain conditions (A. Cambón et al. Int. J. Pharm. 2013, 445, 47-57) in order to obtain a clear picture of the solution behavior of this class or block copolymers and to understand their biological activity. These block copolymers are characterized by possessing long BO blocks and extremely lengthy central EO ones, which provide them with a rich rheological behavior characterized by the formation of flowerlike micelles with sizes ranging from 20 to 40 nm in aqueous solution and the presence of intermicellar bridging even at low copolymers concentrations as denoted by atomic force microscopy. Bridging is also clearly observed by analyzing the rheological response of these block copolymers both storage and loss moduli upon changes on time, temperature, and or concentration. Strikingly, the relatively wide Poisson distribution of the polymeric chains make the present copolymers behave rather distinctly to conventional associative thickeners. The observed rich

  1. Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers

    PubMed Central

    2016-01-01

    Polymers that conduct protons in the hydrated state are of crucial importance in a wide variety of clean energy applications such as hydrogen fuel cells and artificial photosynthesis. Phosphonated and sulfonated polymers are known to conduct protons at low water content. In this paper, we report on the synthesis phosphonated peptoid diblock copolymers, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNeh-b-pNpm), with volume fractions of pNpm (ϕNpm) values ranging from 0.13 to 0.44 and dispersity (Đ) ≤ 1.0003. The morphologies of the dry block copolypeptoids were determined by transmission electron microscopy and in both the dry and hydrated states by synchrotron small-angle X-ray scattering. Dry samples with ϕNpm > 0.13 exhibited a lamellar morphology. Upon hydration, the lowest molecular weight sample transitioned to a hexagonally packed cylinder morphology, while the others maintained their dry morphologies. Water uptake of all of the ordered samples was 8.1 ± 1.1 water molecules per phosphonate group. In spite of this, the proton conductivity of the ordered pNeh-b-pNpm copolymers ranged from 0.002 to 0.008 S/cm. We demonstrate that proton conductivity is maximized in high molecular weight, symmetric pNeh-b-pNpm copolymers. PMID:27134312

  2. A X-Ray Scattering of Ordering in Block Copolymers.

    NASA Astrophysics Data System (ADS)

    Harkless, Curtis Ray

    1990-01-01

    The block copolymer, a novel system for studying the kinetics of first-order phase transitions, is investigated. Solutions of the block copolymer polystyrene-polybutadiene exhibit two types of phase transitions presently of great interest to the science community. Studies of the process by which these transformations occur can broaden our understanding of kinetic phenomena and aid in the identification of universal features such as nonequilibrium scaling. This thesis represents the first attempt to probe the kinetics of these transitions using synchrotron x-ray diffraction. The block copolymer molecule is composed of two different polymer chains joined by a covalent bond. When the chains are incompatible mesophases form through the process of microphase separation. The system also exhibits an ordering transition which results in a characteristic superlattice of the microdomains. A brief discussion of first-order phase transition kinetics is given followed by a detailed review of the relevant literature on block copolymers. High quality diblock and triblock copolymer solutions were prepared. The structure of each system was determined from the x-ray scattering profiles as a function of temperature after which kinetic measurements were performed. Each kinetic measurement involved annealing the sample above the dissolution temperature and rapidly quenching the sample temperature to a fixed point below. The subsequent transformation process was observed through the x-ray scattering profile. Due to the resolution obtained at the synchrotron, the scattering contributions from the ordered and disordered states are identified and separated for the first time. As a result several new features are observed such as the presence of fine structure in the x-ray scattering profile. Fast kinetic measurements reveal that transformation occurs as a two-stage process and that the ordering transition exhibits an unexpected crossover in behavior consistent with two dimensional

  3. Metal Nanoparticle/Block Copolymer Composite Assembly and Disassembly.

    PubMed

    Li, Zihui; Sai, Hiroaki; Warren, Scott C; Kamperman, Marleen; Arora, Hitesh; Gruner, Sol M; Wiesner, Ulrich

    2009-01-01

    Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organic-inorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,N-di-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-3-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of sub-1 nm Pt NPs was confirmed by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images. Estimations of the Pt NP ligand head group density based on HAADF-STEM images and thermogravimetric analysis (TGA) data yielded results comparable to what has been found for alkanethiol self-assembled monolayers (SAMs) on flat Pt {111} surfaces. Changing the volume fraction of Pt NPs in block copolymer-NP composites yielded hybrids with spherical micellar, wormlike micellar, lamellar and inverse hexagonal morphologies. Disassembly of hybrids with spherical, wormlike micellar, and lamellar morphologies generated isolated metal-NP based nano-spheres, cylinders and sheets, respectively. Results suggest the existence of powerful design criteria for the formation of metal-based nanostructures from designer blocked macromolecules.

  4. Metal Nanoparticle/Block Copolymer Composite Assembly and Disassembly

    PubMed Central

    Li, Zihui; Sai, Hiroaki; Warren, Scott C.; Kamperman, Marleen; Arora, Hitesh; Gruner, Sol M.; Wiesner, Ulrich

    2010-01-01

    Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organic-inorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,N-di-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-3-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of sub-1 nm Pt NPs was confirmed by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images. Estimations of the Pt NP ligand head group density based on HAADF-STEM images and thermogravimetric analysis (TGA) data yielded results comparable to what has been found for alkanethiol self-assembled monolayers (SAMs) on flat Pt {111} surfaces. Changing the volume fraction of Pt NPs in block copolymer-NP composites yielded hybrids with spherical micellar, wormlike micellar, lamellar and inverse hexagonal morphologies. Disassembly of hybrids with spherical, wormlike micellar, and lamellar morphologies generated isolated metal-NP based nano-spheres, cylinders and sheets, respectively. Results suggest the existence of powerful design criteria for the formation of metal-based nanostructures from designer blocked macromolecules. PMID:21103025

  5. Synthesis of an Amphiphilic Brush Copolymer by a Highly Efficient "Grafting onto" Approach via CO2 Chemistry.

    PubMed

    Zhang, Ying-Ying; Li, Yang; Zhou, Xian-Jing; Zhang, Xing-Hong; Du, Bin-Yang; Fan, Zhi-Qiang

    2015-05-01

    A novel and robust route for the synthesis of a new amphiphilic brush copolymer, poly(glycidyl methacrylate)-graft-polyethylene glycol (PGMA-g-PEG), with high grafting densities of 97%-98% through a "grafting onto" method via carbon dioxide chemistry is reported. PGMA-g-PEG can self-assemble and form stable spherical core-shell micelles in aqueous solution. Besides, the obtained PGMA-g-PEG polymer contains hydroxyurethane structures as the junction sites between the PGMA backbone and PEG side chain, which can be used for further modification. PMID:25823716

  6. Effect of some parameters on the synthesis and the physico-chemical properties of new amphiphilic starch-g-copolymers.

    PubMed

    Worzakowska, Marta; Grochowicz, Marta

    2015-10-01

    The detailed studies on the graft copolymerization of phenyl methacrylate onto gelatinized potato starch in water using potassium persulfate as radical initiator were presented. The different reaction parameters such as effect of initiator concentration, starch to monomer ratio, reaction temperature and reaction time were studied in terms of grafting efficiency, grafting percent and percent homopolymer formation. It was found that grafting process of aromatic methacrylate monomer onto potato starch backbone allowed obtaining new amphiphilic copolymers with different physicochemical properties as compared to non-modified starch. The influence of the copolymer structure on the swelling behavior in polar and non-polar solvents, moisture absorbance, gelatinization properties, acid and base resistance, surface morphology and thermal properties was discussed. PMID:26076635

  7. Amphiphilic triblock copolymers with PEGylated hydrocarbon structures as environmentally friendly marine antifouling and fouling-release coatings.

    PubMed

    Zhou, Zhaoli; Calabrese, David R; Taylor, Warren; Finlay, John A; Callow, Maureen E; Callow, James A; Fischer, Daniel; Kramer, Edward J; Ober, Christopher K

    2014-01-01

    The ideal marine antifouling (AF)/fouling-release (FR) coating should be non-toxic, while effectively either resisting the attachment of marine organisms (AF) or significantly reducing their strength of attachment (FR). Many recent studies have shown that amphiphilic polymeric materials provide a promising solution to producing such coatings due to their surface dual functionality. In this work, poly(ethylene glycol) (PEG) of different molecular weights (Mw = 350, 550) was coupled to a saturated difunctional alkyl alcohol to generate amphiphilic surfactants (PEG-hydrocarbon-OH). The resulting macromolecules were then used as side chains to covalently modify a pre-synthesized PS8 K-b-P(E/B)25 K-b-PI10 K (SEBI or K3) triblock copolymer, and the final polymers were applied to glass substrata through an established multilayer surface coating technique to prepare fouling resistant coatings. The coated surfaces were characterized with AFM, XPS and NEXAFS, and evaluated in laboratory assays with two important fouling algae, Ulva linza (a green macroalga) and Navicula incerta, a biofilm-forming diatom. The results suggest that these polymer-coated surfaces undergo surface reconstruction upon changing the contact medium (polymer/air vs polymer/water), due to the preferential interfacial aggregation of the PEG segment on the surface in water. The amphiphilic polymer-coated surfaces showed promising results as both AF and FR coatings. The sample with longer PEG chain lengths (Mw = 550 g mol(-1)) exhibited excellent properties against both algae, highlighting the importance of the chemical structures on ultimate biological performance. Besides reporting synthesis and characterization of this new type of amphiphilic surface material, this work also provides insight into the nature of PEG/hydrocarbon amphiphilic coatings, and this understanding may help in the design of future generations of fluorine-free, environmentally friendly AF/FR polymeric coatings. PMID:24730510

  8. Amphiphilic triblock copolymers with PEGylated hydrocarbon structures as environmentally friendly marine antifouling and fouling-release coatings.

    PubMed

    Zhou, Zhaoli; Calabrese, David R; Taylor, Warren; Finlay, John A; Callow, Maureen E; Callow, James A; Fischer, Daniel; Kramer, Edward J; Ober, Christopher K

    2014-01-01

    The ideal marine antifouling (AF)/fouling-release (FR) coating should be non-toxic, while effectively either resisting the attachment of marine organisms (AF) or significantly reducing their strength of attachment (FR). Many recent studies have shown that amphiphilic polymeric materials provide a promising solution to producing such coatings due to their surface dual functionality. In this work, poly(ethylene glycol) (PEG) of different molecular weights (Mw = 350, 550) was coupled to a saturated difunctional alkyl alcohol to generate amphiphilic surfactants (PEG-hydrocarbon-OH). The resulting macromolecules were then used as side chains to covalently modify a pre-synthesized PS8 K-b-P(E/B)25 K-b-PI10 K (SEBI or K3) triblock copolymer, and the final polymers were applied to glass substrata through an established multilayer surface coating technique to prepare fouling resistant coatings. The coated surfaces were characterized with AFM, XPS and NEXAFS, and evaluated in laboratory assays with two important fouling algae, Ulva linza (a green macroalga) and Navicula incerta, a biofilm-forming diatom. The results suggest that these polymer-coated surfaces undergo surface reconstruction upon changing the contact medium (polymer/air vs polymer/water), due to the preferential interfacial aggregation of the PEG segment on the surface in water. The amphiphilic polymer-coated surfaces showed promising results as both AF and FR coatings. The sample with longer PEG chain lengths (Mw = 550 g mol(-1)) exhibited excellent properties against both algae, highlighting the importance of the chemical structures on ultimate biological performance. Besides reporting synthesis and characterization of this new type of amphiphilic surface material, this work also provides insight into the nature of PEG/hydrocarbon amphiphilic coatings, and this understanding may help in the design of future generations of fluorine-free, environmentally friendly AF/FR polymeric coatings.

  9. Nanostructured assemblies from amphiphilic ABC multiblock polymers

    NASA Astrophysics Data System (ADS)

    Hillmyer, Marc A.

    2012-02-01

    Amphiphilic AB diblock copolymers containing a water compatible segment can self-assemble in aqueous media to give supramolecular structures that include simple spherical micelles and macromolecular vesicles termed polymersomes. Amphiphilic ABA triblocks with hydrophobic end blocks can adopt analogous structures but can also form gels at high polymer concentrations. The structural and chemical diversity demonstrated in block copolymer micelles and gels makes them attractive for applications ranging from drug delivery to personal care products to nanoreactors. The inclusion of a third block in amphiphilic ABC triblock systems can lead to a much wider array of self-assembled structures that depend not only on composition but also on block sequence, architecture and incompatibility considerations. I will present our recent efforts on tuning micelle and gel structure and behavior using controlled architecture ABC triblocks. The combination of diverse polymer segments into a single macromolecule is a powerful method for development of self-assembled structures with both new form and new function.

  10. John H. Dillon Medal Lecture: Molecular Heterogeneity in Block Copolymer Self-Assembly

    NASA Astrophysics Data System (ADS)

    Mahanthappa, Mahesh

    2013-03-01

    Narrow molecular weight dispersity in block copolymers has long been considered necessary for well-defined, periodic structure formation, by analogy to various crystallization processes. Consequently, much attention has focused on narrow dispersity copolymers derived from controlled and ``living'' polymerization techniques. However, these methods restrict the palette of functional monomers amenable to block copolymerization, thus constraining the physical and chemical properties of the resulting materials. New polymer syntheses enable access to a ``Pandora's Box'' of block copolymers with unusual chemical functionalities and useful physical properties, at the expense of introducing significant segmental dispersities into the resulting copolymers. The development and use of these functional materials requires basic understanding of the physical implications of continuous segmental dispersity on block copolymer phase behavior. Our work aims to understand the physical principles underlying polydisperse ABA-type triblock copolymer self-assembly, in order to transform segmental dispersity into a predictable and useful tool for manipulating block copolymer morphology. We have systematically demonstrated that mid-segment dispersity in ABA triblock copolymers does not preclude the formation of classical, structurally periodic, microphase separated morphologies. Mid-segment dispersity instead shifts the locations of the composition-dependent phase windows, dilates the microdomains, and unexpectedly stabilizes the microphase separated ABA triblock copolymer melts. Studies of three different polydisperse copolymer systems have provided general insights into the consequences of chain length heterogeneity on block copolymer self-assembly.

  11. Effect of Sequence Features on Assembly of Spider Silk Block Copolymers

    PubMed Central

    Tokareva, Olena S.; Lin, Shangchao; Jacobsen, Matthew M.; Huang, Wenwen; Rizzo, Daniel; Li, David; Simon, Marc; Staii, Cristian; Cebe, Peggy; Wong, Joyce Y.; Buehler, Markus J.; Kaplan, David L.

    2014-01-01

    Bioengineered spider silk block copolymers were studied to understand the effect of protein chain length and sequence chemistry on the formation of secondary structure and materials assembly. Using a combination of in vitro protein design and assembly studies, we demonstrate that silk block copolymers possessing multiple repetitive units self-assemble into lamellar microstructures. Additionally, the study provides insights into the assembly behavior of spider silk block copolymers in concentrated salt solutions. PMID:24613991

  12. Simple, generalizable route to highly aligned block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Qiang, Zhe; Cavicchi, Kevin; Vogt, Bryan

    2015-03-01

    Macroscopic alignment of block copolymer domains in thin films is desired for many applications, such as cell responsive surfaces or optical polarizers. Alignment generally requires specialized tools that apply external fields, shear force gradient, or produce topological patterned substrates. This requirement limits the broad academic application of aligned BCPs. Here, we describe a simple modification of commonly utilized solvent vapor annealing (SVA) process for macroscopic alignment of BCPs. Adhering a flat, crosslinked elastomer pad to the BCP film leads to differential swelling between the elastomer pad and BCP to produce a shear force that aligns the ordered BCP domains. The role of elastomer properties, solvent quality, drying rate and degree of segregation of the block copolymer will be discussed to provide generalized rules for alignment with this technique. Cylindrical nanostructures formed in polystyrene-block-polydimethylsiloxane can be transformed into arrays of silica lines and increasing the thickness from a monolayer to bilayer can effectively halve the spacing of the lines. These results illustrate a generalized method for BCP alignment and a potential route for the generation of complex hierarchical assembled structures.

  13. Thin film structure of symmetric rod-coil block copolymers.

    SciTech Connect

    Olsen, B. D.; Li, X.; Wang, J.; Segalman, R. A.; Univ. of Califormia at Berkeley; LBNL

    2007-04-03

    Poly(alkoxyphenylenevinylene-b-isoprene) (PPV-b-PI) rod-coil block copolymers demonstrate novel structures due to the rodlike PPV block. Thin films of the polymers self-assemble into lamellar microphases upon thermal annealing with the lamellae oriented primarily parallel to the substrate. The parallel lamellae show symmetric wetting of PI at both the substrate and vacuum interfaces. Grains of lamellae with parallel orientation are characterized by irregular polygon shapes and are bounded by defect regions where the lamellae are oriented out of the plane of the film. Grazing-incidence small-angle X-ray scattering (GISAXS) shows that these out-of-plane lamellae are strongly oriented perpendicular to the film. The perpendicular lamellae are much straighter than those typically observed in coil-coil block copolymers due to the high bending energy of the liquid crystalline rod nanodomains. Islands or holes form in the films, and domain spacings estimated from the island/hole heights are equal to the bulk domain spacing. The perpendicular 'defect' lamellae mediate the change in thickness required to transition between islands or holes and the surrounding region. Increasing film thickness results in an increasing fraction of the surface covered by perpendicular lamellae, presumably due to limited penetration of the substrate orienting field into the film. At great enough thickness total reorientation of the lamellar structure from parallel to perpendicular orientation at the vacuum interface is observed.

  14. Understanding the surface chemistry of amphiphilic copolymer thin films in aqueous environments

    NASA Astrophysics Data System (ADS)

    Buss, Hilda; Lynd, Nathaniel; Zuckermann, Ronald; Kramer, Ed; Segalman, Rachel

    2014-03-01

    Controlling the surface chemistry of polymer coatings which are stable in aqueous environment is a complex problem which depends heavily on the hydrophobicity of the polymer. Poly(styrene)- b-(ethyleneoxide-co-allylgycidylether)- b-poly(styrene) [PS- b-(PEO-co-AGE)- b-PS] triblock copolymers functionalized at the pendant allyl groups with fluorinated moieties are a promising class of polymers for applications in antifouling coatings. These polymers gain their water stability from the PS blocks and their antifouling character from the PEO block. Surface active fluorinated groups are used to direct the surface chemistry of the film during annealing. However, the surface can rearrange or become damaged upon immersion in water. Near edge X-ray absorption fine structure spectroscopy (NEXAFS) of films after soaking in water shows that the surface composition as characterized by the PS and PEO content in the first 6 nm of the film is directly related to the relative sizes of the PS and the P(EO-co-AGE) blocks as well as the fluorine content.

  15. Gamma radiation induced degradation in PE-PP block copolymer

    SciTech Connect

    Ravi, H. R.; Sreepad, H. R.; Ahmed, Khaleel; Govindaiah, T. N.

    2012-06-05

    In the present investigation, effect of gamma irradiation on the PP-PE block copolymer has been studied. The polymer has been subjected to gamma irradiation from 100 to 500 Mrad dosages. Characterization of the polymer using XRD and FTIR was done both before irradiation and after irradiation in each step. Effect of irradiation on the electrical properties of the material has also been studied. FTIR study shows that the sample loses C - C stretching mode of vibration but gains C=C stretching mode of vibration after irradiation. Present investigation clearly indicates that though the electrical conductivity increases in the material, it undergoes degradation and shows brittleness due to irradiation.

  16. Surfaces of Fluorinated Pyridinium Block Copolymers with Enhanced Antibacterial Activity

    SciTech Connect

    Krishnan,S.; Ward, R.; Hexemer, A.; Sohn, K.; Lee, K.; Angert, E.; Fischer, D.; Kramer, E.; Ober, C.

    2006-01-01

    Polystyrene-b-poly(4-vinylpyridine) copolymers were quaternized with 1-bromohexane and 6-perfluorooctyl-1-bromohexane. Surfaces prepared from these polymers were characterized by contact angle measurements, near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy. The fluorinated pyridinium surfaces showed enhanced antibacterial activity compared to their nonfluorinated counterparts. Even a polymer with a relatively low molecular weight pyridinium block showed high antimicrobial activity. The bactericidal effect was found to be related to the molecular composition and organization in the top 2-3 nm of the surface and increased with increasing hydrophilicity and pyridinium concentration of the surface.

  17. Perspective: Evolutionary design of granular media and block copolymer patterns

    NASA Astrophysics Data System (ADS)

    Jaeger, Heinrich M.; de Pablo, Juan J.

    2016-05-01

    The creation of new materials "by design" is a process that starts from desired materials properties and proceeds to identify requirements for the constituent components. Such process is challenging because it inverts the typical modeling approach, which starts from given micro-level components to predict macro-level properties. We describe how to tackle this inverse problem using concepts from evolutionary computation. These concepts have widespread applicability and open up new opportunities for design as well as discovery. Here we apply them to design tasks involving two very different classes of soft materials, shape-optimized granular media and nanopatterned block copolymer thin films.

  18. Gamma radiation induced degradation in PE-PP block copolymer

    NASA Astrophysics Data System (ADS)

    Ravi, H. R.; Sreepad, H. R.; Ahmed, Khaleel; Govindaiah, T. N.

    2012-06-01

    In the present investigation, effect of gamma irradiation on the PP-PE block copolymer has been studied. The polymer has been subjected to gamma irradiation from 100 to 500 Mrad dosages. Characterization of the polymer using XRD and FTIR was done both before irradiation and after irradiation in each step. Effect of irradiation on the electrical properties of the material has also been studied. FTIR study shows that the sample loses C - C stretching mode of vibration but gains C=C stretching mode of vibration after irradiation. Present investigation clearly indicates that though the electrical conductivity increases in the material, it undergoes degradation and shows brittleness due to irradiation.

  19. (Electro)Mechanical Properties of Olefinic Block Copolymers

    NASA Astrophysics Data System (ADS)

    Spontak, Richard

    2014-03-01

    Conventional styrenic triblock copolymers (SBCs) swollen with a midblock-selective oil have been previously shown to exhibit excellent electromechanical properties as dielectric elastomers. In this class of electroactive polymers, compliant electrodes applied as active areas to opposing surfaces of an elastomer attract each other, and thus compress the elastomer due to the onset of a Maxwell stress, upon application of an external electric field. This isochoric process is accompanied by an increase in lateral area, which yields the electroactuation strain (measuring beyond 300% in SBC systems). Performance parameters such as the Maxwell stress, transverse strain, dielectric breakdown, energy density and electromechanical efficiency are determined directly from the applied electric field and resulting electroactuation strain. In this study, the same principle used to evaluate SBC systems is extended to olefinic block copolymers (OBCs), which can be described as randomly-coupled multiblock copolymers that consist of crystallizable polyethylene hard segments and rubbery poly(ethylene-co-octene) soft segments. Considerations governing the development of a methodology to fabricate electroresponsive OBC systems are first discussed for several OBCs differing in composition and bulk properties. Evidence of electroactuation in selectively-solvated OBC systems is presented and performance metrics measured therefrom are quantitatively compared with dielectric elastomers derived from SBC and related materials.

  20. Coatings with Thermally Switchable Surface Energy Produced From Block Copolymer Films

    NASA Astrophysics Data System (ADS)

    Davis, Raleigh; Register, Richard

    2015-03-01

    Polymer-based coatings are employed across a wide array of sectors. One application of such coatings is to impart a prescribed surface energy, i . e . hydrophilic or hydrophobic character. The present work explores an approach to create surfaces with thermally switchable wetting behavior by employing coatings based on block copolymers which possess both hydrophilic and hydrophobic segments. The amphiphilic block copolymers were synthesized by coupling allyl-ended poly(ethylene oxide) (PEO) and hydride-ended poly(dimethylsiloxane) (PDMS) oligomers via a Pt catalyst. One PEO-PDMS diblock possessed an order-disorder-transition-temperature (TODT) of 64°C as characterized by small angle x-ray scattering. Above the TODT the polymer is a disordered melt, but below this temperature it self-assembles into alternating lamellae with a repeat spacing of 7.7 nm. When cooled through the TODT in vacuum or dry air, the PDMS-enriched domains wet the film's surface, producing a hydrophobic surface with a contact angle (CA) ~ 90° as measured from CA goniometry. However, when cooled under water or in humid air, a PEO-rich hydrophilic surface is produced, yielding CAs ranging from 20-40°. The coatings can then be reversibly switched between the two states by reheating above the TODT, exposing to the appropriate environment, and re-cooling, ideally ``locking in'' the structure until the next processing cycle. The TODT, and thus the switching temperature, can be continuously tuned by blending with PEO-PDMS diblocks of different molecular weights.

  1. Cooperative catalysis with block copolymer micelles: a combinatorial approach.

    PubMed

    Bukhryakov, Konstantin V; Desyatkin, Victor G; O'Shea, John-Paul; Almahdali, Sarah R; Solovyeva, Vera; Rodionov, Valentin O

    2015-02-01

    A rapid approach to identifying complementary catalytic groups using combinations of functional polymers is presented. Amphiphilic polymers with "clickable" hydrophobic blocks were used to create a library of functional polymers, each bearing a single functionality. The polymers were combined in water, yielding mixed micelles. As the functional groups were colocalized in the hydrophobic microphase, they could act cooperatively, giving rise to new modes of catalysis. The multipolymer "clumps" were screened for catalytic activity, both in the presence and absence of metal ions. A number of catalyst candidates were identified across a wide range of model reaction types. One of the catalytic systems discovered was used to perform a number of preparative-scale syntheses. Our approach provides easy access to a range of enzyme-inspired cooperative catalysts.

  2. Enhancing in vivo circulation and siRNA delivery with biodegradable polyethylenimine-graft-polycaprolactone-block-poly(ethylene glycol) copolymers.

    PubMed

    Zheng, Mengyao; Librizzi, Damiano; Kılıç, Ayşe; Liu, Yu; Renz, Harald; Merkel, Olivia M; Kissel, Thomas

    2012-09-01

    The purpose of this study was to enhance the in vivo blood circulation time and siRNA delivery efficiency of biodegradable copolymers polyethylenimine-graft-polycaprolactone-block-poly(ethylene glycol) (hy-PEI-g-PCL-b-PEG) by introducing high graft densities of PCL-PEG chains. SYBR(®) Gold and heparin assays indicated improved stability of siRNA/copolymer-complexes with a graft density of 5. At N/P 1, only 40% siRNA condensation was achieved with non-grafted polymer, but 95% siRNA was condensed with copolymer PEI25k-(PCL570-PEG5k)(5). Intracellular uptake studies with confocal laser scanning microscopy and flow cytometry showed that the cellular uptake was increased with graft density, and copolymer PEI25k-(PCL570-PEG5k)(5) was able to deliver siRNA much more efficiently into the cytosol than into the nucleus. The in vitro knockdown effect of siRNA/hyPEI-g-PCL-b-PEG was also significantly improved with increasing graft density, and the most potent copolymer PEI25k-(PCL570-PEG5k)(5) knocked down 84.43% of the GAPDH expression. Complexes of both the copolymers with graft density 3 and 5 circulated much longer than unmodified PEI25 kDa and free siRNA, leading to a longer elimination half-life, a slower clearance and a three- or fourfold increase of the AUC compared to free siRNA, respectively. We demonstrated that the graft density of the amphiphilic chains can enhance the siRNA delivery efficiency and blood circulation, which highlights the development of safe and efficient non-viral polymeric siRNA nanocarriers that are especially stable and provide longer circulation in vivo.

  3. Melt-Miscibility in Block Copolymers Containing Polyethylene and Substituted Polynorbornene Blocks

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    2015-03-01

    Block copolymers containing a crystallizable block, such as polyethylene (PE), and a high-Tg amorphous block are potentially interesting materials since the rigid glassy block can mitigate the poor yield strength of the PE crystals. However, chemical incompatibility between blocks, quantified by the Flory interaction parameter χ or the interaction energy density X, drives microphase separation at low temperatures or high chain lengths. To prepare a high molecular weight PE-containing block copolymer that is easy to process (i.e. with a disordered low-viscosity melt) it is necessary to select amorphous blocks that have low mixing energies with PE. The only suitable polymers currently known are chemically similar to PE and therefore have similarly low glass transition temperatures. We investigate a series of both low- and high-Tg polymers based on substituted norbornene monomers, polymerized via ring-opening metathesis polymerization (ROMP). Several ROMP polymers of this type exhibit high Tg and low interaction energy against PE. For example, hydrogenated poly(cyclohexyl norbornene) has Tg = 88 oC and has interaction energy density XhPCyN - PE ~ 0.8 MPa, comparable to the interaction energy density between PE and hydrogenated polyisoprene. The miscibility of an amorphous block can be further tuned by statistical copolymerization of norbornene units with aromatic side-groups (high Hildebrand solubility parameter) and norbornene units with aliphatic side-groups (low Hildebrand solubility parameter).

  4. Insertion Mechanism of a Poly(ethylene oxide)-poly(butylene oxide) Block Copolymer into a DPPC Monolayer

    SciTech Connect

    Leiske, Danielle L.; Meckes, Brian; Miller, Chad E.; Wu, Cynthia; Walker, Travis W.; Lin, Binhua; Meron, Mati; Ketelson, Howard A.; Toney, Michael F.; Fuller, Gerald G.

    2012-02-06

    Interactions between amphiphilic block copolymers and lipids are of medical interest for applications such as drug delivery and the restoration of damaged cell membranes. A series of monodisperse poly(ethylene oxide)-poly(butylene oxide) (EOBO) block copolymers were obtained with two ratios of hydrophilic/hydrophobic block lengths. We have explored the surface activity of EOBO at a clean interface and under 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayers as a simple cell membrane model. At the same subphase concentration, EOBO achieved higher equilibrium surface pressures under DPPC compared to a bare interface, and the surface activity was improved with longer poly(butylene oxide) blocks. Further investigation of the DPPC/EOBO monolayers showed that combined films exhibited similar surface rheology compared to pure DPPC at the same surface pressures. DPPC/EOBO phase separation was observed in fluorescently doped monolayers, and within the liquid-expanded liquid-condensed coexistence region for DPPC, EOBO did not drastically alter the liquid-condensed domain shapes. Grazing incidence X-ray diffraction (GIXD) and X-ray reflectivity (XRR) quantitatively confirmed that the lattice spacings and tilt of DPPC in lipid-rich regions of the monolayer were nearly equivalent to those of a pure DPPC monolayer at the same surface pressures.

  5. Reflectivity studies on adsorbed block copolymers under shear

    SciTech Connect

    Smith, G.S.; Wages, S.; Baker, S.M.; Toprakcioglu, C.; Hadziioannou, G.

    1994-12-01

    The authors report neutron reflectivity data on (poly)styrene-(poly)ethylene oxide (PS-PEO) diblock copolymers adsorbed onto quartz from the selective solvent cyclohexane (a non-solvent for PEO and a poor solvent for PS). The PEO ``anchor block`` adsorbs strongly to form a thin layer on the quartz substrate, while the deuterated PS chains dangle into the solvent. They find that under static conditions the density profile of the PS block in a poor solvent can be well described by a Schultz function which is indicative of a polymer ``mushroom.`` Furthermore, they have studied the same system under shear at shear rates from 0--400s{sup {minus}1}. They find that there is a dramatic increase in the thickness of the PS layer under shear in cyclohexane and that the relaxation time from the shear-on profile back to the static profile is on the order of several days.

  6. Silver-enhanced block copolymer membranes with biocidal activity.

    PubMed

    Madhavan, Poornima; Hong, Pei-Ying; Sougrat, Rachid; Nunes, Suzana P

    2014-01-01

    Silver nanoparticles were deposited on the surface and pore walls of block copolymer membranes with highly ordered pore structure. Pyridine blocks constitute the pore surfaces, complexing silver ions and promoting a homogeneous distribution. Nanoparticles were then formed by reduction with sodium borohydride. The morphology varied with the preparation conditions (pH and silver ion concentration), as confirmed by field emission scanning and transmission electron microscopy. Silver has a strong biocide activity, which for membranes can bring the advantage of minimizing the growth of bacteria and formation of biofilm. The membranes with nanoparticles prepared under different pH values and ion concentrations were incubated with Pseudomonas aeruginosa and compared with the control. The strongest biocidal activity was achieved with membranes containing membranes prepared under pH 9. Under these conditions, the best distribution with small particle size was observed by microscopy.

  7. Hollow ZIF-8 Nanoworms from Block Copolymer Templates.

    PubMed

    Yu, Haizhou; Qiu, Xiaoyan; Neelakanda, Pradeep; Deng, Lin; Khashab, Niveen M; Nunes, Suzana P; Peinemann, Klaus-Viktor

    2015-01-01

    Recently two quite different types of "nano-containers" have been recognized as attractive potential drug carriers; these are wormlike filamenteous micelles ("filomicelles") on the one hand and metal organic frameworks on the other hand. In this work we combine these two concepts. We report for the first time the manufacturing of metal organic framework nanotubes with a hollow core. These worm-like tubes are about 200 nm thick and several μm long. The preparation is simple: we first produce long and flexible filament-shaped micelles by block copolymer self-assembly. These filomicelles serve as templates to grow a very thin layer of interconnected ZIF-8 crystals on their surface. Finally the block copolymer is removed by solvent extraction and the hollow ZIF-8 nanotubes remain. These ZIF-NTs are surprisingly stable and withstand purification by centrifugation. The synthesis method is straightforward and can easily be applied for other metal organic framework materials. The ZIF-8 NTs exhibit high loading capacity for the model anti cancer drug doxorubicin (DOX) with a pH-triggered release. Hence, a prolonged circulation in the blood stream and a targeted drug release behavior can be expected.

  8. Molecular exchange in block copolymer micelles: when corona chains overlap

    NASA Astrophysics Data System (ADS)

    Lu, Jie; Lodge, Timothy; Bates, Frank; Choi, Soohyung

    2013-03-01

    The chain exchange kinetics of poly(styrene-b-ethylenepropylene) (PS-PEP) diblock copolymer micelles in squalane (C30H62) was investigated using time-resolved small angle neutron scattering (TR-SANS). The solvent is a mixture of h-squalane and d-squalane that contrast-matches a mixed 50/50 h/d PS micelle core. As isotope labeled chains exchange, the core contrast decreases, leading to a reduction in scattering intensity. This strategy therefore allows direct probing of the chain exchange rate. Separate copolymer micellar solutions containing either deuterium labeled (dPS) or normal (hPS) poly(styrene) core blocks were prepared and mixed at room temperature, below the core glass transition temperature. The samples were heated to several temperatures (around 100 °C) and monitored by TR-SANS every 5 min. As polymer concentration was increased from 1% to 15% by volume, we observed a significant slowing down of chain exchange rate. Similar retarded kinetics was found when part of the solvent in the 1% solution was replaced by homopolymer PEP (comparable size as corona block). Furthermore, if all the solvent is replaced with PEP, no exchange was detected for up to 3hr at 200 °C. These results will be discussed in terms of a molecular model for chain exchange Infineum, Iprime, NIST, ORNL

  9. Hollow ZIF-8 Nanoworms from Block Copolymer Templates

    PubMed Central

    Yu, Haizhou; Qiu, Xiaoyan; Neelakanda, Pradeep; Deng, Lin; Khashab, Niveen M.; Nunes, Suzana P.; Peinemann, Klaus-Viktor

    2015-01-01

    Recently two quite different types of “nano-containers” have been recognized as attractive potential drug carriers; these are wormlike filamenteous micelles (“filomicelles”) on the one hand and metal organic frameworks on the other hand. In this work we combine these two concepts. We report for the first time the manufacturing of metal organic framework nanotubes with a hollow core. These worm-like tubes are about 200 nm thick and several μm long. The preparation is simple: we first produce long and flexible filament-shaped micelles by block copolymer self-assembly. These filomicelles serve as templates to grow a very thin layer of interconnected ZIF-8 crystals on their surface. Finally the block copolymer is removed by solvent extraction and the hollow ZIF-8 nanotubes remain. These ZIF-NTs are surprisingly stable and withstand purification by centrifugation. The synthesis method is straightforward and can easily be applied for other metal organic framework materials. The ZIF-8 NTs exhibit high loading capacity for the model anti cancer drug doxorubicin (DOX) with a pH-triggered release. Hence, a prolonged circulation in the blood stream and a targeted drug release behavior can be expected. PMID:26471862

  10. Single Helix to Double Gyroid in Chiral Block Copolymers

    SciTech Connect

    C Chen; H Hsueh; Y Chiang; R Ho; S Akasaka; H Hasegawa

    2011-12-31

    An order-order phase transition of chiral block copolymers (BCPs*) from single helix to double gyroid (H* {yields} G) through a nucleation and growth process was demonstrated. The H* and G phases can be obtained by solution casting from fast and slow solvent evaporation, respectively, suggesting that the H* phase is a metastable phase. Consequently, the coexistence of H* and G phases can be found in the solution-cast samples from intermediate solvent evaporation. To truly examine the transition mechanism of the H* {yields} G, electron tomography was carried out to directly visualize the morphological evolution in real space, in particular, the transition zone at interface. Unlike the mechanisms for the transitions of block copolymers (BCPs) by considering the interdomain spacing matching, a significant mismatch in the lattices for the H* {yields} G was found. Consequently, the transition may require an adjustment on the geometric dimensions to justify corresponding lattice mismatch. As a result, the morphological observations from electron tomography offer new insights into BCP phase transitions.

  11. Synthesis and antibacterial activity of nisin-containing block copolymers.

    PubMed

    Joshi, Pranav R; McGuire, Joseph; Neff, Jennifer A

    2009-10-01

    Nisin, an antibacterial peptide proven to be an effective inhibitor of Gram-positive bacteria, was incorporated into novel block copolymer constructs and tested for retained antibacterial activity. Covalent coupling was achieved by chemical modification of the N-terminal isoleucine to introduce a thiol group. Thiolated-nisin derivatives were then linked to poly[ethylene oxide]-poly[propylene oxide]-poly[ethylene oxide] (PEO-PPO-PEO) triblocks that had been end-activated such that terminal hydroxyl groups of the PEO chains were replaced with pyridyl disulfide moieties. The nisin-containing block copolymers were separated from free nisin by dialysis and showed antimicrobial activity against the Gram-positive indicator strain Pediococcus pentosaceus. The contribution to antimicrobial activity from nisin that was covalently linked was not distinguished from the contribution of nisin that had associated with the PEO-PPO-PEO triblocks through noncovalent interactions. However, nisin that was covalently linked showed activity upon reduction of the disulfide bond and release from the end-activated PEO. PMID:19358262

  12. Interaction between Albumin and Pluronic F127 Block Copolymer Revealed by Global and Local Physicochemical Profiling.

    PubMed

    Neacsu, Maria Victoria; Matei, Iulia; Micutz, Marin; Staicu, Teodora; Precupas, Aurica; Popa, Vlad Tudor; Salifoglou, Athanasios; Ionita, Gabriela

    2016-05-12

    The interaction of human serum albumin (HSA) with amphiphilic block copolymer Pluronic F127 has been investigated by several physical methods. Interest in studying this system stems from a broad range of bioactivities involving both macromolecules. Serum albumins constitute a significant class of proteins in the circulatory system, acting as carriers for a wide spectrum of compounds or assemblies. Pluronic block copolymers have revealed their capacity to ferry a variety of biologically active compounds. Circular dichroism, rheological measurements, and differential scanning microcalorimetry (μDSC) were employed to get insight into the interaction betweeen the two macromolecules. The results reveal that Pluronic F127 induces conformational changes to albumin if it is organized in a micellar form, while albumin influences the self-assembly of Pluronic F127 into micelles or gels. F127 micelles, however, induce smaller conformational changes compared to ionic surfactants. The μDSC thermograms obtained for HSA and/or F127 show that HSA shifts the critical micellar temperature (cmt) to lower values, while concurrently the HSA denaturation behavior is influenced by F127, depending on its concentration. Rheological measurements on solutions of F127 17% have shown that a sol-to-gel transition occurs at higher temperatures in the presence of HSA and the resulting gel is weaker. The global profile on HSA/F127 systems was complemented by local information provided by EPR measurements. A series of X-band EPR experiments was performed with spin probes 4-(N,N'-dimethyl-N-hexadecyl)ammonium-2,2',6,6'-tetramethylpiperidine-1-oxyl iodide (CAT16) and 5-doxyl stearic acid (5-DSA). These spin probes bind to albumin sites and are sensitive to phase transformations in Pluronic block copolymer solutions. For a given F127 concentration, the spin probe binds only to HSA below cmt and migrates to the F127 micelles above cmt. The collective data suggest soft interactions between the

  13. Tuning Cationic Block Copolymer Micelle Size by pH and Ionic Strength.

    PubMed

    Sprouse, Dustin; Jiang, Yaming; Laaser, Jennifer E; Lodge, Timothy P; Reineke, Theresa M

    2016-09-12

    The formation, morphology, and pH and ionic strength responses of cationic block copolymer micelles in aqueous solutions have been examined in detail to provide insight into the future development of cationic micelles for complexation with polyanions such as DNA. Diblock polymers composed of a hydrophilic/cationic block of N,N-dimethylaminoethyl methacrylate (DMAEMA) and a hydrophobic/nonionic block of n-butyl methacrylate (BMA) were synthesized [denoted as DMAEMA-b-BMA (X-Y), where X = DMAEMA molecular weight and Y = molecular weight of BMA in kDa]. Four variants were created with block molecular weights of 14-13, 14-23, 27-14, 27-29 kDa and low dispersities less than 1.10. The amphiphilic polymers self-assembled in aqueous conditions into core-shell micelles that ranged in size from 25-80 nm. These cationic micelles were extensively characterized in terms of size and net charge in different buffers over a wide range of ionic strength (0.02-1 M) and pH (5-10) conditions. The micelle core is kinetically trapped, and the corona contracts with increasing pH and ionic strength, consistent with previous work on micelles with glassy polystyrene cores, indicating that the corona properties are independent of the dynamics of the micelle core. The contraction and extension of the corona scales with solution ionic strength and charge fraction of the amine groups. The aggregation numbers of the micelles were obtained by static light scattering, and the Rg/Rh ratios are close to that of a hard sphere. The zeta potentials of the micelles were positive up to two pH units above the corona pKa, suggesting that applications relying on micelle charge for stability should be viable over a wide range of solution conditions. PMID:27487088

  14. Master curve captures the effect of domain morphology on ethanol pervaporation through block copolymer membranes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We report on the effect of changing nanoscale morphology on pervaporation of ethanol/water mixtures through block copolymer membranes. Experiments were conducted using polystyrene-b-polybutadiene-b-polystyrene (SBS) copolymers with polybutadiene (PB) as the ethanol transporting block, using an 8 wt%...

  15. Hierarchical Manipulation of Block Copolymer Patterns on 3D Topographic Substrates: Beyond Graphoepitaxy.

    PubMed

    Park, Sungjune; Cheng, Xiao; Böker, Alexander; Tsarkova, Larisa

    2016-08-01

    Templates of complex nanopatterns in a form of hierarchically sequenced dots and stripes can be generated in block copolymer films on lithography-free 3D topographic substrates. The approach exploits thickness- and swelling-responsive morphological behavior of block copolymers, and demonstrates novel possibilities of topography-guided registration of nanopatterns due to periodic confinement and spontaneous orthogonal flow-fields. PMID:27270877

  16. Morphological study of biodegradable PEO/PLA block copolymers.

    PubMed

    Younes, H; Cohn, D

    1987-11-01

    A series of PEO/PLA copolymers, covering a wide range of compositions and segmental lengths, was synthesized, and their morphology was investigated by means of DSC and IR studies. For matrices comprising PEO chains with molecular weights below 3400, no soft-segment crystallinity was detected. When long hard segments were present, essentially monophasic, semicrystalline polymers were obtained, with PLA blocks melting around 130 degrees C. Polymers containing longer soft segments (PEO 6000) exhibited a two-phase matrix, with both components being able to crystallize. The relative degree of crystallinity of PEO and PLA blocks was also determined. The thermal history of the sample strongly affected the morphology of the matrix, especially when both blocks were long enough to crystallize. To further explore these polymers, solvent cast films were prepared and their morphology assessed. Casting from acetone, which is an excellent solvent for PLA, resulted in hard blocks exhibiting lower degrees of crystallinity, while methanol had a similar effect on PEO soft segments. PMID:3680315

  17. Multifunctional Poly(N-vinylcarbazole)-Based Block Copolymers and their Nanofabrication and Photosensitizing Properties.

    PubMed

    Tam, Wing Yan; Mak, Chris S K; Ng, Alan Man Ching; Djurišić, Aleksandra B; Chan, Wai Kin

    2009-04-20

    The synthesis of poly(N-vinylcarbazole)-based block copolymers functionalized with rhenium diimine complexes or pendant terpyridine ligands is reported. The copolymers are synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, and they exhibit interesting morphological properties as a result of the phase separation between different blocks. The rhenium complex polymer block may function as a photosensitizer, while the terpyridine-containing polymer block can be used as the template for nanofabrication by selective deposition of zinc complexes.

  18. Phase behavior of multi-arm star-shaped polystyrene-block-poly(methyl methacrylate) copolymer

    NASA Astrophysics Data System (ADS)

    Jang, Sangshin; Moon, Hong Chul; Bae, Dusik; Kwak, Jonghen; Kim, Jin Kon

    2013-03-01

    We synthesized star-shaped polystyrene-block-poly(methyl methacrylate) copolymer (PS- b-PMMA) by utilizing α-cyclodextrin (α-CD) as a core of the star-shaped block copolymer. Eighteen hydroxyl groups on α-CD were transformed to bromine by the reaction with α-bromoisobutyryl bromide. We found that the number of bromine substituted arms per one α-CD was higher than 16, which was determined by nuclear magnetic resonance and Matrix-assisted laser desorption/ionization. We could control molecular weight of block copolymers by changing polymerization times. The block copolymers were characterized by gel permeation chromatography and nuclear magnetic resonance. Phase behaviors of these star-shaped block copolymers were investigated by small angle X-ray scattering and transmission electron microscopy.

  19. Continuous concentric lamellar block copolymer nanofibers with long range order.

    PubMed

    Ma, Minglin; Titievsky, Kirill; Thomas, Edwin L; Rutledge, Gregory C

    2009-04-01

    Fibers with long-range ordered internal structures have applications in various areas such as photonic band gap fibers, optical waveguides, wearable power, sensors, and sustained drug release. Up to now, such fibers have been formed by melt extrusion or drawing from a macroscopic preformed rod and were typically limited to diameters >10 microm with internal features >1 microm (Abouraddy, A. F.; et al. Nat. Mater. 2007, 6, 336). We describe a new class of continuous fibers and fibrous membranes with long-range ordered concentric lamellar structure that have fiber diameters and feature sizes 2-3 orders of magnitude smaller than those made by conventional methods. These fibers are created through confined self-assembly of block copolymers within core-shell electrospun filaments. In contrast to the copolymer in bulk or thin films, the domains of the concentric lamellar structure are shown here to vary quantitatively with (radial) position and to exhibit a novel dislocation that accommodates variations in fiber diameter robustly, permitting for the first time the realization of long-range order in technologically meaningful, continuous fibers with approximately 300 nm diameter and 50 nm radial period. PMID:19351195

  20. Nanowire polarizers by guided self-assembly of block copolymers

    NASA Astrophysics Data System (ADS)

    Roberts, Philip M. S.; Baum, Alexandra; Karamath, James; Evans, Allan; Shibata, Satoshi; Walton, Harry

    2014-01-01

    Wire-grid polarizers (WGPs) are currently limited by their wafer-scale manufacturing methods to sizes of approximately 12 to 18 in. For large-size displays, a new method for the production of large-area WGPs is required. Large-area WGPs were simulated using the finite-difference-time-domain method, and a scaleable method for their production based on a block copolymer (BCP)-nanostructured template was implemented. The nanostructured template is globally aligned through the use of a cylinder-forming liquid crystal (LC) diblock copolymer, which is first aligned on a rubbed polyimide substrate. A surface-relief template is produced using the differential dry etch rates of the cylinder-forming component and LC polymer matrix component of the BCP. The template is metalized to produce a WGP. Polarizers of arbitrary size with polarization efficiency up to 0.6 have been made in close agreement with calculated values for idealized structures. The choice of the cylinder-forming polymer is critical to the degree of alignment of the template, and the thermal stability of the LC polymer matrix is critical to the stability of the template during etching.

  1. Self-assembly of miktoarm star-like ABn block copolymers: from wet to dry brushes.

    PubMed

    Xu, Yuci; Wang, Chao; Zhong, Shuo; Li, Weihua; Lin, Zhiqun

    2015-03-10

    Self-assembly of miktoarm star-like ABn block copolymer in both selective solvent (A- or B-selective) and miscible homopolymer matrix (A or B homopolymer), that is, formation of micelles, was for the first time investigated by theoretical calculations based on self-consistent mean field theory. Interestingly, the calculation revealed that the size of micelles in solvent was smaller than that in homopolymer under the same conditions. In B-selective solvent, with increasing number of B blocks n in miktoarm star-like ABn block copolymer at a fixed volume fraction of A block, the micellar size decreased gradually. In stark contrast, when miktoarm star-like ABn block copolymer dissolved in B homopolymer matrix at molecular weight ratio of B homopolymer to ABn block copolymer fH = 0.30, the overall micellar size decreased nonmonotonically as the number of B blocks n in ABn block copolymer increased. The largest micelle was formed in AB2 (i.e., n = 2). This intriguing finding can be attributed to a wet-to-dry brush transition that occurred from n = 1 to n = 2 in the micellization of miktoarm star-like ABn block copolymer. Moreover, the micellization behaviors of miktoarm star-like ABn block copolymer in A-selective solvent and A homopolymer matrix were also explored, where the overall micellar size in both scenarios was found to decrease monotonically as n in ABn block copolymer increased. These self-assembled nanostructures composed of miktoarm star-like ABn block copolymers may promise a wide range of applications in size-dependent drug delivery and bionanotechnology.

  2. Calorimetric study on pH-responsive block copolymer grafted lipid bilayers: rational design and development of liposomes.

    PubMed

    Pippa, Natassa; Chountoulesi, Maria; Kyrili, Aimilia; Meristoudi, Anastasia; Pispas, Stergios; Demetzos, Costas

    2016-09-01

    This study is focused on chimeric advanced drug delivery nanosystems and specifically on pH-sensitive liposomes, combining lipids and pH-responsive amphiphilic block copolymers. Chimeric liposomes composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and two different forms of block copolymers, i.e. poly(n-butylacrylate)-b-poly(acrylic acid) (PnBA-b-PAA) at 70 and 85% content of PAA at six different molar ratios, each form respectively. PAA block exhibits pH-responsiveness, because of the regulative group of -COOH. -COOH is protonated under acidic pH (pKa ca. 4.2), while remains ionized under basic or neutral pH, leading to liposomes repulse and eventually stability. Lipid bilayers were prepared composed of DPPC and PnBA-b-PAA. Experiments were carried out using differential scanning calorimetry (DSC) in order to investigate their thermotropic properties. DSC indicated disappearance of pre-transition at all chimeric lipid bilayers and slight thermotropic changes of the main transition temperature. Chimeric liposomes have been prepared and their physicochemical characteristics have been explored by measuring the size, size distribution and ζ-potential, owned to the presence of pH-responsive polymer. At percentages containing medium to high amounts of the polymer, chimeric liposomes were found to retain their size during the stability studies. These results were well correlated with those indicated in the DSC measurements of lipid bilayers incorporating polymers in order to explain their physicochemical behavior. The incorporation of the appropriate amount of these novel pH-responsive block copolymers affects thus the cooperativity, the liposomal stabilization and imparts pH-responsiveness.

  3. Sprayable Elastic Conductors Based on Block Copolymer Silver Nanoparticle Composites

    PubMed Central

    2015-01-01

    Block copolymer silver nanoparticle composite elastic conductors were fabricated through solution blow spinning and subsequent nanoparticle nucleation. The reported technique allows for conformal deposition onto nonplanar substrates. We additionally demonstrated the ability to tune the strain dependence of the electrical properties by adjusting nanoparticle precursor concentration or localized nanoparticle nucleation. The stretchable fiber mats were able to display electrical conductivity values as high as 2000 ± 200 S/cm with only a 12% increase in resistance after 400 cycles of 150% strain. Stretchable elastic conductors with similar and higher bulk conductivity have not achieved comparable stability of electrical properties. These unique electromechanical characteristics are primarily the result of structural changes during mechanical deformation. The versatility of this approach was demonstrated by constructing a stretchable light emitting diode circuit and a strain sensor on planar and nonplanar substrates. PMID:25491507

  4. Correlative infrared nanospectroscopic and nanomechanical imaging of block copolymer microdomains.

    PubMed

    Pollard, Benjamin; Raschke, Markus B

    2016-01-01

    Intermolecular interactions and nanoscale phase separation govern the properties of many molecular soft-matter systems. Here, we combine infrared vibrational scattering scanning near-field optical microscopy (IR s-SNOM) with force-distance spectroscopy for simultaneous characterization of both nanoscale optical and nanomechanical molecular properties through hybrid imaging. The resulting multichannel images and correlative analysis of chemical composition, spectral IR line shape, modulus, adhesion, deformation, and dissipation acquired for a thin film of a nanophase separated block copolymer (PS-b-PMMA) reveal complex structural variations, in particular at domain interfaces, not resolved in any individual signal channel alone. These variations suggest that regions of multicomponent chemical composition, such as the interfacial mixing regions between microdomains, are correlated with high spatial heterogeneity in nanoscale material properties. PMID:27335750

  5. Correlative infrared nanospectroscopic and nanomechanical imaging of block copolymer microdomains.

    PubMed

    Pollard, Benjamin; Raschke, Markus B

    2016-01-01

    Intermolecular interactions and nanoscale phase separation govern the properties of many molecular soft-matter systems. Here, we combine infrared vibrational scattering scanning near-field optical microscopy (IR s-SNOM) with force-distance spectroscopy for simultaneous characterization of both nanoscale optical and nanomechanical molecular properties through hybrid imaging. The resulting multichannel images and correlative analysis of chemical composition, spectral IR line shape, modulus, adhesion, deformation, and dissipation acquired for a thin film of a nanophase separated block copolymer (PS-b-PMMA) reveal complex structural variations, in particular at domain interfaces, not resolved in any individual signal channel alone. These variations suggest that regions of multicomponent chemical composition, such as the interfacial mixing regions between microdomains, are correlated with high spatial heterogeneity in nanoscale material properties.

  6. Correlative infrared nanospectroscopic and nanomechanical imaging of block copolymer microdomains

    PubMed Central

    Pollard, Benjamin

    2016-01-01

    Summary Intermolecular interactions and nanoscale phase separation govern the properties of many molecular soft-matter systems. Here, we combine infrared vibrational scattering scanning near-field optical microscopy (IR s-SNOM) with force–distance spectroscopy for simultaneous characterization of both nanoscale optical and nanomechanical molecular properties through hybrid imaging. The resulting multichannel images and correlative analysis of chemical composition, spectral IR line shape, modulus, adhesion, deformation, and dissipation acquired for a thin film of a nanophase separated block copolymer (PS-b-PMMA) reveal complex structural variations, in particular at domain interfaces, not resolved in any individual signal channel alone. These variations suggest that regions of multicomponent chemical composition, such as the interfacial mixing regions between microdomains, are correlated with high spatial heterogeneity in nanoscale material properties. PMID:27335750

  7. Application of poly(ethylene glycol)-distearoylphosphatidylethanolamine (PEG-DSPE) block copolymers and their derivatives as nanomaterials in drug delivery.

    PubMed

    Wang, Rongrong; Xiao, Renzhong; Zeng, Zhaowu; Xu, Lili; Wang, Junjie

    2012-01-01

    Poly(ethylene glycol)-distearoylphosphatidylethanolamine (PEG-DSPE) block copolymers are biocompatible and amphiphilic polymers that can be widely utilized in the preparation of liposomes, polymeric nanoparticles, polymer hybrid nanoparticles, solid lipid nanoparticles, lipid-polymer hybrid nanoparticles, and microemulsions. Particularly, the terminal groups of PEG can be activated and linked to various targeting ligands, which can prolong the circulation time, improve the drug bioavailability, reduce undesirable side effects, and especially target specific cells, tissues, and even the intracellular localization in organelles. This review herein aims to describe recent developments in drug carriers exploiting PEG-DSPE block copolymers and their derivatives, and the incorporation of different ligands to the end groups of PEG-DSPE to target delivery, focusing on their modification approaches, advantages, applications, and the probable associated drawbacks. PMID:22904628

  8. Water distributions in PS-b-P(S-g-PEO) block grafted copolymer system in aqueous solutions revealed by contrast variation SANS study

    SciTech Connect

    Chen, Wei-Ren; Hong, Kunlun; Li, Xin; Liu, Emily; Liu, Yun; Shew, Chwen-Yang; Smith, Gregory Scott

    2010-01-01

    In this report, we present a contrast variation small angle neutron scattering (SANS) study of PS-b-P(S-g-PEO) block graft copolymers in aqueous media at a concentration of 10 mg/ml. Through varying the solvent D2O/H2O ratio, the scattering contributions from the water molecules and the micellar constituent components can be determined. Based on the commonly used core-shell model, a theoretical coherent scattering cross section incorporating the effect of water penetration is developed and used to analyze the SANS I(Q), we have successfully quantified the micellar structure and the number of - water molecules associated with the core and corona. We have found that the overall micellar hydration level increase with the increase in the molecular weight of hydrophilic PEO side chains. This study provides key information in understanding solvent distributions within self-assembled amphiphilic block grafted copolymers.

  9. Selective separation of similarly sized proteins with tunable nanoporous block copolymer membranes.

    PubMed

    Qiu, Xiaoyan; Yu, Haizhou; Karunakaran, Madhavan; Pradeep, Neelakanda; Nunes, Suzana P; Peinemann, Klaus-Viktor

    2013-01-22

    An integral asymmetric membrane was fabricated in a fast and one-step process by combining the self-assembly of an amphiphilic block copolymer (PS-b-P4VP) with nonsolvent-induced phase separation. The structure was found to be composed of a thin layer of densely packed highly ordered cylindrical channels with uniform pore sizes perpendicular to the surface on top of a nonordered sponge-like layer. The as-assembled membrane obtained a water flux of more than 3200 L m(-2) h(-1) bar(-1), which was at least an order of magnitude higher than the water fluxes of commercially available membranes with comparable pore sizes, making this membrane particularly well suited to size-selective and charge-based separation of biomolecules. To test the performance of the membrane, we conducted diffusion experiments at the physiological pH of 7.4 using bovine serum albumin (BSA) and globulin-γ, two proteins with different diameters but too close in size (2-fold difference in molecular mass) to be efficiently separated via conventional dialysis membrane processes. The diffusion rate differed by a factor of 87, the highest value reported to date. We also analyzed charge-based diffusive transport and separation of two proteins of similar molecular weight (BSA and bovine hemoglobin (BHb)) through the membrane as a function of external pH. The membrane achieved a selectivity of about 10 at pH 4.7, the isoelectric point (pI) of BSA. We then positively charged the membrane to improve the separation selectivity. With the modified membrane BSA was completely blocked when the pH was 7.0, the pI of BHb, while BHb was completely blocked at pH 4.7. Our results demonstrate the potential of our asymmetric membrane to efficiently separate biological substances/pharmaceuticals in bioscience, biotechnology, and biomedicine applications.

  10. Selective separation of similarly sized proteins with tunable nanoporous block copolymer membranes.

    PubMed

    Qiu, Xiaoyan; Yu, Haizhou; Karunakaran, Madhavan; Pradeep, Neelakanda; Nunes, Suzana P; Peinemann, Klaus-Viktor

    2013-01-22

    An integral asymmetric membrane was fabricated in a fast and one-step process by combining the self-assembly of an amphiphilic block copolymer (PS-b-P4VP) with nonsolvent-induced phase separation. The structure was found to be composed of a thin layer of densely packed highly ordered cylindrical channels with uniform pore sizes perpendicular to the surface on top of a nonordered sponge-like layer. The as-assembled membrane obtained a water flux of more than 3200 L m(-2) h(-1) bar(-1), which was at least an order of magnitude higher than the water fluxes of commercially available membranes with comparable pore sizes, making this membrane particularly well suited to size-selective and charge-based separation of biomolecules. To test the performance of the membrane, we conducted diffusion experiments at the physiological pH of 7.4 using bovine serum albumin (BSA) and globulin-γ, two proteins with different diameters but too close in size (2-fold difference in molecular mass) to be efficiently separated via conventional dialysis membrane processes. The diffusion rate differed by a factor of 87, the highest value reported to date. We also analyzed charge-based diffusive transport and separation of two proteins of similar molecular weight (BSA and bovine hemoglobin (BHb)) through the membrane as a function of external pH. The membrane achieved a selectivity of about 10 at pH 4.7, the isoelectric point (pI) of BSA. We then positively charged the membrane to improve the separation selectivity. With the modified membrane BSA was completely blocked when the pH was 7.0, the pI of BHb, while BHb was completely blocked at pH 4.7. Our results demonstrate the potential of our asymmetric membrane to efficiently separate biological substances/pharmaceuticals in bioscience, biotechnology, and biomedicine applications. PMID:23252799

  11. Nanopatterning of ultrananocrystalline diamond thin films via block copolymer lithography.

    SciTech Connect

    Ramanathan, M.; Darling, S. B.; Sumant, A. V.; Auciello, O.

    2010-07-01

    Nanopatterning of diamond surfaces is critical for the development of diamond-based microelectromechanical system/nanoelectromechanical system (MEMS/NEMS), such as resonators or switches. Micro-/nanopatterning of diamond materials is typically done using photolithography or electron beam lithography combined with reactive ion etching (RIE). In this work, we demonstrate a simple process, block copolymer (BCP) lithography, for nanopatterning of ultrananocrystalline diamond (UNCD) films to produce nanostructures suitable for the fabrication of NEMS based on UNCD. In BCP lithography, nanoscale self-assembled polymeric domains serve as an etch mask for pattern transfer. The authors used thin films of a cylinder-forming organic-inorganic BCP, poly(styrene-block-ferrocenyldimethylsilane), PS-b-PFS, as an etch mask on the surface of UNCD films. Orientational control of the etch masking cylindrical PFS blocks is achieved by manipulating the polymer film thickness in concert with the annealing treatment. We have observed that the surface roughness of UNCD layers plays an important role in transferring the pattern. Oxygen RIE was used to etch the exposed areas of the UNCD film underneath the BCP. Arrays of both UNCD posts and wirelike structures have been created using the same starting polymeric materials as the etch mask.

  12. Dynamics of Chain Exchange in Block Copolymer Micelles

    NASA Astrophysics Data System (ADS)

    Lodge, Timothy

    Block copolymer micelles are rarely at equilibrium. The primary reason is the large number of repeat units in the insoluble block, Ncore, which makes the thermodynamic penalty for extracting a single chain (``unimer exchange'') substantial. As a consequence, the critical micelle concentration (CMC) is rarely accessed experimentally; however, in the proximity of a critical micelle temperature (CMT), equilibration is possible. We have been using time-resolved small angle neutron scattering (TR-SANS) to obtain a detailed picture of the mechanisms and time scales for chain exchange, at or near equilibrium. Our model system is poly(styrene)-block-poly(ethylene-alt-propylene)) (PS-PEP), in the PEP-selective solvent squalane (C30H62) . Equivalent micelles with either normal (hPS) or perdeuterated (dPS) cores are initially mixed in a blend of isotopically substituted squalane, designed to contrast-match a 50:50 hPS:dPS core. Samples are then annealed at a target temperature, and chain exchange is revealed quantitatively by the temporal decay in scattered intensity. The rate of exchange as function of concentration, temperature, Ncore, Ncorona, and chain architecture (diblock versus triblock) will be discussed.

  13. Directed Nanorod Assembly Using Block Copolymer-Based Supramolecules

    NASA Astrophysics Data System (ADS)

    Thorkelsson, Kari; Mastroianni, Alexander; Ercius, Peter; Xu, Ting

    2013-03-01

    Nanorods display many unique electrical, mechanical, and optical properties unavailable in traditional bulk materials, and are attractive building blocks toward functional materials. The collective properties of anisotropic building blocks often depend strongly on their spatial arrangements, interparticle ordering, and macroscopic alignment. We have systematically investigated the phase behavior of nanocomposites composed of nanorods and block copolymer (BCP)-based supramolecules forming spherical, cylindrical and lamellar morphologies. Initial exploration showed that the nanorods can be readily dispersed in polymeric matrix and the overall morphology of nanorod-containing supramolecular nanocomposite depends on the nanorod-polymer interactions, inter-rod interactions and entropy associated with polymer chain deformation. The energetic contributions from the components of the system can be tailored to disperse nanorods with control over inter-rod ordering and the alignment of nanorods within BCP microdomains. By varying the supramolecular morphology and composition, arrays, sheets, and interconnected networks of nanorods are demonstrated that may prove useful for fabrication of optically and electrically active nanodevices.

  14. Reversible Switching of Block Copolymer Nanopatterns by Orthogonal Electric Fields.

    PubMed

    Liedel, Clemens; Lewin, Christian; Tsarkova, Larisa; Böker, Alexander

    2015-12-01

    It is demonstrated that the orientation of striped patterns can be reversibly switched between two perpendicular in-plane orientations upon exposure to electric fields. The results on thin films of symmetric polystyrene-block-poly(2-vinyl pyridine) polymer in the intermediate segregation regime disclose two types of reorientation mechanisms from perpendicular to parallel relative to the electric field orientation. Domains orient via grain rotation and via formation of defects such as stretched undulations and temporal phase transitions. The contribution of additional fields to the structural evolution is also addressed to elucidate the generality of the observed phenomena. In particular solvent effects are considered. This study reveals the stabilization of the meta-stable in-plane oriented lamella due to sequential swelling and quenching of the film. Further, the reorientation behavior of lamella domains blended with selective nanoparticles is addressed, which affect the interfacial tensions of the blocks and hence introduce another internal field to the studied system. Switching the orientation of aligned block copolymer patterns between two orthogonal directions may open new applications of nanomaterials as switchable electric nanowires or optical gratings. PMID:26449286

  15. Fluorinated polyphenylenevinylene (PPV) block co-polymers for nanophotonics

    NASA Astrophysics Data System (ADS)

    Sun, Sam-Shajing; Nguyen, Thuong; Brooks, Jaleesa

    2013-09-01

    Polymer based optoelectronic materials and thin film devices exhibit great potential in future space applications due to their flexibility, light weight, large light absorption coefficient, and promising radiation tolerance in space environment as compared to their inorganic semiconductor counterparts. Since carbon-fluorine (C-F) chemical bonds are much stronger than the carbon-hydrogen (C-H) bonds, fluorinated polymer films offer great potential for space applications due their expected resistance to oxidation, thermal stability, excellent wear properties, and low coefficients of friction. Their use in a space environment is extremely attractive since they are expected to retain their lubricating characteristics in vacuum, unlike many solid lubricants. Current existing polymer photovoltaic materials and devices suffer low photoelectric power conversion efficiencies due to a number factors including poor morphologies at nano scale that hinder the charge separation and transport. This paper reports our recent work on a fluorinated DBfA type block copolymer system where the donor (D) block contains a donor substituted and hydrocarbon based polyphenylenevinylene (PPV), acceptor (fA) block contains a fluorinated and a sulfone acceptor substituted polyphenylenevinylene (f-PPV), and B is a non-conjugated and flexible bridge unit. Preliminary studies reveal DBfA exhibits better nano phase morphologies and over 100 times more efficient optoelectronic conversion efficiencies as compared to D/fA blend.

  16. Molecular origin of photovoltaic performance in donor-block-acceptor all-conjugated block copolymers

    SciTech Connect

    Smith, Kendall A.; Lin, Yen -Hao; Mok, Jorge W.; Yager, Kevin G.; Strzalka, Joseph; Nie, Wanyi; Mohite, Aditya D.; Verduzco, Rafael

    2015-11-03

    All-conjugated block copolymers may be an effective route to self-assembled photovoltaic devices, but we lack basic information on the relationship between molecular characteristics and photovoltaic performance. Here, we synthesize a library of poly(3-hexylthiophene) (P3HT) block poly((9,9-dialkylfluorene)-2,7-diyl-alt-[4,7-bis(alkylthiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT) donor-block-acceptor all-conjugated block copolymers and carry out a comprehensive study of processing conditions, crystallinity, domain sizes, and side-chain structure on photovoltaic device performance. We find that all block copolymers studied exhibit an out-of-plane crystal orientation after deposition, and on thermal annealing at high temperatures the crystal orientation flips to an in-plane orientation. By varying processing conditions on polymer photovoltaic devices, we show that the crystal orientation has only a modest effect (15-20%) on photovoltaic performance. The addition of side-chains to the PFTBT block is found to decrease photovoltaic power conversion efficiencies by at least an order of magnitude. Through grazing-incidence X-ray measurements we find that the addition of side-chains to the PFTBT acceptor block results in weak segregation and small (< 10 nm) block copolymer self-assembled donor and acceptor domains. This work is the most comprehensive to date on all-conjugated block copolymer systems and suggests that photovoltaic performance of block copolymers depends strongly on the miscibility of donor and acceptor blocks, which impacts donor and acceptor domain sizes and purity. Lastly, strategies for improving the device performance of block copolymer photovoltaics should seek to increase segregation between donor and acceptor polymer domains.

  17. Amphiphilic Graft Copolymers as a Versatile Binder for Various Electrodes of High-Performance Lithium-Ion Batteries.

    PubMed

    Lee, Jung-In; Kang, Hyojin; Park, Kwang Hyun; Shin, Myoungsoo; Hong, Dongki; Cho, Hye Jin; Kang, Na-Ri; Lee, Jungho; Lee, Sang Myeon; Kim, Ju-Young; Kim, Choon Ki; Park, Hyesung; Choi, Nam-Soon; Park, Soojin; Yang, Changduk

    2016-06-01

    It is known that grafting one polymer onto another polymer backbone is a powerful strategy capable of combining dual benefits from each parent polymer. Thus amphiphilic graft copolymer precursors (poly(vinylidene difluoride)-graft-poly(tert-butylacrylate) (PVDF-g-PtBA)) have been developed via atom transfer radical polymerization, and demonstrated its outstanding properties as a promising binder for high-performance lithium-ion battery (LIB) by using in situ pyrolytic transformation of PtBA to poly(acrylic acid) segments. In addition to its superior mechanical properties and accommodation capability of volume expansion, the Si anode with PVDF-g-PtBA exhibits the excellent charge and discharge capacities of 2672 and 2958 mAh g(-1) with the capacity retention of 84% after 50 cycles. More meaningfully, the graft copolymer binder shows good operating characteristics in both LiN0.5 M1.5 O4 cathode and neural graphite anode, respectively. By containing such diverse features, a graft copolymer-loaded LiN0.5 M1.5 O4 /Si-NG full cell has been successfully achieved, which delivers energy density as high as 546 Wh kg(-1) with cycle retention of ≈70% after 50 cycles (1 C). For the first time, this work sheds new light on the unique nature of the graft copolymer binders in LIB application, which will provide a practical solution for volume expansion and low efficiency problems, leading to a high-energy-density lithium-ion chemistry. PMID:27119208

  18. Tough Block Copolymer Organogels and Elastomers as Short Fiber Composites

    NASA Astrophysics Data System (ADS)

    Kramer, Edward J.

    2012-02-01

    The origins of the exceptional toughness and elastomeric properties of gels and elastomers from block copolymers with semicrystalline syndiotactic polypropylene blocks will be discussed. Using synchrotron X-radiation small angle (SAXS) and wide angle X-ray scattering (WAXS) experiments were simultaneously performed during step cycle tensile deformation of these elastomers and gels. From these results the toughness can be attributed to the formation, orientation and elongation of the crystalline fibrils along the tensile direction. The true stress and true strain ɛH during each cycle were recorded, including the true strain at zero load ɛH,p after each cycle that resulted from the plastic deformation of the sPP crystals in the gel or elastomer. The initial Young's modulus Einit and maximum tangent modulus Emax in each cycle undergo dramatic changes as a function of ɛH,p, with Einit decreasing for ɛH,p <= 0.1 and then increasing slowly as ɛH,p increases to 1 while Emax increases rapidly over the entire range of ɛH,p resulting in a ratio of Emax/Einit > 100 to 1000 at the highest maximum (nominal) strain. Based on SAXS patterns from the deformed and relaxed gels, as well as on previous results on deformation of semicrystalline random copolymers by Strobl and coworkers, we propose that the initial decrease in Einit and increase in Emax with ɛH,p are due to a breakup of the network of the original sPP crystal lamellae and the conversion of the sPP lamellae into fibrils whose aspect ratio increases with further plastic deformation, respectively. The gel elastic properties can be understood quantitatively as those of a short fiber composite with a highly deformable matrix. At zero stress the random copolymer midblock chains that connect the fibrils cause these to make all angles to the tensile axis (low Einit), while at the maximum strain the stiff, crystalline sPP fibrils align with the tensile axis producing a strong, relatively stiff gel. The evolution of the

  19. Thermodynamics of Surfactants, Block Copolymers and Their Mixtures in Water: The Role of the Isothermal Calorimetry

    PubMed Central

    De Lisi, Rosario; Milioto, Stefania; Muratore, Nicola

    2009-01-01

    The thermodynamics of conventional surfactants, block copolymers and their mixtures in water was described to the light of the enthalpy function. The two methodologies, i.e. the van’t Hoff approach and the isothermal calorimetry, used to determine the enthalpy of micellization of pure surfactants and block copolymers were described. The van’t Hoff method was critically discussed. The aqueous copolymer+surfactant mixtures were analyzed by means of the isothermal titration calorimetry and the enthalpy of transfer of the copolymer from the water to the aqueous surfactant solutions. Thermodynamic models were presented to show the procedure to extract straightforward molecular insights from the bulk properties. PMID:19742173

  20. Using click chemistry to modify block copolymers and their morphologies

    NASA Astrophysics Data System (ADS)

    Wollbold, Johannes

    Microphase separated block copolymers (BCPs) are emerging as promising templates and scaffolds for the fabrication of nanostructured materials. To achieve the desired nanostructures, it is necessary to establish convenient approaches to control the morphology of BCPs. It remains challenging to induce morphological transitions of BCPs via external fields. Click chemistry, especially alkyne/azide click chemistry, has been widely used to synthesize novel functionalized materials. Here, we demonstrate that alkyne/azide click chemistry can be used as an efficient approach to chemically modify BCPs and therefore induce morphological transitions. Alkyne-functionalized diblock copolymers (di-BCPs) poly(ethylene oxide)- block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) have been successfully synthesized. When the di-BCP is blended with an azide additive Rhodamine B azide and annealed at elevated temperatures, click reaction occurs between the two components. With the Rhodamine B structure attached to the polymer backbone, the di-BCP shows dramatic change in the interactions between the two blocks and the volume fraction of each block. As a result, morphological transitions, such as disorder-to-order transitions (DOTs) and order-to-order transitions (OOTs), are observed. The reaction kinetics and morphology evolution during the click chemistry induced DOTs have been investigated by in-situ and ex-situ characterizations, and fast kinetics properties are observed. Microphase separated morphologies after the DOTs or OOTs are dictated by the composition of neat di-BCPs and the mole ratio between the alkyne and azide groups. The DOTs of PEO-b-P(nBMA-r-PgMA) di-BCPs induced by alkyne/azide click chemistry have also been achieved in thin film geometries, with comparable kinetics to bulk samples. The orientation of the microdomains is dependent on the grafting density of Rhodamine B structure as well as film thickness. At higher grafting densities

  1. Poly(lactide)-block-poly([epsilon]-caprolactone-co-[epsilon]-decalactone)-block-poly(lactide) copolymer elastomers

    SciTech Connect

    Schneiderman, Deborah K.; Hill, Erin M.; Martello, Mark T.; Hillmyer, Marc A.

    2015-08-28

    Batch ring opening transesterification copolymerization of ε-caprolactone and ε-decalactone was used to generate statistical copolymers over a wide range of compositions and molar masses. Reactivity ratios determined for this monomer pair, rCL = 5.9 and rDL = 0.03, reveal ε-caprolactone is added preferentially regardless of the propagating chain end. Relative to poly(ε-caprolactone) the crystallinity and melting point of these statistical copolymers were depressed by the addition of ε-decalactone; copolymers containing greater than 31 mol% (46 wt%) ε-decalactone were amorphous. Poly(lactide)-block-poly(ε-caprolactone-co-ε-decalactone)-block-poly(lactide) triblock polymers were also prepared and used to explore the influence of midblock composition on the temperature dependent Flory-Huggins interaction parameter (χ). In addition, uniaxial extension tests were used to determine the effects of midblock composition, poly(lactide) content, and molar mass on the mechanical properties of these new elastomeric triblocks.

  2. Kinetic assembly of block copolymers in solution helical cylindrical micelles and patchy nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhong, Sheng

    There is always an interest to understand how molecules behave under different conditions. One application of this knowledge is to self-assemble molecules into increasingly complex structures in a simple fashion. Self-assembly of amphiphilic block copolymer in solution has produced a large variety of nanostructures through the manipulation in polymer chemistry, assembly environment, and additives. Moreover, some reports suggest the formation of many polymeric assemblies is driven by kinetic process. The goal of this dissertation is to study the influence of kinetics on the assembly of block copolymer. The study shows kinetic control can be a very effective way to make novel polymeric nanostructures. Two examples discussed here are helical cylindrical micelles and patchy nanoparticles. Helical cylindrical micelles are made from the co-assembly of amphiphilic triblock copolymer poly(acrylic acid)-block-poly(methyl acrylate)- block-polystyrene and organoamine molecules in a mixture of tetrahydrofuran (THF) and water (H2O). This system has already shown promise of achieving many assembled structures. The unique aspects about this system are the use of amine molecules to complex with acid groups and the existence of cosolvent system. Application of amine molecules offers a convenient control over assembled morphology and the introduction of PMA-PS selective solvent, THF, promotes the mobility of the polymer chains. In this study, multivalent organoamine molecules, such as diethylenetriamine and triethylenetetramine, are used to interact with block copolymer in THF/water mixture. As expected, the assembled morphologies are dependent on the polymer architecture, selection and quantity of the organoamine molecules, and solution composition. Under the right conditions, unprecedented, multimicrometer-long, supramolecular helical cylindrical micelles are formed. Both single-stranded and double-stranded helices are found in the same system. These helical structures share

  3. Unexpected consequences of block polydispersity on the self-assembly of ABA triblock copolymers.

    PubMed

    Widin, Joan M; Schmitt, Adam K; Schmitt, Andrew L; Im, Kyuhyun; Mahanthappa, Mahesh K

    2012-02-29

    Controlled/"living" polymerizations and tandem polymerization methodologies offer enticing opportunities to enchain a wide variety of monomers into new, functional block copolymer materials with unusual physical properties. However, the use of these synthetic methods often introduces nontrivial molecular weight polydispersities, a type of chain length heterogeneity, into one or more of the copolymer blocks. While the self-assembly behavior of monodisperse AB diblock and ABA triblock copolymers is both experimentally and theoretically well understood, the effects of broadening the copolymer molecular weight distribution on block copolymer phase behavior are less well-explored. We report the melt-phase self-assembly behavior of SBS triblock copolymers (S = poly(styrene) and B = poly(1,4-butadiene)) comprised of a broad polydispersity B block (M(w)/M(n) = 1.73-2.00) flanked by relatively narrow dispersity S blocks (M(w)/M(n) = 1.09-1.36), in order to identify the effects of chain length heterogeneity on block copolymer self-assembly. Based on synchrotron small-angle X-ray scattering and transmission electron microscopy analyses of seventeen SBS triblock copolymers with poly(1,4-butadiene) volume fractions 0.27 ≤ f(B) ≤ 0.82, we demonstrate that polydisperse SBS triblock copolymers self-assemble into periodic structures with unexpectedly enhanced stabilities that greatly exceed those of equivalent monodisperse copolymers. The unprecedented stabilities of these polydisperse microphase separated melts are discussed in the context of a complete morphology diagram for this system, which demonstrates that narrow dispersity copolymers are not required for periodic nanoscale assembly. PMID:22280467

  4. Unexpected Consequences of Block Polydispersity on the Self-Assembly of ABA Triblock Copolymers

    SciTech Connect

    Widin, Joan M.; Schmitt, Adam K.; Schmitt, Andrew L.; Im, Kyuhyun; Mahanthappa, Mahesh K.

    2012-05-09

    Controlled/'living' polymerizations and tandem polymerization methodologies offer enticing opportunities to enchain a wide variety of monomers into new, functional block copolymer materials with unusual physical properties. However, the use of these synthetic methods often introduces nontrivial molecular weight polydispersities, a type of chain length heterogeneity, into one or more of the copolymer blocks. While the self-assembly behavior of monodisperse AB diblock and ABA triblock copolymers is both experimentally and theoretically well understood, the effects of broadening the copolymer molecular weight distribution on block copolymer phase behavior are less well-explored. We report the melt-phase self-assembly behavior of SBS triblock copolymers (S = poly(styrene) and B = poly(1,4-butadiene)) comprised of a broad polydispersity B block (M{sub w}/M{sub n} = 1.73-2.00) flanked by relatively narrow dispersity S blocks (M{sub w}/M{sub n} = 1.09-1.36), in order to identify the effects of chain length heterogeneity on block copolymer self-assembly. Based on synchrotron small-angle X-ray scattering and transmission electron microscopy analyses of seventeen SBS triblock copolymers with poly(1,4-butadiene) volume fractions 0.27 {le} f{sub B} {le} 0.82, we demonstrate that polydisperse SBS triblock copolymers self-assemble into periodic structures with unexpectedly enhanced stabilities that greatly exceed those of equivalent monodisperse copolymers. The unprecedented stabilities of these polydisperse microphase separated melts are discussed in the context of a complete morphology diagram for this system, which demonstrates that narrow dispersity copolymers are not required for periodic nanoscale assembly.

  5. How to Place Block Copolymer Molecules at the Interface of a Binary Blend

    NASA Astrophysics Data System (ADS)

    Chen, Zhong-Ren; Xu, Yuci; Zhong, Shuo

    2015-03-01

    Block copolymers have been used to reduce the domain size of immiscible polymer blends and thus improve the mechanical and other properties. The effectiveness of this method, however, depends on the percentage of these polymeric surfactants residing at the interface of the blend. In fact, theoretical as well as experimental work indicate that a large percentage of block copolymers form micelles in the bulk of one or both of the component polymers. These micelles may serve as weak spots initiating crack propagation. Previous work have been focused on the design of molecular architecture and synthesis of new block copolymers to address this problem. In this presentation, a simple mixing strategy is applied to make each block copolymer molecule stay at the interface. As one example, when this strategy is used to mix natural rubber (NR) with butadiene rubber (BR), a small amount of low molecular weight block copolymer (LIR) improves both processing characteristics such as melt viscosity and mechanical properties of cured samples, such as crack resistance. AFM micrographs show the much smaller domain size; and an original real-time monitoring system reveals the lowest crack growth rate. Using a model A/B/A-B binary blend, we have witnessed by microscopy that all block copolymer molecules form micelles at the first mixing step, and all of these micelles are disappeared and all block copolymer molecules stay at the interface after the second mixing step.

  6. Liquid crystal alignment in electro-responsive nanostructured thermosetting materials based on block copolymer dispersed liquid crystal

    NASA Astrophysics Data System (ADS)

    Tercjak, A.; Garcia, I.; Mondragon, I.

    2008-07-01

    Novel well-defined nanostructured thermosetting systems were prepared by modification of a diglicydylether of bisphenol-A epoxy resin (DGEBA) with 10 or 15 wt% amphiphilic poly(styrene-b-ethylene oxide) block copolymer (PSEO) and 30 or 40 wt% low molecular weight liquid crystal 4'-(hexyl)-4-biphenyl-carbonitrile (HBC) using m-xylylenediamine (MXDA) as a curing agent. The competition between well-defined nanostructured materials and the ability for alignment of the liquid crystal phase in the materials obtained has been studied by atomic and electrostatic force microscopy, AFM and EFM, respectively. Based on our knowledge, this is the first time that addition of an adequate amount (10 wt%) of a block copolymer to 40 wt% HBC-(DGEBA/MXDA) leads to a well-organized nanostructured thermosetting system (between a hexagonal and worm-like ordered structure), which is also electro-responsive with high rate contrast. This behavior was confirmed using electrostatic force microscopy (EFM), by means of the response of the HBC liquid crystal phase to the voltage applied to the EFM tip. In contrast, though materials containing 15 wt% PSEO and 30 wt% HBC also form a well-defined nanostructured thermosetting system, they do not show such a high contrast between the uncharged and charged surface.

  7. Drying of films formed by ordered poly(ethylene oxide)-poly(propylene oxide) block copolymer gels.

    PubMed

    Gu, Zhiyong; Alexandridis, Paschalis

    2005-03-01

    The drying of hydrogel films formed by poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) block copolymers (Pluronic P105 and Pluronic L64) is investigated at various air relative humidity (RH) conditions in the range 11-94%. These amphiphilic block copolymers self-assemble to form a variety of ordered (lyotropic liquid crystalline) structures as the water content decreases. The amount of water lost increases linearly with the drying time initially (constant rate region, stage I). After this linear region, a falling rate is observed (stage II). The drying rate increases with decreasing RH, thus greatly shortening the drying time. A decrease of the initial film thickness or a decrease in the initial water content shortens the drying time; however, the drying mechanism remains the same. Analysis of the experimental data shows that the hydration level in the Pluronic hydrogel mainly determines the drying rate, rather than the type of ordered structure formed. Two distinct regions (liquid/gel and solid/crystalline) are observed in the drying isotherm for PEO-PPO block copolymers and homopolymer poly(ethylene glycol)s. A model for one-dimensional water diffusion is used to fit the experimental drying results at different RH, initial film thickness, and initial water content conditions. The model accounts for the shrinkage of the film during drying and for a water diffusion coefficient that is a function of the water concentration in the film. For the experimental conditions considered here, the Biot number (Bi) is less than unity and the drying is mainly limited by evaporation at the film surface. The diffusion model is used to obtain information for cases where Bi > 1.

  8. Dynamics of structure formation in crystallizable block copolymers

    SciTech Connect

    Rangarajan, P.; Register, R.A.; Adamson, D.H.

    1995-12-31

    Isothermal crystallization of polyolefin diblock copolymers from homogeneous and weakly segregated melts has been tracked using simultaneous, synchrotron-based small and wide-angle x-ray scattering (SAXS and WAXS). The polymers are prepared by hydrogenating polydiene diblocks, and contain crystallizable polyethylene ({open_quotes}E{close_quotes}; hydrogenated high 1,4-polybutadiene) blocks and a variety of amorphous polyolefin blocks. All polymers exhibit a well-ordered lamellar morphology at room temperature, as evidenced by 2-3 clear SAXS reflections, even for compositions containing as little as 12% E. In polymers crystallizing from homogeneous melts, the WAXS reflections from the E crystallites grow in parallel with the 3-4 SAXS reflections, so microphase separation is driven by crystallization. These structures, which are reminiscent of strong segregation (as indicated by the multiple SAXS reflections), are obtained by cooling only 20{degrees}C below the melting point. For a polymer having a weakly segregated melt, crystallization eradicates the melt morphology, but larger domain spacings were observed for higher crystallization temperatures, unlike the path-independent values obtained on crystallization from single-phase melts, suggesting that melt segregation hinders the development of the equilibrium crystallization-driven structure.

  9. Bicontinuous ceramics with high surface area from block copolymer templates.

    PubMed

    Hsueh, Han-Yu; Ho, Rong-Ming

    2012-06-01

    Mesoporous polymers with gyroid nanochannels can be fabricated from the self-assembly of degradable block copolymer, polystyrene-b-poly(L-lactide) (PS-PLLA), followed by hydrolysis of PLLA block. Well-defined polymer/ceramic nanohybrid materials with inorganic gyroid nanostructures in a PS matrix can be obtained by using the mesoporous PS as a template for sol-gel reaction. Titanium tetraisopropoxide (TTIP) is used as a precursor to give a model system for the fabrication of metal oxide nanostructures from reactive transition metal alkoxides. By controlling the rates of capillary-driven pore filling and sol-gel reaction, the templated synthesis can be well-developed. Also, by taking advantage of calcination, bicontinuous TiO(2) with controlled crystalline phase (i.e., anatase phase) can be fabricated after removal of the PS template and crystallization of TiO(2) by calcination leading to high photocatalytic efficiency. This new approach provides an easy way to fabricate high-surface-area and high-porosity ceramics with self-supporting structure and controlled crystalline phase for practical applications. As a result, a platform technology to fabricate precisely controlled polymer/ceramic nanohybrids and mesoporous ceramic materials can be established. PMID:22530553

  10. A density functional theory of chiral block copolymer melts.

    PubMed

    Wang, Shih-Hao; Kawakatsu, Toshihiro; Chen, Peilong; Lu, Chun-Yi David

    2013-05-21

    A density functional theory is developed for the diblock copolymer melt, where one block contains the segment orientation dependent chiral interaction. In addition to the standard (scalar) pair interaction between the two types of monomers, the chiral block has the additional pairwise interaction, which is linear in the tangent vectors of the segments. We construct a density functional, which contains both the scalar density field and the vector chain alignment field. The quadratic part of the density functional comes from the mean field theory of the microscopic model, whereas the fourth order terms are introduced phenomenologically in the spatially local form. From the stability analysis of this model, we find that the additional chiral interaction shifts the order-disorder transition, which is consistent with the behavior of experimental system. Further numerical calculation reveals a new metastable chiral helical cylinder structure, which is similar to the one found experimentally. Another similar metastable structure but with zigzag modulation is also observed. As the helical and zigzag structures disappear when the chiral interaction is switched off, we understand that the chiral effect is the driving force for the formation of these exotic metastable structures.

  11. Surface Modification of Block Copolymer Through Sulfur Containing Plasma Treatment.

    PubMed

    Choi, Sang Wook; Shin, Jae Hee; Jeon, Min Hwan; Mun, Jeong Ho; Kim, Sang Ouk; Yeom, Geun Young; Kim, Kyong Nam

    2015-10-01

    Some of the important issues of block copolymer (BCP) as an application to the potential low cost next generation lithography are thermal stability and deformation during pattern transfer process in addition to defect density, line edge/width roughness, etc. In this study, sulfur containing plasma treatment was used to modify the BCP and the effects of the plasma on the properties of plasma treated BCP were investigated. The polystyrene hole pattern obtained from polystyrene polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) was initially degraded when the polystyrene hole was annealed at 190 °C for 15 min. However, when the hole pattern was treated using sulfur containing plasmas using H2S or SF6 up to 2 min, possibly due to the sulfurization of the polystyrene hole surface, no change in the hole pattern was observed after the annealing even though there is a slight change in hole shapes during the plasma treatment. The optimized plasma treated polystyrene pattern showed the superior characteristics as the mask layer by showing better thermal stability, higher chemical inertness, and higher etch selectivity during plasma etching. PMID:26726468

  12. Electric-Field-Induced Alignment of Block Copolymer/Nanoparticle Blends

    SciTech Connect

    Liedel, Clemens; Schindler, Kerstin; Pavan, Mariela J.; Lewin, Christian; Pester, Christian W; Ruppel, Markus A; Urban, Volker S; Shenhar, Roy; Boker, Alexander

    2013-01-01

    External electric fi elds readily align birefringent block-copolymer mesophases. In this study the effect of gold nanoparticles on the electric-fi eld-induced alignment of a lamellae-forming polystyrene- block -poly(2-vinylpyridine) copolymer is assessed. Nanoparticles are homogeneously dispersed in the styrenic phase and promote the quantitative alignment of lamellar domains by substantially lowering the critical field strength above which alignment proceeds. The results suggest that the electric-fi eldassisted alignment of nanostructured block copolymer/nanoparticle composites may offer a simple way to greatly mitigate structural and orientational defects of such fi lms under benign experimental conditions.

  13. Electric-field-induced alignment of block copolymer/nanoparticle blends.

    PubMed

    Liedel, Clemens; Schindler, Kerstin A; Pavan, Mariela J; Lewin, Christian; Pester, Christian W; Ruppel, Markus; Urban, Volker S; Shenhar, Roy; Böker, Alexander

    2013-10-11

    External electric fields readily align birefringent block-copolymer mesophases. In this study the effect of gold nanoparticles on the electric-field-induced alignment of a lamellae-forming polystyrene-block-poly(2-vinylpyridine) copolymer is assessed. Nanoparticles are homogeneously dispersed in the styrenic phase and promote the quantitative alignment of lamellar domains by substantially lowering the critical field strength above which alignment proceeds. The results suggest that the electric-field-assisted alignment of nanostructured block copolymer/nanoparticle composites may offer a simple way to greatly mitigate structural and orientational defects of such films under benign experimental conditions. PMID:23495246

  14. Non-immunogenic, hydrophilic/cationic block copolymers and uses thereof

    DOEpatents

    Scales, Charles W.; Huang, Faqing; McCormick, Charles L.

    2010-05-18

    The present invention provides novel non-immunogenic, hydrophilic/cationic block copolymers comprising a neutral-hydrophilic polymer and a cationic polymer, wherein both polymers have well-defined chain-end functionality. A representative example of such a block copolymer comprises poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) and poly(N-[3-(dimethylamino)propyl]methacrylamide) (PDMAPMA). Also provided is a synthesis method thereof in aqueous media via reversible addition fragmentation chain transfer (RAFT) polymerization. Further provided are uses of these block copolymers as drug delivery vehicles and protection agents.

  15. Anti-Biofouling Effect of PEG-Grafted Block Copolymer Synthesized by RAFT Polymerization.

    PubMed

    Kim, Seon-Mi; Han, Sang Suk; Kim, A Young; Choi, Beom-Jin; Paik, Hyun-Jong; Lee, Inwon; Park, Hyun; Chun, Ho Hwan; Cho, Youngjin; Hwang, Do-Hoon

    2015-10-01

    Poly(glycidyl methadrylate-block-styrene) (PGMA-b-PS), a block copolymer consisting of glycidyl methacrylate and styrene, was synthesized via reversible addition-fragmentation chain transfer living polymerization. The synthesized PGMA-b-PS was then grafted with low-molecular-weight polyethylene glycol (PEG) via epoxy ring opening to give PGMA-g-PEG-b-PS, which was evaluated as an anti-biofouling coating material. As a preliminary test for the anti-biofouling effect, a protein adsorption experiment was performed on the synthesized block copolymer surface. The block copolymers were spin-coated onto silicon wafers, and protein adsorption experiments were carried out using fluorescein isothiocyanate conjugate-labeled bovine serum albumin. The fluorescence intensity of the protein adsorbed on the block copolymer surface was compared with that of a polystyrene film as a reference. The synthesized PGMA-g-PEG-b-PS film showed much lower fluorescence intensity than that of the PS film.

  16. A strategy to explore stable and metastable ordered phases of block copolymers.

    PubMed

    Xu, Weiquan; Jiang, Kai; Zhang, Pingwen; Shi, An-Chang

    2013-05-01

    Block copolymers with their rich phase behavior and ordering transitions have become a paradigm for the study of structured soft materials. A major challenge in the study of the phase behavior of block copolymers is to obtain different stable and metastable phases of the system. A strategy to discover complex ordered phases of block copolymers within the self-consistent field theory framework is developed by a combination of fast algorithms and novel initialization procedures. This strategy allows the generation of a large number of candidate structures, which can then be used to construct phase diagrams. Application of the strategy is illustrated using ABC star triblock copolymers as an example. A large number of candidate structures, including many three-dimensionally ordered phases, of the system are obtained and categorized. A phase diagram is constructed for symmetrically interacting ABC star triblock copolymers. PMID:23551204

  17. Efficacy of Different Block Copolymers in Facilitating Microemulsion Phases in Polymer Blend Systems

    NASA Astrophysics Data System (ADS)

    Pandav, Gunja; Ganesan, Venkat

    2014-03-01

    Polymeric microemulsions are formed in a narrow range of phase diagram when a blend of immiscible homopolymers is compatibilized by copolymers. In this study, we consider the ternary blend system of A and B homopolymers mixed with block copolymers containing A and B segments, and probe the efficacy of different copolymer configurations in promoting the formation of microemulsion phases. Specifically, we consider: (a) Monodisperse diblock copolymers; (b) Diblock copolymers with bidisperse molecular weights (MW); (c) Block copolymers having MW polydispersity in one of the blocks; (d) Diblock copolymers having monodisperse MW but bidispersity in average composition; and (e) Gradient copolymers exhibiting a linear variation in the average composition. Using single chain in mean field simulations effected in two dimensions, we probe the onset of formation and the width of the bicontinuous microemulsion channel in the ternary phase diagram of homopolymer blended with compatibilizer. We rationalize our results by explicitly quantifying the interfacial activity and the influence of fluctuation effects in the respective copolymer systems.

  18. Glucose-Responsive Hybrid Nanoassemblies in Aqueous Solutions: Ordered Phenylboronic Acid within Intermixed Poly(4-hydroxystyrene)-block-poly(ethylene oxide) Block Copolymer.

    PubMed

    Matuszewska, Alicja; Uchman, Mariusz; Adamczyk-Woźniak, Agnieszka; Sporzyński, Andrzej; Pispas, Stergios; Kováčik, Lubomír; Štěpánek, Miroslav

    2015-12-14

    Coassembly behavior of the double hydrophilic block copolymer poly(4-hydroxystyrene)-block-poly(ethylene oxide) (PHOS-PEO) with three amphiphilic phenylboronic acids (PBA) differing in hydrophobicity, 4-dodecyloxyphenylboronic acid (C12), 4-octyloxyphenylboronic acid (C8), and 4-isobutoxyphenylboronic acid (i-Bu) was studied in alkaline aqueous solutions and in mixtures of NaOHaq/THF by spin-echo (1)H NMR spectroscopy, dynamic and electrophoretic light scattering, and SAXS. The study reveals that only the coassembly of C12 with PHOS-PEO provides spherical nanoparticles with intermixed PHOS and PEO blocks, containing densely packed C12 micelles. NMR measurements have shown that spatial proximity of PHOS-PEO and C12 leads to the formation of ester bonds between -OH of PHOS block and hydroxyl groups of -B(OH)2. Due to the presence of PBA moieties, the release of compounds with 1,2- or 1,3-dihydroxy groups loaded in the coassembled PHOS-PEO/PBA nanoparticles by covalent binding to PBA can be triggered by addition of a surplus of glucose that bind to PBA competitively. The latter feature has been confirmed by fluorescence measurements using Alizarin Red as a model compound. Nanoparticles were proved to exhibit swelling in response to glucose as detected by light scattering.

  19. pH-Sensitive micelles self-assembled from amphiphilic copolymer brush for delivery of poorly water-soluble drugs.

    PubMed

    Yang, You Qiang; Zheng, Ling Shan; Guo, Xin Dong; Qian, Yu; Zhang, Li Juan

    2011-01-10

    A novel pH-sensitive amphiphilic copolymer brush poly(methyl methacrylate-co-methacrylic acid)-b-poly(poly(ethylene glycol) methyl ether monomethacrylate) [P(MMA-co-MAA)-b-PPEGMA] was defined and synthesized by atom transfer radical polymerization (ATRP) technique. The molecular structures and characteristics of this copolymer and its precursors were confirmed by (1)H NMR, FT-IR, and GPC. The CMC of P(MMA-co-MAA)-b-PPEGMA in aqueous medium was determined to be 1-4 mg/L. This copolymer could self-assemble into micelles in aqueous solution with an average size of 120-250 nm determined by DLS. The morphologies of the micelles were found to be spherical by SEM and TEM. Ibuprofen (IBU), a poorly water-soluble drug, was selected as the model drug and wrapped into the core of micelles via dialysis method. Drug entrapment efficiency reached to 90%. The in vitro release behavior of IBU from these micelles was pH-dependent. The cumulative release percent of IBU was less than 20% of the initial drug content in simulated gastric fluid (SGF, pH 1.2) over 12 h, but 90% was released in simulated intestinal fluid (SIF, pH 7.4) within 6 h. The release profiles showed that the P(MMA-co-MAA)-b-PPEGMA micelles could inhibit the premature burst drug release under the intestinal conditions. All the results indicate that the P(MMA-co-MAA)-b-PPEGMA micelle may be a potential oral drug delivery carrier for poorly water-soluble drugs. PMID:21121600

  20. Surface-induced ordering for confined random block copolymers

    NASA Astrophysics Data System (ADS)

    Gutman, Lorin; Chakraborty, Arup K.

    1994-12-01

    Motivated by practical issues that pertain to polymer adhesion, we consider the equilibrium behavior of a dilute solution of ideal A-B random block copolymers confined between two solid surfaces. We develop a general theory for the situation wherein the A-A, B-B, and A-B intersegment interactions are different, and furthermore, the A and B segments interact differently with the solid surfaces. Random block copolymers constitute a class of materials wherein a quenched disorder (the sequence distribution) is carried by the fluid whose statistical properties are of interest. In our theory, we perform quenched disorder averages using the replica trick. The nonlocal terms in our action functional are decoupled by introducing a set of random fields. The resulting equations for the propagator are analyzed within the framework of eigenfunction expansions. Since we consider long chains in confined geometries, we invoke the ground state approximation. We also carry out the functional integrals over the random fields using saddle points. Our theory does not treat the segment-surface interactions within a mean field approximation. Our analysis leads to a set of nonlinear self-consistent-field equations. We have solved our general equations numerically for a particular problem. In order to isolate and highlight the effects of dissimilar segment-surface interactions, we consider a case wherein the intersegment interactions are all alike (of the excluded volume type), while the A segments are attracted to the solid surfaces and the B units are repelled. For this specific problem we find that, above a threshold value of the fraction of attractive segments, significant microphase ordering is induced by the surface. This leads to damped oscillations in the composition profile. This onset of significant surface-induced composition fluctuations is accompanied by an ``adsorption-desorption transition'' which corresponds to a qualitative change in the shape of the total segment density

  1. Crystallization and Microphase Separation in Chiral Block Copolymers

    NASA Astrophysics Data System (ADS)

    Ho, Rong-Ming

    2012-02-01

    Block copolymers composed of chiral entities, denoted as chiral block copolymers (BCP*s), were designed to fabricate helical architectures from self-assembly. A helical phase (denoted H*) was discovered in the self-assembly of poly(styrene)-b-poly(L-lactide) (PS-PLLA) BCPs*. To examine the phase behavior of the PS-PLLA, self-assembled superstructures resulting from the competition between crystallization and microphase separation of the PS-PLLA in solution were examined. A kinetically controlled process by changing non-solvent addition rate was utilized to control the BCP* self-assembly. Single-crystal lozenge lamellae were obtained by the slow self-assembly (i.e., slow non-solvent addition rate) of PS-PLLA whereas amorphous helical ribbon superstructures were obtained from the fast self-assembly (i.e., fast non-solvent addition rate). As a result, the formation of helical architectures from the self-assembly of the PS-PLLA reflects the impact of chirality on microphase separation, but the chiral effect might be overwhelmed by crystallization. Consequently, various crystalline PS-PLLA nanostructures in bulk were obtained by controlling the crystallization temperature of PLLA (Tc,PLLA) at which crystalline helices and crystalline cylinders occur while Tc,PLLA=x Tg,PS, respectively. Anisotropic arrangement of the PLLA crystallites grown within the microdomains was identified. The formation of this exclusive crystalline growth is attributed to the spatial confinement effect for crystallization. While Tc,PLLA=x Tg,PS, the preferential growth may modulate the curvature of microdomains by shifting the molecular chains to access the fast path for crystalline growth due to the increase in chain mobility. As a result, a spring-like behavior of the helical nanostructure

  2. Fluorosilicone multi-block copolymers tethering quaternary ammonium salt groups for antimicrobial purpose

    NASA Astrophysics Data System (ADS)

    Zhou, Fang; Qin, Xiaoshuai; Li, Yancai; Ren, Lixia; Zhao, Yunhui; Yuan, Xiaoyan

    2015-08-01

    Symmetrically structured fluorosilicone multi-block copolymers containing poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(hexafluorobutyl methacrylate) (PHFBMA) were sequentially synthesized via reversible addition-fragmentation chain transfer polymerization, using a polydimethylsiloxane (PDMS) chain transfer agent with dithiocarbonate groups at both ends. Then, the CBABC-type block copolymers were quaternized with n-octyliodide to tether quaternary ammonium salt (QAS) groups in the PDMAEMA blocks for the antimicrobial use. The obtained fluorosilicone copolymers showed clear variations in the C-N+ composition and surface morphology on their films depending on the content of the PHFBMA blocks, which were characterized by X-ray photoelectron spectroscopy and atomic force microscopy, respectively. The results indicated that the symmetrical CBABC structure favored PDMS and QAS tethered blocks migrating to the film surface. With the mass percentage of the PHFBMA increased from 0 to 32.5%, the surface roughness of the copolymer film decreased gradually with a tendency to form a smooth surface. Owing to the surface properties, fluorosilicone multi-block copolymers containing a certain amount of PHFBMA with higher C-N+ content and relatively smooth morphology demonstrated obvious antimicrobial activity against Gram-positive bacteria, Bacillus subtilis and Gram-negative bacteria, Escherichia coli. The functionalized multi-block copolymers based on fluorosilicone and QAS groups would have potential applications in antimicrobial coatings.

  3. Method of producing nanopatterned articles using surface-reconstructed block copolymer films

    SciTech Connect

    Russell, Thomas P; Park, Soojin; Wang, Jia-Yu; Kim, Bokyung

    2013-08-27

    Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

  4. Phase Behavior of Star-shaped polystyrene-block-poly(methyl methacrylate) Copolymers

    NASA Astrophysics Data System (ADS)

    Jang, Sangshin; Moon, Hongchul; Lee, Youngmin; Kim, Jin Kon

    2012-02-01

    Star-shaped polystyrene-block-poly(methyl methacrylate) copolymer (PS-b-PMMA) was synthesized by utilizing α-cyclodextrin (α-CD) as a junction point of the star-shaped block copolymer. Eighteen hydroxyl groups on α-CD were substituted with bromine by the reaction with α-bromoisobutyryl bromide for atom transfer radical polymerization. We found that the number of bromine substituted arms per one α-CD was higher than 16 measured by nuclear magnetic resonance and Matrix-assisted laser desorption/ionization. We could control molecular weight of this unusual kind of block copolymer depending on polymerization times. Those polymers were characterized by gel permeation chromatography and nuclear magnetic resonance. Phase behavior of these star-shaped block copolymers were investigated.

  5. Theoretical and Experimental Investigations of Contact Hole Shrink using PS-PMMA Block Copolymers

    NASA Astrophysics Data System (ADS)

    Ginzburg, Valeriy; Hustad, Phillip; Weinhold, Jeffrey; Sharma, Rahul; Chuang, Vivian; Trefonas, Peter

    2012-02-01

    One possible application of block copolymer directed self-assembly (DSA) involves rectification or ``shrink'' of contact holes in a polarity switched photoresist (see, e.g., J. Cheng et al., ACS Nano 8, 4815 [2010]). The block copolymer (e.g., PS-PMMA) undergoes ordering inside the cylindrical hole; the central (PMMA) domain is then etched out so that the hole diameter is effectively reduced. We utilize strong segregation theory (SST) and numerical self-consistent field theory (SCFT) to calculate the phase behavior of the block copolymers as function of their molecular weight and composition, as well as the contact hole diameter and the surface chemistry of the walls. The model predictions were compared with experimental data, and a good agreement was found. The results illustrate how modeling can serve to guide block copolymer selection for DSA contact hole rectification application.

  6. Arrangement of C60 via the self-assembly of post-functionalizable polyisocyanate block copolymer.

    PubMed

    Min, Joonkeun; Shah, Priyank N; Chae, Chang-Geun; Lee, Jae-Suk

    2012-12-13

    Poly(furfuryl isocyanate) (PFIC), which includes the reactive furan group, was synthesized by anionic polymerization using a sodium benzhydroxide (Na-BH), self-assembly initiator. We determined the optimum polymerization conditions by varying both the reaction time and the molar ratio of the monomer to the initiator. Block copolymer, poly(furfuryl isocyanate)-b-poly(n-hexyl isocyanate), was synthesized under optimized polymerization conditions. The PFIC was modified by Diels-Alder reactions with C60 for functionalization. Transmission electron microscopy (TEM) was used to study the self-assembly of block copolymers and modified block copolymer with C60. C60 formed highly ordered aggregates on the PFIC domains via self-assembly of the block copolymer.

  7. Complexation-tailored morphology of asymmetric block copolymer membranes.

    PubMed

    Madhavan, Poornima; Peinemann, Klaus-Viktor; Nunes, Suzana P

    2013-08-14

    Hydrogen-bond formation between polystyrene-b-poly (4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) and -OH/-COOH functionalized organic molecules was used to tune morphology of asymmetric nanoporous membranes prepared by simultaneous self-assembly and nonsolvent induced phase separation. The morphologies were characterized by field emmision scanning electron microscopy (FESEM) and atomic force microscopy (AFM). Hydrogen bonds were confirmed by infrared (IR), and the results were correlated to rheology characterization. The OH-functionalized organic molecules direct the morphology into hexagonal order. COOH-functionalized molecules led to both lamellar and hexagonal structures. Micelle formation in solutions and their sizes were determined using dynamic light scattering (DLS) measurements and water fluxes of 600-3200 L/m(2)·h·bar were obtained. The pore size of the plain BCP membrane was smaller than with additives. The following series of additives led to pores with hexagonal order with increasing pore size: terephthalic acid (COOH-bifunctionalized) < rutin (OH-multifunctionalized) < 9-anthracenemethanol (OH-monofunctionalized) < 3,5-dihydroxybenzyl alcohol (OH-trifunctionalized).

  8. Direct Nanorod Assembly Using Block Copolymer-Based Supramolecules

    NASA Astrophysics Data System (ADS)

    Thorkelsson, Kari; Mastroianni, Alexander; Ercius, Peter; Xu, Ting

    2012-02-01

    One-dimensional nanomaterials with high aspect ratios, such as nanorods, exhibit unique and useful anisotropic optical, magnetic, and electrical properties. The collective properties of 1-D nanomaterials depend on their spatial arrangements, interparticle ordering, and macroscopic alignment. Developing routes to control their organization with high precision is critical to generate functional materials. We have investigated the co-assemblies of nanorods and block copolymer (BCP)-based supramolecules that self-assemble into spherical, lamellar and cylindrical morphologies. By varying energetic contributions from the rod-rod interactions and the deformation of the supramolecule, a wide library of nanorod assemblies including highly aligned arrays, continuous networks, and clusters can be readily accessed. Since macroscopic alignment of BCP microdomains can be obtained by application of external fields, present studies open up a new route to manipulate macroscopic alignments of nanorods. Fundamentally, these studies have demonstrated that in these blends, the energetic contributions from the polymer chain deformation and rod-rod interactions are comparable and can be tailored to disperse nanorods with control over inter-rod ordering and their relative alignment.

  9. Host-Guest Self-assembly in Block Copolymer Blends

    PubMed Central

    Park, Woon Ik; Kim, YongJoo; Jeong, Jae Won; Kim, Kyungho; Yoo, Jung-Keun; Hur, Yoon Hyung; Kim, Jong Min; Thomas, Edwin L.; Alexander-Katz, Alfredo; Jung, Yeon Sik

    2013-01-01

    Ultrafine, uniform nanostructures with excellent functionalities can be formed by self-assembly of block copolymer (BCP) thin films. However, extension of their geometric variability is not straightforward due to their limited thin film morphologies. Here, we report that unusual and spontaneous positioning between host and guest BCP microdomains, even in the absence of H-bond linkages, can create hybridized morphologies that cannot be formed from a neat BCP. Our self-consistent field theory (SCFT) simulation results theoretically support that the precise registration of a spherical BCP microdomain (guest, B-b-C) at the center of a perforated lamellar BCP nanostructure (host, A-b-B) can energetically stabilize the blended morphology. As an exemplary application of the hybrid nanotemplate, a nanoring-type Ge2Sb2Te5 (GST) phase-change memory device with an extremely low switching current is demonstrated. These results suggest the possibility of a new pathway to construct more diverse and complex nanostructures using controlled blending of various BCPs. PMID:24217036

  10. Multilayer block copolymer meshes by orthogonal self-assembly

    PubMed Central

    Tavakkoli K. G., Amir; Nicaise, Samuel M.; Gadelrab, Karim R.; Alexander-Katz, Alfredo; Ross, Caroline A.; Berggren, Karl K.

    2016-01-01

    Continued scaling-down of lithographic-pattern feature sizes has brought templated self-assembly of block copolymers (BCPs) into the forefront of nanofabrication research. Technologies now exist that facilitate significant control over otherwise unorganized assembly of BCP microdomains to form both long-range and locally complex monolayer patterns. In contrast, the extension of this control into multilayers or 3D structures of BCP microdomains remains limited, despite the possible technological applications in next-generation devices. Here, we develop and analyse an orthogonal self-assembly method in which multiple layers of distinct-molecular-weight BCPs naturally produce nanomesh structures of cylindrical microdomains without requiring layer-by-layer alignment or high-resolution lithographic templating. The mechanisms for orthogonal self-assembly are investigated with both experiment and simulation, and we determine that the control over height and chemical preference of templates are critical process parameters. The method is employed to produce nanomeshes with the shapes of circles and Y-intersections, and is extended to produce three layers of orthogonally oriented cylinders. PMID:26796218

  11. Ultraslow dynamics in asymmetric block copolymers with nanospherical domains.

    PubMed

    Mandare, Prashant; Winter, H Henning

    2006-01-01

    Low shear rate and low frequency measurements focused on the extremely slow dynamics of a three-dimensional body-centered cubic (BCC) structure of an asymmetric block copolymer under nanophase-separated conditions. The material studied was poly(styrene-b-ethylene-co-butylene-b-styrene) swollen in a hydrocarbon oil selective for the midblock. Transient viscosities during start-up of shear flow at extremely low shear rates are governed by very long relaxation times and by a modulus that is nearly the same as the plateau modulus obtained from oscillatory shear experiments. Only at extremely low shear rates a zero shear viscosity could be attained. Its very high value is close to the viscosity calculated from stress relaxation experiments. The steady shear viscosity decreases by several orders of magnitude when increasing the shear rate. SAXS experiments on samples sheared even at very low rates indicated loss of the BCC order that was present in the annealed samples before shearing. The SAXS profile recorded on such a sample showed a first-order maximum followed by a broad shoulder indicating a liquid-like short-range order of PS nanospheres in the swollen EB matrix.

  12. Non-crosslinked, amorphous, block copolymer electrolyte for batteries

    DOEpatents

    Mayes, Anne M.; Ceder, Gerbrand; Chiang, Yet-Ming; Sadoway, Donald R.; Aydinol, Mehmet K.; Soo, Philip P.; Jang, Young-Il; Huang, Biying

    2006-04-11

    Solid battery components are provided. A block copolymeric electrolyte is non-crosslinked and non-glassy through the entire range of typical battery service temperatures, that is, through the entire range of at least from about 0.degree. C. to about 70.degree. C. The chains of which the copolymer is made each include at least one ionically-conductive block and at least one second block immiscible with the ionically-conductive block. The chains form an amorphous association and are arranged in an ordered nanostructure including a continuous matrix of amorphous ionically-conductive domains and amorphous second domains that are immiscible with the ionically-conductive domains. A compound is provided that has a formula of Li.sub.xM.sub.yN.sub.zO.sub.2. M and N are each metal atoms or a main group elements, and x, y and z are each numbers from about 0 to about 1. y and z are chosen such that a formal charge on the M.sub.yN.sub.z portion of the compound is (4-x). In certain embodiments, these compounds are used in the cathodes of rechargeable batteries. The present invention also includes methods of predicting the potential utility of metal dichalgogenide compounds for use in lithium intercalation compounds. It also provides methods for processing lithium intercalation oxides with the structure and compositional homogeneity necessary to realize the increased formation energies of said compounds. An article is made of a dimensionally-stable, interpenetrating microstructure of a first phase including a first component and a second phase, immiscible with the first phase, including a second component. The first and second phases define interphase boundaries between them, and at least one particle is positioned between a first phase and a second phase at an interphase boundary. When the first and second phases are electronically-conductive and ionically-conductive polymers, respectively, and the particles are ion host particles, the arrangement is an electrode of a battery.

  13. Interactions between block copolymers and single-walled carbon nanotubes in aqueous solutions: a small-angle neutron scattering study.

    PubMed

    Granite, Meirav; Radulescu, Aurel; Pyckhout-Hintzen, Wim; Cohen, Yachin

    2011-01-18

    The amphiphilic copolymers of the Pluronic family are known to be excellent dispersants for single-walled carbon nanotubes (SWCNT) in water, especially F108 and F127, which have rather long end-blocks of poly(ethylene oxide) (PEO). In this study, the structure of the CNT/polymer hybrid formed in water is evaluated by measurements of small-angle neutron scattering (SANS) with contrast variation, as supported by cryo-transmission electron microscopy (cryo-TEM) imaging. The homogeneous, stable, inklike dispersions exhibited very small isolated bundles of carbon nanotubes in cryo-TEM images. SANS experiments were conducted at different D(2)O/H(2)O content of the dispersing solvent. The data for both systems showed surprisingly minimal intensity values at 70% D(2)O solvent composition, which is much higher than the expected value of 17% D(2)O that is based on the scattering length density (SLD) of PEO. At this near match point, the data exhibited a q(-1) power law relation of intensity to the scattering vector (q), indicating rodlike entities. Two models are evaluated, as extensions to Pederson's block copolymer micelles models. One is loosely adsorbed polymer chains on a rodlike CNT bundle. In the other, the hydrophobic block is considered to form a continuous hydrated shell on the CNT surface, whereas the hydrophilic blocks emanate into the solvent. Both models were found to fit the experimental data reasonably well. The model fit required special considerations of the tight association of water molecules around PEO chains and slight isotopic selectivity.

  14. Understanding and controlling morphology formation in Langmuir-Blodgett block copolymer films using PS-P4VP and PS-P4VP/PDP.

    PubMed

    Perepichka, Iryna I; Lu, Qing; Badia, Antonella; Bazuin, C Geraldine

    2013-04-01

    This contribution offers a comprehensive understanding of the factors that govern the morphologies of Langmuir-Blodgett (LB) monolayers of amphiphilic diblock copolymers (BCs). This is achieved by a detailed investigation of a wide range of polystyrene-poly(4-vinyl pyridine) (PS-P4VP) block copolymers, in contrast to much more limited ranges in previous studies. Parameters that are varied include the block ratios (mainly for similar total molecular weights, occasionally other total molecular weights), the presence or not of 3-n-pentadecylphenol (PDP, usually equimolar with VP, with which it hydrogen bonds), the spreading solution concentration ("low" and "high"), and the LB technique (standard vs "solvent-assisted"). Our observations are compared with previously published results on other amphiphilic diblock copolymers, which had given rise to contradictory interpretations of morphology formation. Based on the accumulated results, we re-establish early literature conclusions that three main categories of LB block copolymer morphologies are obtained depending on the block ratio, termed planar, strand, and dot regimes. The block composition boundaries in terms of mol % block content are shown to be similar for all BCs having alkyl chain substituents on the hydrophilic block (such as PS-P4VP/PDP) and are shifted to higher values for BCs with no alkyl chain substituents (such as PS-P4VP). This is attributed to the higher surface area per repeat unit of the hydrophilic block monolayer on the water surface for the former, as supported by the onset and limiting areas of the Langmuir isotherms for the BCs in the dot regime. 2D phase diagrams are discussed in terms of relative effective surface areas of the two blocks. We identify and discuss how kinetic effects on morphology formation, which have been highlighted in more recent literature, are superposed on the compositional effects. The kinetic effects are shown to depend on the morphology regime, most strongly

  15. The packing of soft materials: Molecular asymmetry, geometric frustration and optimal lattices in block copolymer melts

    NASA Astrophysics Data System (ADS)

    Grason, Gregory M.

    Melts of block copolymers provide an ideal route to engineering well-controlled structures on nanometer length scales. Through the control of only a few thermodynamic parameters, these systems can be tuned to self-assemble into periodic structures of an astounding variety. It is known that geometry plays a particularly important role in determining equilibrium structure since phase behavior of copolymer melts is generically insensitive to detail at the monomeric scale. Here, we explore a particular way in which the geometry of packing objects in three dimensions frustrates the internal configurations of segregated block copolymer domains. In particular, we find that lattices of spherical micelles are sensitive to the periodic structure of the lattice arrangement because these micelles are forced to occupy the non-ideal, polyhedral unit cells of the lattice. By analyzing the energetics of block copolymer melts in the limit of strongly-segregated domains, we find that the interfaces which separate unlike polymer domains tend to adopt the polyhedral shape of the lattice unit cell, and this tendency is entirely controlled by the specific copolymer architecture. Furthermore, in the limit where interfaces are perfectly polyhedral, a remarkable simplicity emerges, and the relative stability of competing lattice arrangements of micelles can be assessed purely in terms of geometric measures of the two-dimensional lattice unit cell. From this analysis we predict the stability of a novel cubic arrangement spherical micelles in block copolymer melts, the A15 lattice. To corroborate our geometric arguments we develop and implement a numerical self-consistent field theory for melts of highly asymmetric block copolymers. This field theory allows us to systematically and efficiently explore the equilibrium phase behavior of asymmetric copolymer melts as a function of molecular architecture. These numerical results bear out the predictions of our geometric analysis and confirm that

  16. Electrically conductive doped block copolymer of polyacetylene and polyisoprene. [Soluble in organic solvents

    DOEpatents

    Aldissi, M.

    1984-06-27

    An electrically conductive block copolymer of polyisoprene and polyacetylene and a method of making the same are disclosed. The polymer is prepared by first polymerizing isoprene with n-butyllithium in a toluene solution to form an active isoprenyllithium polymer. The active polymer is reacted with an equimolar amount of titanium butoxide and subsequently exposed to gaseous acetylene. A block copolymer of polyisoprene and polyacetylene is formed. The copolymer is soluble in common solvents and may be doped with I/sub 2/ to give it an electrical conductivity in the metallic regime.

  17. Tunable Encapsulation Structure of Block Copolymer Coated Single-Walled Carbon Nanotubes in Aqueous Solution

    DOE PAGES

    Han, Youngkyu; Ahn, Suk-Kyun; Zhang, Zhe; Smith, Gregory Scott; Do, Changwoo

    2015-05-15

    The nano-sized and shape-tunable molecular building blocks can provide great opportunities for the fabrication of precisely controlled nanostructures. In this work, we have fabricated a molecular building block of single-walled carbon nanotubes (SWNTs) coated by PPO-PEO-PPO block copolymers whose encapsulation structure can be controlled via temperature or addition of small molecules. The structure and optical properties of SWNT-block copolymers have been investigated by small angle neutron scattering (SANS), ultraviolet-visible (UV-vis) spectroscopy, atomic force microscopy (AFM), and molecular dynamics (MD) simulation. The structure of the hydrated block copolymer layer surrounding SWNT can be controlled reversibly by varying temperature as well asmore » by irreversibly adding 5-methylsalicylic acid (5MS). Increasing hydrophobicity of the polymers with temperature and strong tendency of 5MS to interact with both block copolymers and orbitals of the SWNTs are likely to be responsible for the significant structural change of the block copolymer encapsulation layer, from loose corona shell to tightly encapsulating compact shell. These result shows an efficient and simple way to fabricate and manipulate carbon-based nano building blocks in aqueous systems with tunable structure.« less

  18. Ionic Interactions for Aqueous Templating of Biofunctional Molecules in Block Copolymer Nanostructures

    NASA Astrophysics Data System (ADS)

    Olsen, Bradley; Kim, Bokyung; Lam, Christopher; Stewart-Sloan, Charlotte; Gkikas, Emmanouil

    2013-03-01

    The use of ionic interactions to direct both biomolecular templating and block copolymer self-assembly into nanopatterned films with only aqueous processing conditions is demonstrated using block copolymers containing both thermally responsive and pH responsive blocks. Reversible addition-fragmentation chain transfer (RAFT) polymerization is employed to synthesize diblock copolymers with one neutral thermoresponsive and one polycationic block and the pH-dependnent complexation between model proteins or biomimetic J-aggregating chromophores and the polycationic block is demonstrated. Spin casting is used to prepare nanostructured films from the protein-block copolymer and chromophore-block copolymer coacervates. After film formation, the lower critical solution temperature (LCST) of the thermoresponsive block allows the nanomaterial to be effectively immobilized in aqueous environments at physiological temperatures, enabling use of the materials for biomolecule immobilization and controlled release. In the case of protein nanotemplating, the ionic environment in which the protein is confined enables the majority of the protein (80%) to retain its activity, even after having been dehydrated in vacuum and confined in the thin film.

  19. Tunable Encapsulation Structure of Block Copolymer Coated Single-Walled Carbon Nanotubes in Aqueous Solution

    SciTech Connect

    Han, Youngkyu; Ahn, Suk-Kyun; Zhang, Zhe; Smith, Gregory Scott; Do, Changwoo

    2015-05-15

    The nano-sized and shape-tunable molecular building blocks can provide great opportunities for the fabrication of precisely controlled nanostructures. In this work, we have fabricated a molecular building block of single-walled carbon nanotubes (SWNTs) coated by PPO-PEO-PPO block copolymers whose encapsulation structure can be controlled via temperature or addition of small molecules. The structure and optical properties of SWNT-block copolymers have been investigated by small angle neutron scattering (SANS), ultraviolet-visible (UV-vis) spectroscopy, atomic force microscopy (AFM), and molecular dynamics (MD) simulation. The structure of the hydrated block copolymer layer surrounding SWNT can be controlled reversibly by varying temperature as well as by irreversibly adding 5-methylsalicylic acid (5MS). Increasing hydrophobicity of the polymers with temperature and strong tendency of 5MS to interact with both block copolymers and orbitals of the SWNTs are likely to be responsible for the significant structural change of the block copolymer encapsulation layer, from loose corona shell to tightly encapsulating compact shell. These result shows an efficient and simple way to fabricate and manipulate carbon-based nano building blocks in aqueous systems with tunable structure.

  20. Mechanism of titania deposition into cylindrical poly(styrene-block-4 vinyl pyridine) block copolymer templates.

    PubMed

    Lou, Qin; Chinthamanipeta, Pavan S; Shipp, Devon A

    2011-12-20

    A simple and effective way for TiO(2) to be deposited on silicon or indium tin oxide (ITO) substrates has been achieved by using a poly(styrene-block-4-vinyl pyridine) (PS-b-P4VP) block copolymer template. In particular, a mechanism for the formation of TiO(2) within the P4VP phase was developed. Within this model, the TiO(2) deposition occurs by swelling of the protonated P4VP segments followed by transport of Ti precursor, probably protonated Ti(OH)(4) given the low pH conditions used, into the swollen P4VP followed by condensation into TiO(2) during the heating/plasma etch processes. TiO(2) nanostructure morphology is affected by pH and deposition temperatures, because these parameters affect the degree of protonation of P4VP segments and diffusion of the titanium(IV) bis(ammonium lactato)dihydroxide (TALH) precursor into the film. A pH range of 2.1-2.5 for silicon substrates and pH = 2.1 for ITO substrates gave the narrower TiO(2) nanostructures distributions, and deposition at 70 °C gave TiO(2) nanostructures with more regular arrangements and smoother surface than those deposited at room temperature. The use of 1,4-diiodobutane as a P4VP cross-linking compound is demonstrated to be a critical parameter for maintaining good cylindrical surface morphology for both the block copolymer template and the TiO(2) nanostructures.

  1. Fabrication and photoactivity of a tunable-void SiO₂-TiO₂ core-shell structure on modified SiO₂ nanospheres by grafting an amphiphilic diblock copolymer using ARGET ATRP.

    PubMed

    Zhao, Minnan; Zhou, Guowei; Zhang, Lei; Li, Xiuyan; Li, Tianduo; Liu, Fangfang

    2014-02-28

    SiO₂-based composites have important applications in various technological fields. In this work, a tunablevoid SiO₂-TiO₂ core-shell structure was successfully prepared for the first time using SiO₂-polymethyl methacrylate (PMMA)-polyoligo(ethylene glycol)methyl ether methacrylate (PO(EO)nMA) (n = 2, 5, and 8). An amphiphilic copolymer was used as the template, and calcination was performed using tetrabutyl titanate (TBT) as the titanium source. SiO₂-PMMA-b-PO(EO)nMA microspheres were first synthesized through activators regenerated by electron transfer-atom transfer radical polymerization. Methyl methacrylate and O(EO)nMA were grafted with different EO unit numbers onto the surface of the halogen functional group of SiO₂. TBT was hydrolyzed along with the PO(EO)nMA chain through hydrogen bonding, and then the SiO₂-TiO₂ core-shell structure was acquired through calcination to remove the polymer. Simultaneously, amorphous TiO₂ crystallized during calcination. A series of characterizations indicated that the amphiphilic block copolymer was grafted onto SiO₂ mesoparticle surfaces, the titania samples existed only in the anatase phase, and the prepared SiO₂-TiO₂ had hierarchically nanoporous structures. The gradient hydrophilicity of the PMMA-b-PO(EO)nMA copolymer template facilitated the hydrolysis of TBT molecules along the PO(EO)nMA to PMMA segments, thereby tuning the space between the core and the shell. In addition, the space was about 6 nm when the EO number was 2, and the space was about 10 nm when the EO numbers were 5 and 8. The photocatalytic activities of the SiO₂-TiO₂ materials were tested on the photodegradation of methyl orange. PMID:24795964

  2. Tuning of Polymeric Nanoparticles by Coassembly of Thermoresponsive Polymers and a Double Hydrophilic Thermoresponsive Block Copolymer.

    PubMed

    Zhang, Qilu; Voorhaar, Lenny; Filippov, Sergey K; Yeşil, Berin Fatma; Hoogenboom, Richard

    2016-05-26

    The coassembly behavior of thermoresponsive statistical copolymers and a double hydrophilic block copolymer having a permanently hydrophilic block and a thermoresponsive block is investigated. By adjusting the hydrophilicity of the thermoresponsive statistical copolymers, hybrid nanoparticles are obtained with various ratios of the two species. Importantly, the size of these nanoparticles can be controlled in between 40 and 250 nm dependent on the TCP and the amount of statistical copolymers in the solution. Simultaneous analysis of static and dynamic light scattering data indicates that the possible structure of nanoparticles varies from hard sphere to less compact architecture and most probably depends on a difference between cloud point temperatures of individual components. This developed coassembly method provides a simple platform for the preparation of defined polymeric nanoparticles. PMID:27144970

  3. High-Tg Polynorbornene-Based Block and Random Copolymers for Butanol Pervaporation Membranes

    NASA Astrophysics Data System (ADS)

    Register, Richard A.; Kim, Dong-Gyun; Takigawa, Tamami; Kashino, Tomomasa; Burtovyy, Oleksandr; Bell, Andrew

    Vinyl addition polymers of substituted norbornene (NB) monomers possess desirably high glass transition temperatures (Tg); however, until very recently, the lack of an applicable living polymerization chemistry has precluded the synthesis of such polymers with controlled architecture, or copolymers with controlled sequence distribution. We have recently synthesized block and random copolymers of NB monomers bearing hydroxyhexafluoroisopropyl and n-butyl substituents (HFANB and BuNB) via living vinyl addition polymerization with Pd-based catalysts. Both series of polymers were cast into the selective skin layers of thin film composite (TFC) membranes, and these organophilic membranes investigated for the isolation of n-butanol from dilute aqueous solution (model fermentation broth) via pervaporation. The block copolymers show well-defined microphase-separated morphologies, both in bulk and as the selective skin layers on TFC membranes, while the random copolymers are homogeneous. Both block and random vinyl addition copolymers are effective as n-butanol pervaporation membranes, with the block copolymers showing a better flux-selectivity balance. While polyHFANB has much higher permeability and n-butanol selectivity than polyBuNB, incorporating BuNB units into the polymer (in either a block or random sequence) limits the swelling of the polyHFANB and thereby improves the n-butanol pervaporation selectivity.

  4. Preparation of Pickering Double Emulsions Using Block Copolymer Worms

    PubMed Central

    2015-01-01

    The rational formulation of Pickering double emulsions is described using a judicious combination of hydrophilic and hydrophobic block copolymer worms as highly anisotropic emulsifiers. More specifically, RAFT dispersion polymerization was utilized to prepare poly(lauryl methacrylate)–poly(benzyl methacrylate) worms at 20% w/w solids in n-dodecane and poly(glycerol monomethacrylate)–poly(2-hydroxypropyl methacrylate)–poly(benzyl methacrylate) worms at 13% w/w solids in water by polymerization-induced self-assembly (PISA). Water-in-oil-in-water (w/o/w) double emulsions can be readily prepared with mean droplet diameters ranging from 30 to 80 μm using a two-stage approach. First, a w/o precursor emulsion comprising 25 μm aqueous droplets is prepared using the hydrophobic worms, followed by encapsulation within oil droplets stabilized by the hydrophilic worms. The double emulsion droplet diameter and number of encapsulated water droplets can be readily varied by adjusting the stirring rate employed during the second stage. For each stage, the droplet volume fraction is relatively high at 0.50. The double emulsion nature of the final formulation was confirmed by optical and fluorescence microscopy studies. Such double emulsions are highly stable to coalescence, with little or no change in droplet diameter being detected over storage at 20 °C for 10 weeks as judged by laser diffraction. Preliminary experiments indicate that the complementary o/w/o emulsions can also be prepared using the same pair of worms by changing the order of homogenization, although somewhat lower droplet volume fractions were required in this case. Finally, we demonstrate that triple and even quadruple emulsions can be formulated using these new highly anisotropic Pickering emulsifiers. PMID:25834923

  5. Preparation of Pickering double emulsions using block copolymer worms.

    PubMed

    Thompson, Kate L; Mable, Charlotte J; Lane, Jacob A; Derry, Mathew J; Fielding, Lee A; Armes, Steven P

    2015-04-14

    The rational formulation of Pickering double emulsions is described using a judicious combination of hydrophilic and hydrophobic block copolymer worms as highly anisotropic emulsifiers. More specifically, RAFT dispersion polymerization was utilized to prepare poly(lauryl methacrylate)-poly(benzyl methacrylate) worms at 20% w/w solids in n-dodecane and poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate)-poly(benzyl methacrylate) worms at 13% w/w solids in water by polymerization-induced self-assembly (PISA). Water-in-oil-in-water (w/o/w) double emulsions can be readily prepared with mean droplet diameters ranging from 30 to 80 μm using a two-stage approach. First, a w/o precursor emulsion comprising 25 μm aqueous droplets is prepared using the hydrophobic worms, followed by encapsulation within oil droplets stabilized by the hydrophilic worms. The double emulsion droplet diameter and number of encapsulated water droplets can be readily varied by adjusting the stirring rate employed during the second stage. For each stage, the droplet volume fraction is relatively high at 0.50. The double emulsion nature of the final formulation was confirmed by optical and fluorescence microscopy studies. Such double emulsions are highly stable to coalescence, with little or no change in droplet diameter being detected over storage at 20 °C for 10 weeks as judged by laser diffraction. Preliminary experiments indicate that the complementary o/w/o emulsions can also be prepared using the same pair of worms by changing the order of homogenization, although somewhat lower droplet volume fractions were required in this case. Finally, we demonstrate that triple and even quadruple emulsions can be formulated using these new highly anisotropic Pickering emulsifiers.

  6. Block-copolymer of polyethylene glycol and polylysine as a carrier of organic iodine: design of long-circulating particulate contrast medium for X-ray computed tomography.

    PubMed

    Trubetskoy, V S; Gazelle, G S; Wolf, G L; Torchilin, V P

    1997-01-01

    In order to obtain small, polymer-stabilized particulate carriers for organic iodine to serve as a contrast agent for X-ray computed tomography (CT) an attempt was made to design a carrier based on polymeric micelles. Here we describe the synthesis of an iodine-containing amphiphilic block-copolymer which can micellize in aqueous solutions. The two blocks of the copolymer consisted of methoxypoly(ethyleneglycol) and poly[epsilon,N-(triiodobenzoyl)-L-lysine]. Upon dispersion in water, the block copolymer formed particles with average diameter 80 nm and iodine content up to 44.7%. The particles start to dissociate to the individual polymeric chains in the concentration range of 0.05-0.5 microM in water at 23 degrees C. Upon intravenous injection at 250 mg of iodine/kg (570 mg of the agent/kg) in rabbits the medium demonstrated exceptional 24 hr half-life in the blood substantiating corona/core structure of the particles with PEG chains protecting the iodine-containing core. The possible use of these particulates as contrast medium for X-ray computed tomography is discussed.

  7. Poly(vinylidene fluoride)/nickel nanocomposites from semicrystalline block copolymer precursors.

    PubMed

    Voet, Vincent S D; Tichelaar, Martijn; Tanase, Stefania; Mittelmeijer-Hazeleger, Marjo C; ten Brinke, Gerrit; Loos, Katja

    2013-01-01

    The fabrication of nanoporous poly(vinylidene fluoride) (PVDF) and PVDF/nickel nanocomposites from semicrystalline block copolymer precursors is reported. Polystyrene-block-poly(vinylidene fluoride)-block-polystyrene (PS-b-PVDF-b-PS) is prepared through functional benzoyl peroxide initiated polymerization of VDF, followed by atom transfer radical polymerization (ATRP) of styrene. The crystallization of PVDF plays a dominant role in the formation of the block copolymer structure, resulting in a spherulitic superstructure with an internal crystalline-amorphous lamellar nanostructure. The block copolymer promotes the formation of the ferroelectric β-polymorph of PVDF. Selective etching of the amorphous regions with nitric acid leads to nanoporous PVDF, which functions as a template for the generation of PVDF/Ni nanocomposites. The lamellar nanostructure and the β-crystalline phase are conserved during the etching procedure and electroless nickel deposition. PMID:23138962

  8. Interactions between plasma and block copolymers used in directed self-assembly patterning

    NASA Astrophysics Data System (ADS)

    Sirard, Stephen; Azarnouche, Laurent; Gurer, Emir; Durand, William; Maher, Michael; Mori, Kazunori; Blachut, Gregory; Janes, Dustin; Asano, Yusuke; Someya, Yasunobu; Hymes, Diane; Graves, David; Ellison, Christopher J.; Willson, C. Grant

    2016-03-01

    The directed self-assembly (DSA) of block copolymers offers a promising route for scaling feature sizes below 20 nm. At these small dimensions, plasmas are often used to define the initial patterns. It is imperative to understand how plasmas interact with each block in order to design processes with sufficient etch contrast and pattern fidelity. Symmetric lamella forming block copolymers including, polystyrene-b-poly(methyl methacrylate) and several high-χ silicon-containing and tin-containing block copolymers were synthesized, along with homopolymers of each block, and exposed to various oxidizing, reducing, and fluorine-based plasma processes. Etch rate kinetics were measured, and plasma modifications of the materials were characterized using XPS, AES, and FTIR. Mechanisms for achieving etch contrast were elucidated and were highly dependent on the block copolymer architecture. For several of the polymers, plasma photoemissions were observed to play an important role in modifying the materials and forming etch-resistant protective layers. Furthermore, it was observed for the silicon- and tin-containing polymers that an initial transient state exists, where the polymers exhibit an enhanced etch rate, prior to the formation of the etch-resistant protective layer. Plasma developed patterns were demonstrated for the differing block copolymer materials with feature sizes ranging from 20 nm down to approximately 5 nm.

  9. Amphiphilic Copolymers of Polyfluorene Methacrylates Exhibiting Tunable Emissions for Ink-Jet Printing.

    PubMed

    Deng, Chao; Ling, Jun

    2016-08-01

    Functionalized polyfluorene receives more and more attention due to its wide applications. Here, the syntheses of three novel polyfluorene-based methacrylate macromonomers exhibiting a vast flexibility for further applications are reported. Their emissions strongly depend on the end groups and thus the macromonomers provide blue, green, and red emissions simultaneously with the same excitation light of 365 nm. Their well-defined copolymers with 2-(dimethylamino) ethyl methacrylate via reversible addition-fragmentation chain transfer polymerization are investigated in detail. These copolymers exhibit high quantum yields in solid film (up to 0.8), and self-assemble into photoluminescent nanoparticles in aqueous solutions with pure blue, green, and red emissions. By simply mixing them, perfect white light emission with high quality is obtained. These aqueous nanoparticles solutions are ready for ink-jet printing to produce exquisite bright and colorful fluorescent pictures. PMID:27310485

  10. Low-Temperature Processable Block Copolymers That Preserve the Function of Blended Proteins.

    PubMed

    Iwasaki, Yasuhiko; Takemoto, Kyohei; Tanaka, Shinya; Taniguchi, Ikuo

    2016-07-11

    Low-temperature processable polymers have attracted increasing interest as ecological materials because of their reduced energy consumption during processing and suitability for making composites with heat-sensitive biomolecules at ambient temperature. In the current study, low-temperature processable biodegradable block copolymers were synthesized by ring-opening polymerization of l-lactide (LLA) using polyphosphoester as a macroinitiator. The polymer films could be processed under a hydraulic pressure of 35 MPa. The block copolymer films swelled in water because the polyphosphoester block was partially hydrated. Interestingly, the swelling ratio of the films changed with temperature. The pressure-induced order-to-disorder transition of the block copolymers was characterized by small-angle X-ray scattering; a crystallinity reduction in the block copolymers was observed after application of pressure. The crystallinity of the block copolymers was recovered after removing the applied pressure. The Young's modulus of the block copolymer films increased as the LLA unit content increased. Moreover, the modulus did not change after multiple processing cycles and the recyclability of the block copolymers was also confirmed. Finally, polymer films with embedded proteinase K as a model protein were prepared. The activity of catalase loaded into the polymer films was evaluated after processing at different temperatures. The activity of catalase was preserved when the polymer films were processed at room temperature but was significantly reduced after high-temperature processing. The suitability of low-temperature processable biodegradable polymers for making biofunctional composites without reducing protein activity was clarified. These materials will be useful for biomedical and therapeutic applications. PMID:27280847

  11. Controlled self-assembly of conjugated rod-coil block copolymers for applications in organic optoelectronics

    NASA Astrophysics Data System (ADS)

    Tao, Yuefei

    Organic electronics are of great interest in manufacturing light weight, mechanical flexible, and inexpensive large area devices. While significant improvements have been made over the last several years and it is now clear that morphology on the lengthscale of exciton diffusion (10nm) is of crucial importance, a clear relationship between structure and device properties has not emerged. This lack of understanding largely emerges from an inability to control morphology on this lengthscale. This thesis will center around an approach, based on block copolymer self-assembly, to generate equilibrium nanostructures on the 10 nm lengthscale of exciton diffusion and study their effects on device performance. Self-assembly of semiconducting block copolymers is complicated by the non-classical chain shape of conjugated polymers. Unlike classical polymers, the chains do not assume a Gaussian coil shape which is stretched near block copolymer interfaces, instead the chains are elongated and liquid crystalline. Previous work has demonstrated how these new molecular interactions and shapes control the phase diagram of so-called rod-coil block copolymers. Here, we will focus on controlling domain size, orientation, and chemical structure. While domain size can be controlled directly through molecular weight, this requires significant additional synthesis of domain size is to be varied. Here, the domain size is controlled by blending homopolymers into a self-assembling rod-coil block copolymer. When coil-like blocks are incorporated, the domains swell, as expected. When rod-like blocks are incorporated, they interdigitate with the rods of the block copolymers. This results in an increase in interfacial area which forces the coils to rearrange and an overall decrease in domain size with increasing rod content. Control over lamellar orientation is crucial in order to design and control charge transport pathways and exciton recombination or separation interfaces. While numerous

  12. Distinct Adsorption Configurations and Self-Assembly Characteristics of Fibrinogen on Chemically Uniform and Alternating Surfaces including Block Copolymer Nanodomains

    PubMed Central

    2015-01-01

    Understanding protein–surface interactions is crucial to solid-state biomedical applications whose functionality is directly correlated with the precise control of the adsorption configuration, surface packing, loading density, and bioactivity of protein molecules. Because of the small dimensions and highly amphiphilic nature of proteins, investigation of protein adsorption performed on nanoscale topology can shed light on subprotein-level interaction preferences. In this study, we examine the adsorption and assembly behavior of a highly elongated protein, fibrinogen, on both chemically uniform (as-is and buffered HF-treated SiO2/Si, and homopolymers of polystyrene and poly(methyl methacrylate)) and varying (polystyrene-block-poly(methyl methacrylate)) surfaces. By focusing on high-resolution imaging of individual protein molecules whose configurations are influenced by protein–surface rather than protein–protein interactions, fibrinogen conformations characteristic to each surface are identified and statistically analyzed for structural similarities/differences in key protein domains. By exploiting block copolymer nanodomains whose repeat distance is commensurate with the length of the individual protein, we determine that fibrinogen exhibits a more neutral tendency for interaction with both polystyrene and poly(methyl methacrylate) blocks relative to the case of common globular proteins. Factors affecting fibrinogen–polymer interactions are discussed in terms of hydrophobic and electrostatic interactions. In addition, assembly and packing attributes of fibrinogen are determined at different loading conditions. Primary orientations of fibrinogen and its rearrangements with respect to the underlying diblock nanodomains associated with different surface coverage are explained by pertinent protein interaction mechanisms. On the basis of two-dimensional stacking behavior, a protein assembly model is proposed for the formation of an extended fibrinogen network

  13. Combinatorial Block Copolymer Ordering on Tunable Rough Substrates

    SciTech Connect

    Kulkarni, Manish M.; Yager, Kevin G.; Sharma, Ashutosh; Karim, Alamgir

    2012-10-25

    Morphology control of block copolymer (BCP) thin films through substrate interaction via controlled roughness parameters is of significant interest for numerous high-tech applications ranging from solar cells to high-density storage media. While effects of substrate surface energy (SE) and roughness (R) on BCP morphology have been individually investigated, their synergistic effects have not been explored in any systematic manner. Interestingly, orientation response of BCP to changes in SE can be similar to what can be accomplished with variations in R. Here we present a novel approach for orienting lamellar BCP films of poly(styrene)-block-poly(methyl methacrylate) (PS-PMMA) on spin-coated xerogel (a dried gel of silica nanoparticle network) substrate with simultaneously tunable surface energy, {gamma}{sub s} {approx} 29-53 mJ/m{sup 2}, by UVO exposure and roughness, R{sub rms} {approx} 0.5-30 nm, by sol-gel processing steps of regulating the catalyst concentration and sol aging time. As in previous BCP orientation studies on 20 nm diameter monodisperse silica nanoparticle coated surface, we find a similar but broadened oscillatory BCP orientation behavior with film thickness due to the random rather than periodic rough surfaces. We also find that higher random roughness amplitude is not the necessary criteria for obtaining a vertical orientation of BCP lamellae. Rather, a high surface fractal dimension (D{sub f} > 2.4) of the rough substrate in conjunction with an optimal substrate surface energy {gamma}{sub s} {approx} 29 mJ/m{sup 2} results in 100% vertically oriented lamellar microdomains. The AFM measured film surface microstructure correlates well with the internal 3D BCP film structure probed by grazing incidence small-angle X-ray scattering (GISAXS) and rotational small-angle neutron scattering (SANS). In contrast to tunable self-assembled monolayer (SAM)-coated substrates, the xerogel films are very durable and retain their chemical properties over period

  14. Poly(vinylidene fluoride)/nickel nanocomposites from semicrystalline block copolymer precursors

    NASA Astrophysics Data System (ADS)

    Voet, Vincent S. D.; Tichelaar, Martijn; Tanase, Stefania; Mittelmeijer-Hazeleger, Marjo C.; ten Brinke, Gerrit; Loos, Katja

    2012-12-01

    The fabrication of nanoporous poly(vinylidene fluoride) (PVDF) and PVDF/nickel nanocomposites from semicrystalline block copolymer precursors is reported. Polystyrene-block-poly(vinylidene fluoride)-block-polystyrene (PS-b-PVDF-b-PS) is prepared through functional benzoyl peroxide initiated polymerization of VDF, followed by atom transfer radical polymerization (ATRP) of styrene. The crystallization of PVDF plays a dominant role in the formation of the block copolymer structure, resulting in a spherulitic superstructure with an internal crystalline-amorphous lamellar nanostructure. The block copolymer promotes the formation of the ferroelectric β-polymorph of PVDF. Selective etching of the amorphous regions with nitric acid leads to nanoporous PVDF, which functions as a template for the generation of PVDF/Ni nanocomposites. The lamellar nanostructure and the β-crystalline phase are conserved during the etching procedure and electroless nickel deposition.The fabrication of nanoporous poly(vinylidene fluoride) (PVDF) and PVDF/nickel nanocomposites from semicrystalline block copolymer precursors is reported. Polystyrene-block-poly(vinylidene fluoride)-block-polystyrene (PS-b-PVDF-b-PS) is prepared through functional benzoyl peroxide initiated polymerization of VDF, followed by atom transfer radical polymerization (ATRP) of styrene. The crystallization of PVDF plays a dominant role in the formation of the block copolymer structure, resulting in a spherulitic superstructure with an internal crystalline-amorphous lamellar nanostructure. The block copolymer promotes the formation of the ferroelectric β-polymorph of PVDF. Selective etching of the amorphous regions with nitric acid leads to nanoporous PVDF, which functions as a template for the generation of PVDF/Ni nanocomposites. The lamellar nanostructure and the β-crystalline phase are conserved during the etching procedure and electroless nickel deposition. Electronic supplementary information (ESI) available

  15. Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

    NASA Technical Reports Server (NTRS)

    Sun, Sam-Shajing; Fan, Zhen; Wang, Yiqing; Taft, Charles; Haliburton, James; Maaref, Shahin

    2002-01-01

    It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

  16. Antimicrobial activity of poly(acrylic acid) block copolymers.

    PubMed

    Gratzl, Günther; Paulik, Christian; Hild, Sabine; Guggenbichler, Josef P; Lackner, Maximilian

    2014-05-01

    The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid-base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure.

  17. Electrochemical redox responsive polymeric micelles formed from amphiphilic supramolecular brushes.

    PubMed

    Feng, Anchao; Yan, Qiang; Zhang, Huijuan; Peng, Liao; Yuan, Jinying

    2014-05-11

    The end-decorated homopolymer poly(ε-caprolactone)-ferrocene threaded onto a β-cyclodextrin-functionalized main-chain polymer can form a class of amphiphilic noncovalent graft copolymers based on the host-guest interactions of the terminal groups on the side chains. These new supramolecular polymer brushes can further self-assemble into micellar aggregates that exhibit reversible assembly and disassembly behavior under an electrochemical redox trigger, which opens up a new route to building dynamic block copolymer topologies.

  18. Patterning square and rectangular arrays using shear-aligned block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Kim, So Youn; Davis, Raleigh L.; Register, Richard A.; Gwyther, Jessica; Nunns, Adam; Manners, Ian; Chaikin, Paul M.

    2014-03-01

    Microphase separation of block copolymers in thin films can generate periodic structures: hexagonally packed arrays of dots from spherical or cylindrical phase block copolymers, or periodic stripes from cylindrical or lamellar phase block copolymers. Square or rectangular patterns, however, do not naturally form by spontaneous self-assembly of a simple diblock copolymer, and are a challenge to create. We present a simple way to create nano-square/rectangular arrays by building up a double-layer film of a cylinder-forming diblock, where each layer is sequentially deposited, shear-aligned independently, and cross-linked. Any block copolymer with at least one crosslinkable block can in principle be employed; in this study we use cylinder-forming polystyrene-b-poly(ferrocenylisopropylmethylsilane) and polystyrene-b-poly(hexylmethacrylate). The pitch of the array is tunable by varying polymer molecular weight. Oxygen reactive ion etching is used to reveal the grid structures, and these grids can in turn form nano-wells in the silicon substrate when the cylinder-forming block is very etch-resistant under the conditions used for silicon etching. Additionally, metal dots ordered in square arrays can be created using these grids as templates, via metal evaporation and lift-off.

  19. Frank-Kasper sigma phase stabilized by tailored architectures of block copolymers

    NASA Astrophysics Data System (ADS)

    Li, Weihua; Liu, Meijiao; Xie, Nan; Qiu, Feng; Shi, An-Chang

    Block copolymer self-assembly forms diverse interesting ordered morphologies, of which the spherical phase is of particular interest because it resembles the similar space symmetry as atomic crystals and has a tunable period on nanoscale. Moreover, the packing lattice of spherical domains dictated by the adjustable competition between the entropic and interfacial energies is programmable. For AB diblock copolymers, it has been known that the stable spherical phase is mainly bcc except for a very narrow region of fcc at the vicinity of the order-disorder transition. When introducing variable number of blocks and architectures to form complex AB-type block copolymers, the A15 phase was predicted as stable. However, a striking experiment observed a new spherical phase, the complex Frank-Kasper sigma phase that consists of 30 spheres in a unit cell, in the PI-b-PLA diblock copolymer as well as a SISO tetrablock terpolymer. Inspired by this experiment, we studied the stability of all known spherical phases of fcc, bcc, A15 and sigma in various block copolymers including conformationally asymmetric AB diblock, ABm miktoarm, and BABC tetrablock copolymers. We have revealed the formation mechanism of the nonclassical A15 and sigma phases due to the tailored architectures.

  20. Microphase separation in thin films of lamellar forming polydisperse di-block copolymers

    SciTech Connect

    Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.; Chen, Jihua; Heller, William T.; Ankner, John F.; Browning, James F.; Kilbey, II, S. Michael; Sumpter, Bobby G.

    2015-02-03

    Despite the ubiquity of polydispersity in chain lengths of di-block copolymers, its effects on microphase separation in thin films have eluded a clear understanding. In this paper, we have studied effects of polydispersity on the microphase separation in thin films of lamellar forming di-block copolymers using self-consistent field theory (SCFT) and neutron reflectivity experiments. Di-block copolymers containing a polydisperse block of poly(glycidylmethacrylate) (PGMA) connected to a near-monodisperse block poly(2-vinyl-4,4-dimethyl-d6 azlactone) (PVDMA-d6) are considered in this work. Effects of chain length polydispersity, film thickness, substrate–monomer and monomer–monomer interactions on the microphase segregation are studied using SCFT. The theoretical study reveals that in comparison to a film created with monodisperse di-block copolymers, an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness. This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index leads to an increase in the effective Kuhn segment length of the polydisperse blocks. It is shown that the conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness decreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. These predictions are verified by results from neutron reflectivity experiments on thin films made from moderately polydisperse PGMA-PVDMA-d6 di-block copolymer deposited on silicon substrates. In conclusion, results from SCFT are used to predict neutron reflectivity profiles, providing a facile and robust route to obtain useful physical insights into the structure of polydisperse diblock copolymers at

  1. Microphase separation in thin films of lamellar forming polydisperse di-block copolymers

    DOE PAGES

    Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.; Chen, Jihua; Heller, William T.; Ankner, John F.; Browning, James F.; Kilbey, II, S. Michael; Sumpter, Bobby G.

    2015-02-03

    Despite the ubiquity of polydispersity in chain lengths of di-block copolymers, its effects on microphase separation in thin films have eluded a clear understanding. In this paper, we have studied effects of polydispersity on the microphase separation in thin films of lamellar forming di-block copolymers using self-consistent field theory (SCFT) and neutron reflectivity experiments. Di-block copolymers containing a polydisperse block of poly(glycidylmethacrylate) (PGMA) connected to a near-monodisperse block poly(2-vinyl-4,4-dimethyl-d6 azlactone) (PVDMA-d6) are considered in this work. Effects of chain length polydispersity, film thickness, substrate–monomer and monomer–monomer interactions on the microphase segregation are studied using SCFT. The theoretical study reveals thatmore » in comparison to a film created with monodisperse di-block copolymers, an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness. This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index leads to an increase in the effective Kuhn segment length of the polydisperse blocks. It is shown that the conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness decreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. These predictions are verified by results from neutron reflectivity experiments on thin films made from moderately polydisperse PGMA-PVDMA-d6 di-block copolymer deposited on silicon substrates. In conclusion, results from SCFT are used to predict neutron reflectivity profiles, providing a facile and robust route to obtain useful physical insights into the structure of polydisperse diblock copolymers at interfaces.« less

  2. Stable domain size and conformational segregation of short and long blocks during microphase separation in random block copolymers

    NASA Astrophysics Data System (ADS)

    Markina, A.; Chertovich, A.

    2015-03-01

    In this Letter we use computer simulations and test microphase separation for AB-diblock copolymers with different block's statistics. We show that the domain size during microphase separation is stable only for the system with large enough polydispersity, namely with exponential (Flory-type) block length distribution. The reason for stable domain size is a conformational segregation of short and long blocks during the increase of the incompatibility in the system. While short blocks became elongated and occupy the surface of the interphase region, long blocks pushed out to the center of the domain and formed their compact conformations.

  3. A Solution-Processable (Tetraaniline-b-Polyethylene Glycol)3 Star-Shaped Rod-Coil Block Copolymer with Enhanced Electrochromic Properties.

    PubMed

    Cao, Linyu; Gong, Chen; Yang, Jiping

    2016-02-01

    A novel electroactive star-shaped rod-coil copolymer composed of a benzene core and three symmetrically positioned tetraaniline-b-poly(ethylene glycol) arms, (TAni-b-PEG)3 rod-coil block copolymer, is synthesized successfully and characterized using Fourier transform infrared spectroscopy (FTIR), UV-vis, (1)H NMR, and matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. Uniform and high-quality (TAni-b-PEG)3 thin films onto indium tin oxide-coated glass surface are fabricated simply from its DMF solution. Resulting (TAni-b-PEG)3 copolymer thin films possess excellent electrochromic properties with a high optical contrast of 73.3%, superb coloration efficiency of 318.5 cm(2) C(-1) at 750 nm. Very short switching times, that is, 2.11 s and 2.14 s for coloring and bleaching times, respectively, are observed as well. The mechanism of these impressive electrochromic properties of (TAni-b-PEG)3 thin films possessed is proposed based on the atomic force microscopy investigation, star-shaped molecular geometry, synergetic electronic and ionic conductivity and amphiphilic self-assembly feature of (TAni-b-PEG)3 copolymer, which can self-assemble to form cylinder pattern consisting of quick pathways for electronic charges and ionic species, respectively. PMID:26663524

  4. Proton Conductivities of Lamellae-Forming Bioinspired Block Copolymer Thin Films Containing Silver Nanoparticles.

    PubMed

    Yabu, Hiroshi; Matsui, Jun; Hara, Mitsuo; Nagano, Shusaku; Matsuo, Yasutaka; Nagao, Yuki

    2016-09-20

    Size-controlled metal nanoparticles (NPs) were spontaneously formed when the amphiphilic diblock copolymers consisting of poly(vinyl catechol) and polystyrene (PVCa-b-PSt) were used as reductants and templates for NPs. In the present study, the proton conductivity of well-aligned lamellae structured PVCa-b-PSt films with Ag NPs was evaluated. We found that the proton conductivity of PVCa-b-PSt film was increased 10-fold by the addition of Ag NPs into the proton conduction channels filled with catechol moieties. In addition, the effect of humidity and the origin of proton conductivity enhancement was investigated. PMID:27589224

  5. Proton Conductivities of Lamellae-Forming Bioinspired Block Copolymer Thin Films Containing Silver Nanoparticles.

    PubMed

    Yabu, Hiroshi; Matsui, Jun; Hara, Mitsuo; Nagano, Shusaku; Matsuo, Yasutaka; Nagao, Yuki

    2016-09-20

    Size-controlled metal nanoparticles (NPs) were spontaneously formed when the amphiphilic diblock copolymers consisting of poly(vinyl catechol) and polystyrene (PVCa-b-PSt) were used as reductants and templates for NPs. In the present study, the proton conductivity of well-aligned lamellae structured PVCa-b-PSt films with Ag NPs was evaluated. We found that the proton conductivity of PVCa-b-PSt film was increased 10-fold by the addition of Ag NPs into the proton conduction channels filled with catechol moieties. In addition, the effect of humidity and the origin of proton conductivity enhancement was investigated.

  6. Block copolymers via living transition metal initiated polymerizations; Change of mechanism and bimetallic initiator approaches

    SciTech Connect

    Novak, B.M.; Deming, T.J.

    1993-12-31

    The authors have been interested in the development of transition metal catalysts for use in living polymerizations to form polymers with well-defined secondary structures, and to precisely incorporate these regular structures into di- and tri-block copolymers. Much of this work has focused on the development of rodlike helical polyisocyanate and polyisocyanide chains that are known to form liquid crystalline, and/or highly regular crystalline phases. The compound [({eta}{sup 3}C{sub 3}H{sub 5})Ni(OC(O)CF{sub 3})]{sub 2} (I), which has been used extensively as a butadiene polymerization catalyst, has been successfully used in the preparation of polyisocyanide - polybutadiene block copolymers. These blocks have been characterized by using gel permeation chromotography, differential scanning calorimetry, {sup 13}C NMR and scanning electron microscopy. Since both monomer polymerizations are living, this block copolymer synthesis is highly versatile with respect to polymer segment chain lengths and the types of monomers used.

  7. Hemocompatibility of styrenic block copolymers for use in prosthetic heart valves.

    PubMed

    Brubert, Jacob; Krajewski, Stefanie; Wendel, Hans Peter; Nair, Sukumaran; Stasiak, Joanna; Moggridge, Geoff D

    2016-02-01

    Certain styrenic thermoplastic block copolymer elastomers can be processed to exhibit anisotropic mechanical properties which may be desirable for imitating biological tissues. The ex-vivo hemocompatibility of four triblock (hard-soft-hard) copolymers with polystyrene hard blocks and polyethylene, polypropylene, polyisoprene, polybutadiene or polyisobutylene soft blocks are tested using the modified Chandler loop method using fresh human blood and direct contact cell proliferation of fibroblasts upon the materials. The hemocompatibility and durability performance of a heparin coating is also evaluated. Measures of platelet and coagulation cascade activation indicate that the test materials are superior to polyester but inferior to expanded polytetrafluoroethylene and bovine pericardium reference materials. Against inflammatory measures the test materials are superior to polyester and bovine pericardium. The addition of a heparin coating results in reduced protein adsorption and ex-vivo hemocompatibility performance superior to all reference materials, in all measures. The tested styrenic thermoplastic block copolymers demonstrate adequate performance for blood contacting applications. PMID:26704549

  8. Multi-block sulfonated poly(phenylene) copolymer proton exchange membranes

    DOEpatents

    Fujimoto, Cy H.; Hibbs, Michael; Ambrosini, Andrea

    2012-02-07

    Improved multi-block sulfonated poly(phenylene) copolymer compositions, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cells, in electrode casting solutions and electrodes. The multi-block architecture has defined, controllable hydrophobic and hydrophilic segments. These improved membranes have better ion transport (proton conductivity) and water swelling properties.

  9. Designer amphiphilic proteins as building blocks for the intracellular formation of organelle-like compartments

    NASA Astrophysics Data System (ADS)

    Huber, Matthias C.; Schreiber, Andreas; von Olshausen, Philipp; Varga, Balázs R.; Kretz, Oliver; Joch, Barbara; Barnert, Sabine; Schubert, Rolf; Eimer, Stefan; Kele, Péter; Schiller, Stefan M.

    2015-01-01

    Nanoscale biological materials formed by the assembly of defined block-domain proteins control the formation of cellular compartments such as organelles. Here, we introduce an approach to intentionally ‘program’ the de novo synthesis and self-assembly of genetically encoded amphiphilic proteins to form cellular compartments, or organelles, in Escherichia coli. These proteins serve as building blocks for the formation of artificial compartments in vivo in a similar way to lipid-based organelles. We investigated the formation of these organelles using epifluorescence microscopy, total internal reflection fluorescence microscopy and transmission electron microscopy. The in vivo modification of these protein-based de novo organelles, by means of site-specific incorporation of unnatural amino acids, allows the introduction of artificial chemical functionalities. Co-localization of membrane proteins results in the formation of functionalized artificial organelles combining artificial and natural cellular function. Adding these protein structures to the cellular machinery may have consequences in nanobiotechnology, synthetic biology and materials science, including the constitution of artificial cells and bio-based metamaterials.

  10. Designer amphiphilic proteins as building blocks for the intracellular formation of organelle-like compartments.

    PubMed

    Huber, Matthias C; Schreiber, Andreas; von Olshausen, Philipp; Varga, Balázs R; Kretz, Oliver; Joch, Barbara; Barnert, Sabine; Schubert, Rolf; Eimer, Stefan; Kele, Péter; Schiller, Stefan M

    2015-01-01

    Nanoscale biological materials formed by the assembly of defined block-domain proteins control the formation of cellular compartments such as organelles. Here, we introduce an approach to intentionally 'program' the de novo synthesis and self-assembly of genetically encoded amphiphilic proteins to form cellular compartments, or organelles, in Escherichia coli. These proteins serve as building blocks for the formation of artificial compartments in vivo in a similar way to lipid-based organelles. We investigated the formation of these organelles using epifluorescence microscopy, total internal reflection fluorescence microscopy and transmission electron microscopy. The in vivo modification of these protein-based de novo organelles, by means of site-specific incorporation of unnatural amino acids, allows the introduction of artificial chemical functionalities. Co-localization of membrane proteins results in the formation of functionalized artificial organelles combining artificial and natural cellular function. Adding these protein structures to the cellular machinery may have consequences in nanobiotechnology, synthetic biology and materials science, including the constitution of artificial cells and bio-based metamaterials. PMID:25362355

  11. Lysine-tagged peptide coupling onto polylactide nanoparticles coated with activated ester-based amphiphilic copolymer: a route to highly peptide-functionalized biodegradable carriers.

    PubMed

    Handké, Nadège; Ficheux, Damien; Rollet, Marion; Delair, Thierry; Mabrouk, Kamel; Bertin, Denis; Gigmes, Didier; Verrier, Bernard; Trimaille, Thomas

    2013-03-01

    Efficient biomolecule conjugation to the surface of biodegradable colloidal carriers is crucial for their targeting efficiency in drug/vaccine delivery applications. We here propose a potent strategy to drastically improve peptide immobilization on biodegradable polylactide (PLA) nanoparticles (NPs). Our approach particularly relies on the use of an amphiphilic block copolymer PLA-b-poly(N-acryloxysuccinimide-co-N-vinylpyrrolidone) (PLA-b-P(NAS-co-NVP)) as NP surface modifier, whose the N-succinimidyl (NS) ester functions of the NAS units along the polymer chain ensure N-terminal amine peptide coupling. The well-known immunostimulatory peptide sequence derived from the human interleukin 1β (IL-1β), VQGEESNDK, was coupled on the NPs of 169 nm mean diameter in phosphate buffer (pH 8, 10 mM). A maximum amount of 2 mg immobilized per gram of NPs (i.e. 0.042 peptidenm(-2)) was obtained. Introduction of a three lysine tag at the peptide N-terminus (KKKVQGEESNDK) resulted in a dramatic improvement of the immobilized peptide amounts (27.5 mg/g NP, i.e. 0.417 peptidenm(-2)). As a comparison, the density of tagged peptide achievable on surfactant free PLA NPs of similar size (140 nm), through classical EDC or EDC/NHS activation of the surface PLA carboxylic end-groups, was found to be 6 mg/g NP (i.e. 0.075 peptidenm(-2)), showing the decisive impact of the P(NAS-co-NVP)-based hairy corona for high peptide coupling. These results demonstrate that combined use of lysine tag and PLA-b-P(NAS-co-NVP) surfactant represents a valuable platform to tune and optimize surface bio-functionalization of PLA-based biodegradable carriers.

  12. The hydration and ordering of lamellar block copolymer films prior to the formation of polymer vesicles

    NASA Astrophysics Data System (ADS)

    Kamata, Yohei; Parnell, Andrew; Dennison, Andrew; Barker, Robert; Gutfreund, Philipp; Skoda, Maximilian; Mai, Shaomin; Jones, Richard

    2012-02-01

    Polymersomes -- vesicles based on self-assembled bilayers in turn composed of amphiphilic copolymers -- are good candidates for molecular delivery systems; hydrophilic molecules can be enclosed within the aqueous core, to be released by a trigger, which disrupts the vesicle's wall. The key to the use of these polymer vesicles as effective molecular delivery system is in the ability to efficiently encapsulate a molecular payload within the vesicle. To understand the formation mechanism of polymer vesicles via the thin film rehydration method, we have evaluated the hydration and ordering of PEO-PBO diblock copolymer thin films in a controlled water vapor atmosphere. We have performed Neutron Reflectivity, Ellipsometry and Atomic Force Microscopy measurements during the hydration process. These results show that the film swells slowly in the initial stage. It then swells rapidly at a certain critical point and makes ordered structure at the same time. The lamellae are gradually oriented parallel to the substrate with increasing water absorption.

  13. Morphological Characterization of Elastin-Mimetic Block Copolymers Utilizing Cryo- and Cryoetch-HRSEM

    NASA Astrophysics Data System (ADS)

    Wright, Elizabeth R.; Conticello, Vincent P.; Apkarian, Robert P.

    2003-06-01

    Elastin-mimetic block copolymers were produced by genetic engineering. Genetically driven synthesis permitted control of the final physiochemical characteristics of the block copolymers. We designed BB and BAB block copolymers in which the A-block was hydrophilic and the B-block was hydrophobic. By designing the copolymers in this manner, it was proposed that they would self-assemble into micellar aggregates that, at high concentration, would form thermoreversible hydrogels. To analyze the three-dimensional fine surface morphology of the copolymers, to the resolution level of a few nanometers, we employed cryo-HRSEM. This method provided vast expanses of the specimen in its frozen hydrated state for survey. In our initial cryo-HRSEM studies, we observed the protein filaments and micelles surrounded by lakes of vitreous ice. Upon examination at low and intermediate magnifications, there was an extensive honeycomb-like filamentous network. To delineate the fine morphology of the hydrogel network at high magnification and to greater depths, we cryoetched away unbound water from the sample surface, in high vacuum, prior to chromium deposition. By using this technique, we were able to visualize for characterization purposes the fine fibril networks formed from the micellar aggregates over the surface of the hydrogel.

  14. Functional block copolymers for applications in advanced materials, energy storage, and lithography

    NASA Astrophysics Data System (ADS)

    Hardy, Christopher George

    Block copolymers spontaneously self-assembly into a wide variety of ordered nanostructures on the length scale of 5 - 100 nm due to the thermodynamic immiscibility between the covalently linked, chemically distinct polymer chains. Incorporating desirable functional groups into block copolymer systems can lead to confinement of the functional group to a specific domain upon microphase separation of the block copolymer. The resulting materials display desirable characteristics of the functional group in a well-ordered nanostructure. Such systems have been utilized in a wide variety of applications including catalysis, ceramic materials, and membranes. This dissertation is focused on the synthesis, characterization, self-assembly and materials processing of various functionalized block copolymer systems. An assortment of monomers functionalized with specific groups were prepared and polymerized by a variety of polymerization techniques including atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, and ring-opening metathesis polymerization. Self-assembly of the functionalized block copolymers led to well defined nanostructures in bulk and thin films. Depending upon the functional group incorporated, the ordered materials were utilized in various applications including ordered catalysts, energy storage, and templates for nanolithography..

  15. Synthesis of manganese oxide supported on mesoporous titanium oxide: Influence of the block copolymer

    SciTech Connect

    Schmit, F.; Bois, L.; Chiriac, R.; Toche, F.; Chassagneux, F.; Besson, M.; Descorme, C.; Khrouz, L.

    2015-01-15

    Manganese oxides supported on mesoporous titanium oxides were synthesized via a sol–gel route using block copolymer self-assembly. The oxides were characterized by X-ray diffraction, infrared spectroscopy, thermal analyses, nitrogen adsorption/desorption, electron microscopy and electronic paramagnetic resonance. A mesoporous anatase containing amorphous manganese oxide particles could be obtained with a 0.2 Mn:Ti molar ratio. At higher manganese loading (0.5 Mn:Ti molar ratio), segregation of crystalline manganese oxide occurred. The influence of block copolymer and manganese salt on the oxide structure was discussed. The evolution of the textural and structural characteristics of the materials upon hydrothermal treatment was also investigated. - Graphical abstract: One-pot amorphous MnO{sub 2} supported on mesoporous anataseTiO{sub 2}. - Highlights: • Mesoporous manganese titanium oxides were synthesized using block copolymer. • Block copolymers form complexes with Mn{sup 2+} from MnCl{sub 2}. • With block copolymer, manganese oxide can be dispersed around the titania crystallites. • With Mn(acac){sub 2}, manganese is dispersed inside titania. • MnOOH crystallizes outside mesoporous titania during hydrothermal treatment.

  16. Thermosensitive PNIPAM-b-HTPB block copolymer micelles: molecular architectures and camptothecin drug release.

    PubMed

    Luo, Yan-Ling; Yang, Xiao-Li; Xu, Feng; Chen, Ya-Shao; Zhang, Bin

    2014-02-01

    Two kinds of thermo-sensitive poly(N-isoproplacrylamide) (PNIPAM) block copolymers, AB4 four-armed star multiblock and linear triblock copolymers, were synthesized by ATRP with hydroxyl-terminated polybutadiene (HTPB) as central blocks, and characterization was performed by (1)H NMR, FT-IR and SEC. The multiblock copolymers could spontaneously assemble into more regular spherical core-shell nanoscale micelles than the linear triblock copolymer. The physicochemical properties were detected by a surface tension technique, nano particle analyzer, TEM, DLS and UV-vis measurements. The multiblock copolymer micelles had lower critical micelle concentration than the linear counterpart, TEM size from 100 to 120 nm and the hydrodynamic diameters below 150 nm. The micelles exhibited thermo-dependent size change, with low critical solution temperature about 33-35 °C. The characteristic parameters were affected by the composition ratios, length of PNIPAM blocks and molecular architectures. The camptothecin release demonstrated that the drug release was thermo-responsive, accompanied by the temperature-induced structural changes of the micelles. MTT assays were performed to evaluate the biocompatibility or cytotoxicity of the prepared copolymer micelles. PMID:24184534

  17. Proteins detection by polymer optical fibers sensitised with overlayers of block and random copolymers

    NASA Astrophysics Data System (ADS)

    El Sachat, Alexandros; Meristoudi, Anastasia; Markos, Christos; Pispas, Stergios; Riziotis, Christos

    2014-03-01

    A low cost and low complexity optical detection method of proteins is presented by employing a detection scheme based on electrostatic interactions, and implemented by sensitization of a polymer optical fibers' (POF) surface by thin overlayers of properly designed sensitive copolymer materials with predesigned charges. This method enables the fast detection of proteins having opposite charge to the overlayer, and also the effective discrimination of differently charged proteins like lysozyme (LYS) and bovine serum albumin (BSA). As sensitive materials the block and the random copolymers of the same monomers were employed, namely the block copolymer poly(styrene-b-2vinylpyridine) (PS-b- P2VP) and the corresponding random copolymer poly(styrene-r-2vinylpyridine) (PS-r-P2VP), of similar composition and molecular weights. Results show systematically different response between the block and the random copolymers, although of the same order of magnitude, drawing thus important conclusions on their applications' techno-economic aspects given that they have significantly different associated manufacturing method and costs. The use of the POF platform, in combination with those adaptable copolymer sensing materials could lead to efficient low cost bio-detection schemes.

  18. Structure and ionic conductivity of block copolymer electrolytes over a wide salt concentration range

    NASA Astrophysics Data System (ADS)

    Chintapalli, Mahati; Le, Thao; Venkatesan, Naveen; Thelen, Jacob; Rojas, Adriana; Balsara, Nitash

    Block copolymer electrolytes are promising materials for safe, long-lasting lithium batteries because of their favorable mechanical and ion transport properties. The morphology, phase behavior, and ionic conductivity of a block copolymer electrolyte, SEO mixed with LiTFSI was studied over a wide, previously unexplored salt concentration range using small angle X-ray scattering, differential scanning calorimetry and ac impedance spectroscopy, respectively. SEO exhibits a maximum in ionic conductivity at twice the salt concentration that PEO, the homopolymer analog of the ion-containing block, does. This finding is contrary to prior studies that examined a more limited range of salt concentrations. In SEO, the phase behavior of the PEO block and LiTFSI closely resembles the phase behavior of homopolymer PEO and LiTFSI. The grain size of the block copolymer morphology was found to decrease with increasing salt concentration, and the ionic conductivity of SEO correlates with decreasing grain size. Structural effects impact the ionic conductivity-salt concentration relationship in block copolymer electrolytes. SEO: polystyrene-block-poly(ethylene oxide); also PS-PEO LiTFSI: lithium bis(trifluoromethanesulfonyl imide

  19. Kinetic control of block copolymer self-assembly into multicompartment and novel geometry nanoparticles

    NASA Astrophysics Data System (ADS)

    Chen, Yingchao; Wang, Xiaojun; Zhang, Ke; Wooley, Karen; Mays, Jimmy; Percec, Virgil; Pochan, Darrin

    2012-02-01

    Micelles with the segregation of hydrophobic blocks trapped in the same nanoparticle core have been produced through co-self-assembly of two block copolymers in THF/water dilute solution. The dissolution of two block copolymer sharing the same polyacrylic acid PAA blocks in THF undergoes consequent aggregation and phase separation through either slow water titration or quick water addition that triggers the micellar formation. The combination and comparison of the two water addition kinetic pathways are the keys of forming multicompartment structures at high water content. Importantly, the addition of organic diamine provides for acid-base complexation with the PAA side chains which, in turn, plays the key role of trapping unlike hydrophobic blocks from different block copolymers into one nanoparticle core. The kinetic control of solution assembly can be applied to other molecular systems such as dendrimers as well as other block copolymer molecules. Transmission electron microscopy, cryogenic transmission electron microscopy, light scattering have been applied to characterize the micelle structures.

  20. Self-Assembly and Critical Aggregation Concentration Measurements of ABA Triblock Copolymers with Varying B Block Types: Model Development, Prediction, and Validation.

    PubMed

    Aydin, Fikret; Chu, Xiaolei; Uppaladadium, Geetartha; Devore, David; Goyal, Ritu; Murthy, N Sanjeeva; Zhang, Zheng; Kohn, Joachim; Dutt, Meenakshi

    2016-04-21

    simulations, and used these results to predict the CAC values of triblock copolymers with higher molecular weights by extrapolation. In parallel, a PEG5K-b-oligo(DTO-SA)-b-PEG5K block copolymer was synthesized, and the CAC value was determined experimentally using the pyrene method. The experimental CAC value agreed well with the CAC value predicted by simulation. These results validate our CG models, and demonstrate an avenue to simulate and predict aggregation characteristics of ABA amphiphilic triblock copolymers with complex structures. PMID:27031284

  1. Manipulating Interfaces through Surface Confinement of Poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone), a Dually Reactive Block Copolymer

    SciTech Connect

    Lokitz, Bradley S; Wei, Jifeng; Hinestrosa Salazar, Juan P; Ivanov, Ilia N; Browning, James B; Ankner, John Francis; Kilbey, II, S Michael; Messman, Jamie M

    2012-01-01

    The assembly of dually reactive, well-defined diblock copolymers incorporating the chemoselective/functional monomer, 4,4-dimethyl-2-vinylazlactone (VDMA) and the surface-reactive monomer glycidyl methacrylate (GMA) is examined to understand how competition between surface attachment and microphase segregation influences interfacial structure. Reaction of the PGMA block with surface hydroxyl groups not only anchors the copolymer to the surface, but limits chain mobility, creating brush-like structures comprising PVDMA blocks, which contain reactive azlactone groups. The block copolymers are spin coated at various solution concentrations and annealed at elevated temperature to optimize film deposition to achieve a molecularly uniform layer. The thickness and structure of the polymer thin films are investigated by ellipsometry, infrared spectroscopy, and neutron reflectometry. The results show that deposition of PGMA-b-PVDMA provides a useful route to control film thickness while preserving azlactone groups that can be further modified with biotin-poly(ethylene glycol)amine to generate designer surfaces. The method described herein offers guidance for creating highly functional surfaces, films, or coatings through the use of dually reactive block copolymers and postpolymerization modification.

  2. Polythiophene-block-poly(γ-benzyl L-glutamate): Synthesis and study of a new rod-rod block copolymer

    SciTech Connect

    Wu, Zong-Quan; Ono, Robert J.; Chen, Zheng; Li, Zicheng; Bielawski, Christopher W.

    2011-01-01

    Coupling of ethynyl terminated poly(3-hexylthiophene) with azide terminated poly(γ-benzyl L-glutamate) afforded the respective block copolymer in good yield and high purity; this material was found to self assemble into hierarchal structures in solution and in the solid state.

  3. Polybenzimidazole block copolymers for fuel cell: synthesis and studies of block length effects on nanophase separation, mechanical properties, and proton conductivity of PEM.

    PubMed

    Maity, Sudhangshu; Jana, Tushar

    2014-05-14

    A series of meta-polybenzimidazole-block-para-polybenzimidazole (m-PBI-b-p-PBI), segmented block copolymers of PBI, were synthesized with various structural motifs and block lengths by condensing the diamine terminated meta-PBI (m-PBI-Am) and acid terminated para-PBI (p-PBI-Ac) oligomers. NMR studies and existence of two distinct glass transition temperatures (Tg), obtained from dynamical mechanical analysis (DMA) results, unequivocally confirmed the formation of block copolymer structure through the current polymerization methodology. Appropriate and careful selection of oligomers chain length enabled us to tailor the block length of block copolymers and also to make varieties of structural motifs. Increasingly distinct Tg peaks with higher block length of segmented block structure attributed the decrease in phase mixing between the meta-PBI and para-PBI blocks, which in turn resulted into nanophase segregated domains. The proton conductivities of proton exchange membrane (PEM) developed from phosphoric acid (PA) doped block copolymer membranes were found to be increasing substantially with increasing block length of copolymers even though PA loading of these membranes did not alter appreciably with varying block length. For example when molecular weight (Mn) of blocks were increased from 1000 to 5500 then the proton conductivities at 160 °C of resulting copolymers increased from 0.05 to 0.11 S/cm. Higher block length induced nanophase separation between the blocks by creating less morphological barrier within the block which facilitated the movement of the proton in the block and hence resulting higher proton conductivity of the PEM. The structural varieties also influenced the phase separation and proton conductivity. In comparison to meta-para random copolymers reported earlier, the current meta-para segmented block copolymers were found to be more suitable for PBI-based PEM.

  4. Morphological and physical characterization of poly(styrene-isobutylene-styrene) block copolymers and ionomers thereof

    NASA Astrophysics Data System (ADS)

    Baugh, Daniel Webster, III

    Poly(styrene-isobutylene-styrene) block copolymers made by living cationic polymerization using a difunctional initiator and the sequential monomer addition technique were analyzed using curve-resolution software in conjunction with high-resolution GPC. Fractional precipitation and selective solvent extraction were applied to a representative sample in order to confirm the identity of contaminating species. The latter were found to be low molecular weight polystyrene homopolymer, diblock copolymer, and higher molecular weight segmented block copolymers formed by intermolecular electrophilic aromatic substitution linking reactions occurring late in the polymerization of the styrene outer blocks. Solvent-cast films of poly(styrene-isobutylene-styrene) (PS-PIB-PS) block copolymers and block ionomers were analyzed using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Four block copolymer samples with center block molecular weights of 52,000 g/mol and PS volume fractions (o sbPS) ranging from 0.17 to 0.31 were studied. All samples exhibited hexagonally packed cylinders of PS within the PIB matrix. Cylinder spacing was in the range 32 to 36 nm for most samples, while cylinder diameters varied from 14 to 21 nm. Porod analysis of the scattering data indicated the presence of isolated phase mixing and sharp phase boundaries. PS-PIB-PS block copolymers and ionomers therefrom were analyzed using dynamic mechanical analysis (DMA) and tensile testing. The study encompassed five block copolymer samples with similar PIB center blocks with molecular weights of approx52,000 g/mol and PS weight fractions ranging from 0.127 to 0.337. Ionomers were prepared from two of these materials by lightly sulfonating the PS outer blocks. Sulfonation levels varied from 1.7 to 4.7 mol % and the sodium and potassium neutralized forms were compared to the parent block copolymers. Dynamic mechanical analysis (DMA) of the block copolymer films indicated the existence

  5. Three-dimensional inverse design of nanopatterns with block copolymers and homopolymers

    NASA Astrophysics Data System (ADS)

    Xu, Dan; Liu, Hong; Zhu, You-Liang; Lu, Zhong-Yuan

    2016-02-01

    We propose a facile inverse design strategy to generate three-dimensional (3D) nanopatterns by using either block copolymers or a binary homopolymer blend via dissipative particle dynamics simulations. We find that the composition window of block copolymers to form a specific 3D morphology can be expanded when the self-assembly of block copolymers is directed by templates. We also find that a binary homopolymer blend can serve as a better candidate in the inverse templating design, since they have similar performances on recovering the target pattern, with much lower cost. This strategy is proved efficient for fabricating templates with desired topographical configuration, and the inverse design idea sheds lights on better control and design of materials with complex nanopatterns.

  6. Three-dimensional inverse design of nanopatterns with block copolymers and homopolymers.

    PubMed

    Xu, Dan; Liu, Hong; Zhu, You-Liang; Lu, Zhong-Yuan

    2016-03-01

    We propose a facile inverse design strategy to generate three-dimensional (3D) nanopatterns by using either block copolymers or a binary homopolymer blend via dissipative particle dynamics simulations. We find that the composition window of block copolymers to form a specific 3D morphology can be expanded when the self-assembly of block copolymers is directed by templates. We also find that a binary homopolymer blend can serve as a better candidate in the inverse templating design, since they have similar performances on recovering the target pattern, with much lower cost. This strategy is proved efficient for fabricating templates with desired topographical configuration, and the inverse design idea sheds lights on better control and design of materials with complex nanopatterns. PMID:26880143

  7. Efficient Synthesis of Cyclic Block Copolymers by Rotaxane Protocol by Linear/Cyclic Topology Transformation.

    PubMed

    Valentina, Stephanie; Ogawa, Takahiro; Nakazono, Kazuko; Aoki, Daisuke; Takata, Toshikazu

    2016-06-20

    High-yielding synthesis of cyclic block copolymer (CBC) using the rotaxane protocol by linear-cyclic polymer topology transformation was first demonstrated. Initial complexation of OH-terminated sec-ammonium salt and a crown ether was followed by the successive living ring-opening polymerizations of two lactones to a linear block copolymer having a rotaxane structure by the final capping of the propagation end. CBC was obtained in a high yield by an exploitation of the mechanical linkage through the translational movement of the rotaxane component to transform polymer structure from linear to cyclic. Furthermore, the change of the polymer topology was translated into a macroscopic change in crystallinity of the block copolymer. PMID:27037975

  8. Charge transfer in the low-temperature radiolysis of styrene-butadiene block copolymers

    SciTech Connect

    Khatipov, S.A.; Edrisov, A.T.; Milinchuk, V.K.

    1995-05-01

    Radiation-induced conductivity of polystyrene, polybutadiene, and styrene-butadiene block copolymers, resulting from irradiation of the samples with fast electrons of 75 keV energy under vacuum at 100 K, was studied. A negative deviation of the radiation-induced conductivity constant A{sub m} from the corresponding additive values was detected upon varying the composition of block copolymers. It is concluded that the interfacial charge transfer from polystyrene to polybutadiene microdomains occurs in the block copolymers. This conclusion is confirmed by the results of investigations of drift mobility of the charge carriers and effects of donor-acceptor admixtures on the radiation-induced conductivity of the polymers studied.

  9. Millisecond ordering of block-copolymer films via photo-thermal gradients

    SciTech Connect

    Majewski, Pawel W.; Yager, Kevin G.

    2015-03-12

    For the promise of self-assembly to be realized, processing techniques must be developed that simultaneously enable control of the nanoscale morphology, rapid assembly, and, ideally, the ability to pattern the nanostructure. Here, we demonstrate how photo-thermal gradients can be used to control the ordering of block-copolymer thin films. Highly localized laser heating leads to intense thermal gradients, which induce a thermophoretic force on morphological defects. This increases the ordering kinetics by at least 3 orders-of-magnitude, compared to conventional oven annealing. By simultaneously exploiting the thermal gradients to induce shear fields, we demonstrate uniaxial alignment of a block-copolymer film in less than a second. Finally, we provide examples of how control of the incident light-field can be used to generate prescribed configurations of block-copolymer nanoscale patterns.

  10. Selective directed self-assembly of coexisting morphologies using block copolymer blends

    NASA Astrophysics Data System (ADS)

    Stein, A.; Wright, G.; Yager, K. G.; Doerk, G. S.; Black, C. T.

    2016-08-01

    Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. Here we expand on traditional DSA chemical patterning. A blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This is in contrast to the typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist.

  11. Efficient Synthesis of Cyclic Block Copolymers by Rotaxane Protocol by Linear/Cyclic Topology Transformation.

    PubMed

    Valentina, Stephanie; Ogawa, Takahiro; Nakazono, Kazuko; Aoki, Daisuke; Takata, Toshikazu

    2016-06-20

    High-yielding synthesis of cyclic block copolymer (CBC) using the rotaxane protocol by linear-cyclic polymer topology transformation was first demonstrated. Initial complexation of OH-terminated sec-ammonium salt and a crown ether was followed by the successive living ring-opening polymerizations of two lactones to a linear block copolymer having a rotaxane structure by the final capping of the propagation end. CBC was obtained in a high yield by an exploitation of the mechanical linkage through the translational movement of the rotaxane component to transform polymer structure from linear to cyclic. Furthermore, the change of the polymer topology was translated into a macroscopic change in crystallinity of the block copolymer.

  12. Ordered porous mesostructured materials from nanoparticle-block copolymer self-assembly

    DOEpatents

    Warren, Scott; Wiesner, Ulrich; DiSalvo, Jr., Francis J

    2013-10-29

    The invention provides mesostructured materials and methods of preparing mesostructured materials including metal-rich mesostructured nanoparticle-block copolymer hybrids, porous metal-nonmetal nanocomposite mesostructures, and ordered metal mesostructures with uniform pores. The nanoparticles can be metal, metal alloy, metal mixture, intermetallic, metal-carbon, metal-ceramic, semiconductor-carbon, semiconductor-ceramic, insulator-carbon or insulator-ceramic nanoparticles, or combinations thereof. A block copolymer/ligand-stabilized nanoparticle solution is cast, resulting in the formation of a metal-rich (or semiconductor-rich or insulator-rich) mesostructured nanoparticle-block copolymer hybrid. The hybrid is heated to an elevated temperature, resulting in the formation of an ordered porous nanocomposite mesostructure. A nonmetal component (e.g., carbon or ceramic) is then removed to produce an ordered mesostructure with ordered and large uniform pores.

  13. Millisecond ordering of block-copolymer films via photo-thermal gradients

    DOE PAGES

    Majewski, Pawel W.; Yager, Kevin G.

    2015-03-12

    For the promise of self-assembly to be realized, processing techniques must be developed that simultaneously enable control of the nanoscale morphology, rapid assembly, and, ideally, the ability to pattern the nanostructure. Here, we demonstrate how photo-thermal gradients can be used to control the ordering of block-copolymer thin films. Highly localized laser heating leads to intense thermal gradients, which induce a thermophoretic force on morphological defects. This increases the ordering kinetics by at least 3 orders-of-magnitude, compared to conventional oven annealing. By simultaneously exploiting the thermal gradients to induce shear fields, we demonstrate uniaxial alignment of a block-copolymer film in lessmore » than a second. Finally, we provide examples of how control of the incident light-field can be used to generate prescribed configurations of block-copolymer nanoscale patterns.« less

  14. Factors Influencing Shear Alignment of Cylinder-Forming Block Copolymer Thin Films

    NASA Astrophysics Data System (ADS)

    Davis, Raleigh; Register, Richard; Chaikin, Paul

    2014-03-01

    Application of shear stress to block copolymers is known to preferentially orient the microdomains in the direction of applied shear. While this phenomenon has been well studied for bulk block copolymer systems, the use of shear stress to align microdomains in block copolymer thin films (typically one to several microdomain layers) is still an active area of research. Numerous experimental factors influence the ease with which orientation is achieved as well as the ultimate quality of alignment observed. The present work investigates several of these factors using a series of cylinder-forming poly(styrene)-poly(hexylmethacrylate) copolymers. Parameters studied include film thickness, block copolymer molecular weight and composition, substrate wetting conditions (controlled via grafted polymer brush layers of either polystyrene or polyhexylmethacrylate), and applied shear stress. Quality of alignment is assessed via atomic force microscopy and subsequent computation of an orientational order parameter and the density of defects in the microdomain lattice. The results are compared to a melting-recrystallization model, thus providing greater insight into the fundamental mechanisms and key parameters which control how microdomains order in response to shear. In general monolayers are observed to align more poorly than thicker films, though the influence of film thickness on orientation depends strongly on polymer composition. Alignment quality is ultimately limited by inherent fluctuations in the cylinder trajectories as well as the presence of isolated dislocations.

  15. Collapse transitions in thermosensitive multi-block copolymers: a Monte Carlo study.

    PubMed

    Rissanou, Anastassia N; Tzeli, Despoina S; Anastasiadis, Spiros H; Bitsanis, Ioannis A

    2014-05-28

    Monte Carlo simulations are performed on a simple cubic lattice to investigate the behavior of a single linear multiblock copolymer chain of various lengths N. The chain of type (AnBn)m consists of alternating A and B blocks, where A are solvophilic and B are solvophobic and N = 2nm. The conformations are classified in five cases of globule formation by the solvophobic blocks of the chain. The dependence of globule characteristics on the molecular weight and on the number of blocks, which participate in their formation, is examined. The focus is on relative high molecular weight blocks (i.e., N in the range of 500-5000 units) and very differing energetic conditions for the two blocks (very good-almost athermal solvent for A and bad solvent for B). A rich phase behavior is observed as a result of the alternating architecture of the multiblock copolymer chain. We trust that thermodynamic equilibrium has been reached for chains of N up to 2000 units; however, for longer chains kinetic entrapments are observed. The comparison among equivalent globules consisting of different number of B-blocks shows that the more the solvophobic blocks constituting the globule the bigger its radius of gyration and the looser its structure. Comparisons between globules formed by the solvophobic blocks of the multiblock copolymer chain and their homopolymer analogs highlight the important role of the solvophilic A-blocks. PMID:24880322

  16. Collapse transitions in thermosensitive multi-block copolymers: A Monte Carlo study

    SciTech Connect

    Rissanou, Anastassia N.; Tzeli, Despoina S.; Anastasiadis, Spiros H.; Bitsanis, Ioannis A.

    2014-05-28

    Monte Carlo simulations are performed on a simple cubic lattice to investigate the behavior of a single linear multiblock copolymer chain of various lengths N. The chain of type (A{sub n}B{sub n}){sub m} consists of alternating A and B blocks, where A are solvophilic and B are solvophobic and N = 2nm. The conformations are classified in five cases of globule formation by the solvophobic blocks of the chain. The dependence of globule characteristics on the molecular weight and on the number of blocks, which participate in their formation, is examined. The focus is on relative high molecular weight blocks (i.e., N in the range of 500–5000 units) and very differing energetic conditions for the two blocks (very good—almost athermal solvent for A and bad solvent for B). A rich phase behavior is observed as a result of the alternating architecture of the multiblock copolymer chain. We trust that thermodynamic equilibrium has been reached for chains of N up to 2000 units; however, for longer chains kinetic entrapments are observed. The comparison among equivalent globules consisting of different number of B-blocks shows that the more the solvophobic blocks constituting the globule the bigger its radius of gyration and the looser its structure. Comparisons between globules formed by the solvophobic blocks of the multiblock copolymer chain and their homopolymer analogs highlight the important role of the solvophilic A-blocks.

  17. Micelles and polymersomes obtained by self-assembly of dextran and polystyrene based block copolymers.

    PubMed

    Houga, Clément; Giermanska, Joanna; Lecommandoux, Sébastien; Borsali, Redouane; Taton, Daniel; Gnanou, Yves; Le Meins, Jean-François

    2009-01-12

    The self-assembly of dextran-block-polystyrene (dex-b-PS) block copolymers was investigated in solution. The hydrophobic PS weight fraction in these block copolymers ranges from 7 to 92% w/w, whereas the average number molar mass of dextran was kept constant at 6600 gmol(-1). Self-assembly by direct dissolution in water could be performed only for block copolymers with a low hydrophobic content (7% w/w), whereas mixtures of tetrahydrofuran and dimethylsulfoxide were required for higher PS content, before transferring the structures into water. Core-shell micelles, ovoïds, and vesicles could be identified upon characterization by light and neutrons scattering, atomic force microscopy, and transmission electron microscopy. Most of the morphologies observed were not expected considering the chemical composition of the block copolymers. Finally, the size and shape of these nanoparticles were fixed upon cross-linking the dextran block through reaction of the hydroxyl groups with divinylsulfone. The role of the dextran conformation on the self-assembly process is discussed.

  18. Formation of Nonclassical Ordered Phases of A B -Type Multiarm Block Copolymers

    NASA Astrophysics Data System (ADS)

    Gao, Ya; Deng, Hanlin; Li, Weihua; Qiu, Feng; Shi, An-Chang

    2016-02-01

    The formation of ordered phases from block copolymers is driven by a delicate balance between the monomer-monomer interaction and chain configurational entropy. The configurational entropy can be regulated by designed chain architecture, resulting in a new entropy-driven mechanism to control the self-assembly of ordered phases from block copolymers. An effective routine to regulate the configurational entropy is to utilize multiarm architecture, in which the entropic contribution to the free energy could be qualitatively controlled by the fraction of bridging configurations. As an illustration of this mechanism, the phase behavior of two A B -type multiarm block copolymers, B0-(Bi-Ai) m and (B1-Ai-B2) m where the minority A blocks form cylindrical or spherical domains, are examined using the self-consistent field theory (SCFT). The SCFT results demonstrate that the packing symmetry of the cylinders or spheres can be controlled by the length of the bridging B blocks. Several nonclassical ordered phases, including a novel square array cylinder with p 4 m m symmetry, are predicted to form from the A B -type multiarm block copolymers.

  19. Emission quenching and charge separation in bridged donor-acceptor block copolymers

    NASA Astrophysics Data System (ADS)

    Bonner, Carl E., Jr.; Sun, Sam-Shajing; Wang, Meina; Vick, Shameika; Winston, Kizzy M.; Ledbetter, Abram J.; Douglas, Lawrence

    2004-11-01

    The optical properties of previously synthesized sulfone and methoxy substituted block co-polymers of poly-phenlyenevinylene (PPV) have been examined. An internal space charge field is formed which has been used to quench the luminescence intensity in these materials by separating optically generated excitons and electron-hole pairs. The absorption and emission spectra and the time dependence of the emission of donor and acceptor derivatized block co-polymers was measured and the quenching of the luminescence was observed and quantified. PPV materials with this internal field have potential applications as solar energy converters and photodetectors.

  20. Azidated Ether-Butadiene-Ether Block Copolymers as Binders for Solid Propellants

    NASA Astrophysics Data System (ADS)

    Cappello, Miriam; Lamia, Pietro; Mura, Claudio; Polacco, Giovanni; Filippi, Sara

    2016-07-01

    Polymeric binders for solid propellants are usually based on hydroxyl-terminated polybutadiene (HTPB), which does not contribute to the overall energy output. Azidic polyethers represent an interesting alternative but may have poorer mechanical properties. Polybutadiene-polyether copolymers may combine the advantages of both. Four different ether-butadiene-ether triblock copolymers were prepared and azidated starting from halogenated and/or tosylated monomers using HTPB as initiator. The presence of the butadiene block complicates the azidation step and reduces the storage stability of the azidic polymer. Nevertheless, the procedure allows modifying the binder properties by varying the type and lengths of the energetic blocks.

  1. Data on macrophage mediated muscle transfection upon delivery of naked plasmid DNA with block copolymers.

    PubMed

    Mahajan, Vivek; Gaymalov, Zagit; Alakhova, Daria; Gupta, Richa; Zucker, Irving H; Kabanov, Alexander V

    2016-06-01

    The data contains 14 figures supporting the research article "Horizontal gene transfer from macrophages to ischemic muscles upon delivery of naked DNA with Pluronic block copolymers" [1]. The data explains the surgical procedure and histological characterization of Murine Hind Limb Ischemia. The data also shows the kinetics of luciferase gene expression, spread of GFP expression through muscle and the colocalization of GFP with cellular markers in ischemic muscles injected with pDNA alone or pDNA/Pluronic. Finally the data shows the effect of Pluronic Block Copolymer to enhance total gene expression (cmv-promoter driven luciferase gene) in coculture of DNA transfected MØs with muscle cells. PMID:27222845

  2. Amphiphilic Graft Copolymer Nanospheres: From Colloidal Self-Assembly to CO2 Capture Membranes.

    PubMed

    Jeon, Harim; Kim, Dong Jun; Park, Min Su; Ryu, Du Yeol; Kim, Jong Hak

    2016-04-13

    Colloidal nanosphere self-assembly effectively generates ordered nanostructures, prompting tremendous interest in many applications such as photonic crystals and templates for inverse opal fabrication. Here we report the self-assembly of low-cost, graft copolymer nanospheres for CO2 capture membranes. Specifically, poly(dimethylsiloxane)-graft-poly(4-vinylpyridine) (PDMS-g-P4VP) is synthesized via one-pot, free radical dispersion polymerization to give discrete monodisperse nanospheres. These nanospheres comprise a surface-anchored highly permeable PDMS layer and internal CO2-philic P4VP spherical core. Their diameter is controllable below the submicrometer range by varying grafting ratios. The colloidal dispersion forms a long-range, close-packed hexagonal array on a substrate by inclined deposition and convective assembly. The array shows dispersion medium-dependent packing characteristics. A thermodynamic correlation is determined using different solvents to obtain stable PDMS-g-P4VP dispersions and interpreted in terms of Flory-Huggins interaction parameter. As a proof-of-concept, the implementation of these nanospheres into membranes simultaneously enhances the CO2 permeability and CO2/N2 selectivity of PDMS-based transport matrixes. Upon physical aging of the solution, the CO2/N2 selectivity is improved up to 26, one of the highest values for highly permeable PDMS-based polymeric membranes. PMID:27004536

  3. Modification of Blend Film Pattern Formation with Block Copolymer Additives

    NASA Astrophysics Data System (ADS)

    Sung, L.; Satija, S. K.; Karim, A.; Douglas, J. F.; Han, C. C.

    1997-03-01

    The kinetics of phase separation and morphology of polymer blend films of polystyrene(PS) and polybutadiene(PB) with and without diblock copolymer(PS-b-PB) is examined by optical and atomic force microscropy. The thicker PS/PB binary blend film (2000 Åexhibited essentially no surface pattern formation while spinodal decomposition-like patterns were exhibited by thinner films (<= 1000 ÅThis change is interpreted in terms of a suppression of surface-directed spinodal decomposition in the thinner films. A change in the coarsening kinetics was also observed in the thin films as the thickness was varied from 1000 Åto 200 Åand was interpreted as a crossover from three (bulk-like) to two-dimensional kinetics(Sung et al., Phys. Rev. Lett. 76), 4368 (1996).. The addition of diblock copolymer changed the characteristic dimension at which the surface patterning occurred and the surface pattern formation required thinner film. Neutron reflectivity measurements were carried out to study the density profile of diblcok copolymer on phase separation transverse to the silicon surface to understand this effect.

  4. Biodegradable DNA-Brush Block Copolymer Spherical Nucleic Acids Enable Transfection Agent-Free Intracellular Gene Regulation.

    PubMed

    Zhang, Chuan; Hao, Liangliang; Calabrese, Colin M; Zhou, Yu; Choi, Chung Hang J; Xing, Hang; Mirkin, Chad A

    2015-10-28

    By grafting multiple DNA strands onto one terminus of a polyester chain, a DNA-brush block copolymer that can assemble into micelle structure is constructed. These micelle spherical nucleic acids have a density of nucleic acids that is substantively higher than linear DNA block copolymer structures, which makes them effective cellular transfection and intracellular gene regulation agents.

  5. Mesoporous monoliths of inverse bicontinuous cubic phases of block copolymer bilayers

    NASA Astrophysics Data System (ADS)

    Park, Chiyoung; La, Yunju; An, Tae Hyun; Jeong, Hu Young; Kang, Sebyung; Joo, Sang Hoon; Ahn, Hyungju; Shin, Tae Joo; Kim, Kyoung Taek

    2015-03-01

    Solution self-assembly of block copolymers into inverse bicontinuous cubic mesophases is a promising new approach for creating porous polymer films and monoliths with highly organized bicontinuous mesoporous networks. Here we report the direct self-assembly of block copolymers with branched hydrophilic blocks into large monoliths consisting of the inverse bicontinuous cubic structures of the block copolymer bilayer. We suggest a facile and scalable method of solution self-assembly by diffusion of water to the block copolymer solution, which results in the unperturbed formation of mesoporous monoliths with large-pore (>25 nm diameter) networks weaved in crystalline lattices. The surface functional groups of the internal large-pore networks are freely accessible for large guest molecules such as protein complexes of which the molecular weight exceeded 100 kDa. The internal double-diamond (Pn3m) networks of large pores within the mesoporous monoliths could be replicated to self-supporting three-dimensional skeletal structures of crystalline titania and mesoporous silica.

  6. Effect of Macromolecular Architecture on the Morphology of Polystyrene Polyisoprene Block Copolymers

    SciTech Connect

    Kumar, Rajeev; Goswami, Monojoy; Mays, Jimmy; Sides, Scott; Sumpter, Bobby G; Dadmun, Mark D; Dyer, Caleb W; Driva, Paraskevi; Chen, Jihua

    2013-01-01

    The impact of block connectivity on the morphologies of four block copolymers of varying architecture containing polystyrene (PS) and polyisoprene (PI) has been studied. The volume fraction of PS and molecular weight are held constant while varying the architecture from a linear PS-PI diblock copolymer to three different miktoarm star architectures: PS2PI, PSPI2, and PS2PI2. Morphologies of the PS2PI and PSPI2 miktoarm stars are different from those observed for the linear copolymer and dependent on the connectivity of the copolymer blocks. The change in morphology with connectivity indicates that combining two chains at a junction point leads to chain crowding, where subsequent excluded volume effects drive the change in morphology for each sample. The PS2PI2 miktoarm star exhibits the same morphology as the linear diblock but with a reduction in the size of the domains. The extent of the decrease in domain size indicates that chain stretching impacts the formation of this morphology. Experimentally observed morphologies for different chain architectures are generally consistent with three-dimensional self-consistent field theory simulations, taking into account conformational asymmetry and experimental uncertainty in the copolymer composition. Furthermore, these results generally agree with analytical theory predictions that account for architectural and conformational asymmetry.

  7. Hierarchical Nanoparticle Topography in Amphiphilic Copolymer Films Controlled by Thermodynamics and Dynamics

    PubMed Central

    Caporizzo, M. A.; Ezzibdeh, R. M.

    2016-01-01

    This study systematically investigates how polymer composition changes nanoparticle (NP) grafting and diffusion in solvated random copolymer thin films. By thermal annealing from 135 to 200 °C, thin films with a range of hydrophobicity are generated by varying acrylic acid content from 2% (SAA2) to 29% (SAA29). Poly(styrene-random-tert butyl acrylate) films, 100 nm thick, that are partially converted to poly(styrene-random-acrylic acid), SAA, reversibly swell in ethanol solutions containing amine-functionalized SiO2 nanoparticles with a diameter of 45 nm. The thermodynamics and kinetics of NP grafting are directly controlled by the AA content in the SAA films. At low AA content, namely SAA4, NP attachment saturates at a monolayer, consistent with a low solubility of NPs in SAA4 due to a weakly negative χ parameter. When the AA content exceeds 4%, NPs sink into the film to form multilayers. These films exhibit hierarchical surface roughness with a RMS roughness greater than the NP size. Using a quartz crystal microbalance, NP incorporation in the film is found to saturate after a mass equivalence of about 3 close-packed layers of NPs have been incorporated within the SAA. The kinetics of NP grafting is observed to scale with AA content. The surface roughness is greatest at intermediate times (5–20 min) for SAA13 films, which also exhibit superhydrophobic wetting. Because clustering and aggregation of the NPs within SAA29 films reduce film transparency, SAA13 films provide both maximum hydrophobicity and transparency. The method in this study is widely applicable because it can be applied to many substrate types, can cover large areas, and retains the amine functionality of the particles which allows for subsequent chemical modification. PMID:25689222

  8. Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides

    NASA Astrophysics Data System (ADS)

    Görl, Daniel; Zhang, Xin; Stepanenko, Vladimir; Würthner, Frank

    2015-05-01

    New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating.

  9. Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides

    PubMed Central

    Görl, Daniel; Zhang, Xin; Stepanenko, Vladimir; Würthner, Frank

    2015-01-01

    New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating. PMID:25959777

  10. Inducing an Order–Order Morphological Transition via Chemical Degradation of Amphiphilic Diblock Copolymer Nano-Objects

    PubMed Central

    2016-01-01

    The disulfide-based cyclic monomer, 3-methylidene-1,9-dioxa-5,12,13-trithiacyclopentadecane-2,8-dione (MTC), is statistically copolymerized with 2-hydroxypropyl methacrylate to form a range of diblock copolymer nano-objects via reversible addition–fragmentation chain transfer (RAFT) polymerization. Poly(glycerol monomethacrylate) (PGMA) is employed as the hydrophilic stabilizer block in this aqueous polymerization-induced self-assembly (PISA) formulation, which affords pure spheres, worms or vesicles depending on the target degree of polymerization for the core-forming block. When relatively low levels (<1 mol %) of MTC are incorporated, high monomer conversions (>99%) are achieved and high blocking efficiencies are observed, as judged by 1H NMR spectroscopy and gel permeation chromatography (GPC), respectively. However, the side reactions that are known to occur when cyclic allylic sulfides such as MTC are statistically copolymerized with methacrylic comonomers lead to relatively broad molecular weight distributions. Nevertheless, the worm-like nanoparticles obtained via PISA can be successfully transformed into spherical nanoparticles by addition of excess tris(2-carboxyethyl)phosphine (TCEP) at pH 8–9. Surprisingly, DLS and TEM studies indicate that the time scale needed for this order–order transition is significantly longer than that required for cleavage of the disulfide bonds located in the worm cores indicated by GPC analysis. This reductive degradation pathway may enable the use of these chemically degradable nanoparticles in biomedical applications, such as drug delivery systems and responsive biomaterials. PMID:27228898

  11. Self-Assembled Asymmetric Block Copolymer Membranes: Bridging the Gap from Ultra- to Nanofiltration.

    PubMed

    Yu, Haizhou; Qiu, Xiaoyan; Moreno, Nicolas; Ma, Zengwei; Calo, Victor Manuel; Nunes, Suzana P; Peinemann, Klaus-Viktor

    2015-11-16

    The self-assembly of block copolymers is an emerging strategy to produce isoporous ultrafiltration membranes. However, thus far, it has not been possible to bridge the gap from ultra- to nanofiltration and decrease the pore size of self-assembled block copolymer membranes to below 5 nm without post-treatment. It is now reported that the self-assembly of blends of two chemically interacting copolymers can lead to highly porous membranes with pore diameters as small as 1.5 nm. The membrane containing an ultraporous, 60 nm thin separation layer can fully reject solutes with molecular weights of 600 g mol(-1) in aqueous solutions with a water flux that is more than one order of magnitude higher than the permeance of commercial nanofiltration membranes. Simulations of the membrane formation process by dissipative particle dynamics (DPD) were used to explain the dramatic observed pore size reduction combined with an increase in water flux. PMID:26388216

  12. Shape-controlled synthesis of gold icosahedra and nanoplates using Pluronic P123 block copolymer and sodium chloride

    SciTech Connect

    Lee, Won-Ki; Cha, Sang-Ho; Kim, Ki-Hyun; Kim, Byung-Woo; Lee, Jong-Chan

    2009-12-15

    Gold icosahedra with an average diameter of about 600 nm were easily prepared by heating an aqueous solution of the amphiphilic block copolymer, poly(ethylene oxide){sub 20}-poly(propylene oxide){sub 70}-poly(ethylene oxide){sub 20} (Pluronic P123), and hydrogen tetrachloroaurate(III) trihydrate (HAuCl{sub 4}.3H{sub 2}O) at 60 deg. C for 25 min. When sodium chloride (NaCl:HAuCl{sub 4} molar ratio=10:1) was added to this aqueous solution, gold nanoplates were produced. The chloride ion was found to be a key component in the formation of the gold nanoplates by facilitating the growth of {l_brace}111{r_brace} oriented hexagonal/triangular gold nanoplates, because similar gold nanoplates were produced when LiCl or KCl was added to the aqueous solution instead of NaCl, while gold nanocrystals having irregular shapes were produced when NaBr or NaI was added. - Graphical abstract: Gold icosahedra were prepared by heating an aqueous solution of Pluronic P123 and HAuCl{sub 4}. When NaCl was added to this solution, gold nanoplates were produced.

  13. Dexamethasone-loaded Block Copolymer Nanoparticles Induce Leukemia Cell Death and Enhances Therapeutic Efficacy: A Novel Application in Pediatric Nanomedicine

    PubMed Central

    Krishnan, Vinu; Xu, Xian; Barwe, Sonali P.; Yang, Xiaowei; Czymmek, Kirk; Waldman, Scott A.; Mason, Robert W.; Jia, Xinqiao; Rajasekaran, Ayyappan K.

    2014-01-01

    Nanotechnology approaches have tremendous potential for enhancing treatment efficacy with lower doses of chemotherapeutics. Nanoparticle-based drug delivery approaches are poorly developed for childhood leukemia. Dexamethasone (Dex) is one of the most common chemotherapeutic drugs used in the treatment of childhood leukemia. In this study, we encapsulated Dex in polymeric nanoparticles and validated their anti-leukemic potential in vitro and in vivo. Nanoparticles (NPs) with an average diameter of 110 nm were assembled from amphiphilic block copolymers poly (ethylene glycol) (PEG) and poly (ε-caprolactone) (PCL) bearing pendant cyclic ketals. The blank nanoparticles were non-toxic to cultured cells in vitro and to mice in vivo. Encapsulation of Dex into the nanoparticles (Dex-NP) did not compromise the bioactivity of the drug. Dex-NPs induced glucocorticoid phosphorylation and showed cytotoxicity similar to the free Dex in leukemic cells. Studies using nanoparticles labeled with fluorescent dyes revealed leukemic cell surface binding and internalization. In vivo biodistribution studies showed NP accumulation in the liver and spleen with subsequent clearance of the particles with time. In a pre-clinical model of leukemia, Dex-NPs significantly improved the quality of life and survival of mice compared to the free drug. To our knowledge, this is the first report showing the efficacy of polymeric nanoparticles to deliver Dex to potentially treat childhood leukemia and reveals that low dose of Dex should be sufficient for inducing cell death and improve survival. PMID:23194373

  14. Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

    NASA Astrophysics Data System (ADS)

    Teran, Alexander Andrew

    Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid

  15. Influence of the block hydrophilicity of AB2 miktoarm star copolymers on cluster formation in solutions.

    PubMed

    Han, Minwoo; Hong, Minhyung; Sim, Eunji

    2011-05-28

    We investigated the formation of various micelle shapes of lipid-like amphiphilic AB(2) miktoarm star copolymers in a solution, by performing dissipative particle dynamics simulations. AB(2) miktoarm star copolymer molecules are modeled with coarse-grained structures that consist of a relatively hydrophilic head (A) group with a single arm and a hydrophobic tail (B) group with double arms. A decrease in the hydrophilicity of the head group leads to a reduction of the polymer-solvent contact area, causing cluster structure changes from spherical micelles to vesicles. Consequently, a spherical exterior with multi-lamellar or cylindrical phase interior structures forms under poor solvent conditions without the introduction of spherical hard-wall containers. Furthermore we observed that, for small head group lengths, vesicles were formed in much wider range of solvent-head interaction strength than for long head groups, indicating that molecules with short head group offer a superior vesicle forming property. A phase diagram, the structure and kinetics of the cluster formation, a density profile, and a detailed shape analysis are presented to discuss the molecular characteristics of potential candidates for drug carriers that require superior and versatile vesicle forming properties. We also show that, under certain solvent-hydrophilic head group interaction conditions, initially formed cylindrical micelles transform to bilayer fragments through redistribution of copolymers within the cluster.

  16. Photovoltaic enhancement of organic solar cells by a bridged donor-acceptor block copolymer approach

    NASA Astrophysics Data System (ADS)

    Sun, Sam-Shajing; Zhang, Cheng; Ledbetter, Abram; Choi, Soobum; Seo, Kang; Bonner, Carl E.; Drees, Martin; Sariciftci, Niyazi Serdar

    2007-01-01

    The authors show that a photovoltaic device composed of a -donor-bridge-acceptor-bridge- type block copolymer thin film exhibits a significant performance improvement over its corresponding donor/acceptor blend (Voc increased from 0.14to1.10V and Jsc increased from 0.017 to 0.058mA/cm2) under identical conditions, where donor is an alkyl derivatized poly-p-phenylenevinylene (PPV) conjugated block, acceptor is a sulfone-alkyl derivatized PPV conjugated block, and bridge is a nonconjugated and flexible unit. The authors attribute such improvement to the block copolymer intrinsic nanophase separation and molecular self-assembly that results in the reduction of the exciton and carrier losses.

  17. Quasi-Block Copolymers Based on a General Polymeric Chain Stopper.

    PubMed

    Sanguramath, Rajashekharayya A; Nealey, Paul F; Shenhar, Roy

    2016-07-11

    Quasi-block copolymers (q-BCPs) are block copolymers consisting of conventional and supramolecular blocks, in which the conventional block is end-terminated by a functionality that interacts with the supramolecular monomer (a "chain stopper" functionality). A new design of q-BCPs based on a general polymeric chain stopper, which consists of polystyrene end-terminated with a sulfonate group (PS-SO3 Li), is described. Through viscosity measurements and a detailed diffusion-ordered NMR spectroscopy study, it is shown that PS-SO3 Li can effectively cap two types of model supramolecular monomers to form q-BCPs in solution. Furthermore, differential scanning calorimetry data and structural characterization of thin films by scanning force microscopy suggests the existence of the q-BCP architecture in the melt. The new design considerably simplifies the synthesis of polymeric chain stoppers; thus promoting the utilization of q-BCPs as smart, nanostructured materials. PMID:27276387

  18. Quasi-Block Copolymers Based on a General Polymeric Chain Stopper.

    PubMed

    Sanguramath, Rajashekharayya A; Nealey, Paul F; Shenhar, Roy

    2016-07-11

    Quasi-block copolymers (q-BCPs) are block copolymers consisting of conventional and supramolecular blocks, in which the conventional block is end-terminated by a functionality that interacts with the supramolecular monomer (a "chain stopper" functionality). A new design of q-BCPs based on a general polymeric chain stopper, which consists of polystyrene end-terminated with a sulfonate group (PS-SO3 Li), is described. Through viscosity measurements and a detailed diffusion-ordered NMR spectroscopy study, it is shown that PS-SO3 Li can effectively cap two types of model supramolecular monomers to form q-BCPs in solution. Furthermore, differential scanning calorimetry data and structural characterization of thin films by scanning force microscopy suggests the existence of the q-BCP architecture in the melt. The new design considerably simplifies the synthesis of polymeric chain stoppers; thus promoting the utilization of q-BCPs as smart, nanostructured materials.

  19. Stability of the fcc structure in block copolymer systems.

    PubMed

    Nonomura, Makiko

    2008-11-19

    The stability of the face-centered cubic (fcc) structure in microphase separated copolymers is investigated by a coarse-grained approach. Direct simulations of the equation for the microphase separation in three dimensions indicate that there is a narrow area above a certain degree of segregation in the phase diagram, where the fcc structure is the most stable structure. By employing the mode expansion, we have confirmed that the fcc structure can form as a metastable structure even in the weak segregation regime.

  20. Shear-alignment of metal-containing block copolymer thin films for nanofabrication

    NASA Astrophysics Data System (ADS)

    Kim, So Youn; Register, Richard; Gwyther, Jessica; Manners, Ian; Chaikin, Paul

    2013-03-01

    Cylinder-forming block copolymers can be used as etch masks for the fabrication of nanowire grids, with both fine resolution and scalability. However, achieving a high aspect ratio in these nanostructures, where reactive ion etching is employed for pattern transfer, requires strong etch contrast between two blocks of the copolymer. We achieve this strong contrast by using metal-containing block copolymers: materials which either contain metal as synthesized, or which can be selectively metallized after deposition as thin films. In the first case, iron-containing polystyrene-b-poly(ferrocenylisopropylmethylsilane) (PS-PFS) forming PFS cylinders was employed, and a spin-coated film was aligned by shearing with a polydimethylsiloxane pad. In the second case, polystyrene-b-poly-2-vinylpyridine (PS-P2VP) was deposited as a film, shear-aligned, and then platinum was selectively sequestered within the P2VP cylinders by brief soaking in an aqueous solution of a Pt salt. In both cases, shear stress produced alignment over centimeter-scale areas; this alignment was retained for PS-P2VP during the selective metallization. The line pattern in these aligned block copolymer thin films is then transferred via reactive ion etching into amorphous silicon deposited onto a quartz wafer to fabricate silicon nanowire grid polarizers which can operate at deep ultraviolet wavelengths.

  1. Anionic polymerization and polyhomologation: an ideal combination to synthesize polyethylene-based block copolymers.

    PubMed

    Zhang, Hefeng; Alkayal, Nazeeha; Gnanou, Yves; Hadjichristidis, Nikos

    2013-10-11

    A novel one-pot methodology combining anionic polymerization and polyhomologation, through a "bridge" molecule (BF3OEt2), was developed for the synthesis of polyethylene (PE)-based block copolymers. The anionically synthesized macroanion reacts with the "bridge" molecule to afford a 3-arm star (trimacromolecular borane) which serves as an initiator for the polyhomologation. PMID:23963373

  2. Interaction of very cold neutrons with a polystyrene-polybutadiene-polystyrene block copolymer

    SciTech Connect

    Antonov, A.V.; Gerasimov, V.I.; Isakov, A.I.; Kuznetsov, S.P.; Meshkov, I.V.; Perekrestenko, A.D.; Tarasov, S.G.

    1985-03-10

    The total interaction cross sections have been studied as a function of the wavelength of very cold neutrons (summation/sub t/(lambda)) in a very-cold-neutron spectrometer (A. V. Antonov et al., Kratk. Soobshch. Fiz. 10, 10 (1977)) with a polystyrene-polybutadiene-polystyrene block copolymer at room temperature and at 99 K.

  3. Single- and Multilayered Nanostructures via Laser-Induced Block Copolymer Self-Assembly

    NASA Astrophysics Data System (ADS)

    Majewski, Pawel; Yager, Kevin; Rahman, Atikur; Black, Charles

    We present a novel method of accelerated self-assembly of block copolymer thin films utilizing laser light, called Laser Zone Annealing (LZA). In our approach, steep temperature transients are induced in block copolymer films by rastering narrowly focused laser line over the light-absorbing substrate. Extremely steep temperature gradients accelerate the process of self-assembly by several orders-of-magnitude compared to conventional oven annealing, and, when coupled to photo-thermal shearing, lead to global alignment of block copolymer domains assessed by GISXAS diffraction studies and real-space SEM imaging. We demonstrate monolithic alignment of various block-copolymer thin films including PS-b-PMMA, PS-b-PEO, PS-b-P2VP, PS-b-PI and observe different responsiveness to the shearing rate depending on the characteristic relaxation timescale of the particular material. Subsequently, we use the aligned polymeric films as templates for synthesis of single- and multi-layered arrays of inorganic, metallic or semiconducting nanowires and nanomeshes and investigate their anisotropic electro-optical properties. Research carried out in part at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

  4. Multiscale Control of Hierarchical Structure in Crystalline Block Copolymer Nanoparticles Using Microfluidics.

    PubMed

    Bains, Aman; Cao, Yimeng; Moffitt, Matthew G

    2015-11-01

    Hierarchical semicrystalline block copolymer nanoparticles are produced in a segmented gas-liquid microfluidic reactor with top-down control of multiscale structural features, including nanoparticle morphologies, sizes, and internal crystallinities. Control of multiscale structure on disparate length scales by a single control variable (flow rate) enables tailoring of drug delivery nanoparticle function including release rates.

  5. Understanding the Dynamics of Magnetic Field Alignment for Rod-Coil Block Copolymers

    NASA Astrophysics Data System (ADS)

    McCulloch, Bryan; Portale, Giuseppe; Bras, Wim; Hexemer, Alexander; Segalman, Rachel A.

    2012-02-01

    Alignment of semiconducting block copolymer nanostructures is crucial to optimize charge transport in these materials. Magnetic fields can act on the liquid crystalline conjugated polymers, inducing alignment in rod-coil block copolymers. By using a combination of small angle x-ray scattering (SAXS) and transmission electron microscopy (TEM) we have studied the magnetic field alignment of poly(alkoxy phenylene vinylene-b-isoprene) (PPV-PI) rod-coil block copolymers. In situ measurements have also shown the magnetic field leads to a stabilization of the ordered phase. Furthermore, there appear to be two distinct timescales for alignment: at short times the alignment of these materials is fast likely caused by preferential growth of aligned domains, and at long times alignment increases by the very slow process of defect annihilation. Further, there is an optimum temperature where the kinetics and thermodynamic driving forces for alignment are balanced, producing very highly aligned samples. Understanding the mechanisms by which alignment occurs has lead to knowledge helping to rationally optimize the magnetic alignment of rod-coil block copolymers.

  6. Phase behavior of ABC-type triple-hydrophilic block copolymers in aqueous solutions.

    PubMed

    Zheng, Lingfei; Wu, Jianqi; Wang, Zheng; Yin, Yuhua; Jiang, Run; Li, Baohui

    2016-07-01

    The phase behavior of symmetric ABC triple-hydrophilic triblock copolymers in concentrated aqueous solutions is investigated using a simulated annealing technique. Two typical cases, in which the hydrophilicity of the middle B-block is either stronger or weaker than that of the end A- and C-blocks, are studied. In these two cases, a variety of phase diagrams are constructed as a function of the volume fraction of the B-block and the copolymer concentration ([Formula: see text] for both non-frustrated and frustrated copolymers. Structures, such as two-color alternatingly packed cylinders or gyroid, and lamellae-in-lamellae etc. that do not occur in the melt system, are obtained in solutions. Rich phase transition sequences, especially re-entrant phase transitions involving complex continuous networks of alternating gyroid and alternating diamond are observed for a given copolymer with decreasing [Formula: see text] . The difference in hydrophilicity among different blocks can result in inhomogeneous distribution of solvent molecules in the morphology, and with the decrease of [Formula: see text] , the distribution of solvent molecules presents a non-monotonic variation. This results in a non-monotonic variation of the effective volume fraction of each domain with the decrease of [Formula: see text] , which induces the re-entrant phase transitions. The presence of a good solvent for all the blocks can cause changes in the effective segregation strengths between different blocks and also in chain conformations, hence can alter the bulk phases and results in the occurrence of new structures and phase transitions. Especially, structures having A-C interfaces or A-C mixed domains can be obtained even in the non-frustrated copolymer systems, and structures obtained in the frustrated systems may be similar to those obtained in the non-frustrated systems. The window of the alternating gyroid structures may occupy a large part of the phase diagram for non

  7. "Near perfect" amphiphilic conetwork based on end-group cross-linking of polydimethylsiloxane triblock copolymer via atom transfer radical polymerization.

    PubMed

    Xu, Jianfeng; Qiu, Ming; Ma, Bomou; He, Chunju

    2014-09-10

    Novel amphiphilic conetworks (APCNs) with uniform channel size were synthesized through end-cross-linking of well-defined amphiphilic triblock copolymers via atom transfer radical polymerization (ATRP). A new ditelechelic polydimethylsiloxane macroinitiator was synthesized to initiate the polymerization of N,N-dimethylacrylamide. The resulting triblock copolymers show well-defined molecular weight with narrow polydisperisty, which are telechelic modified by allylamine and fully cross-linked with polyhydrosiloxanes through hydrosilylation. Transmission electron microscopy shows that the APCN has the behavior of microphase separation with small channel size and uniform phase domain. The resulting APCNs with idealized microstructure exhibit a combination of excellent properties, i.e., superhigh mechanical strength (4 ± 1 MPa) and elongation ratio (175 ± 25%), outstanding oxygen permeability (350 ± 150 barrers), a high water uptake property, and excellent biocompatibility, indicating that in this way, "near perfect" networks are obtained. These results are better than those reported in the literature, suggesting a promising semipermeable barrier for islet encapsulation in relative biomaterial fields.

  8. Hierarchical self-assembly of spider silk-like block copolymers

    NASA Astrophysics Data System (ADS)

    Krishnaji, Sreevidhya; Huang, Wenwen; Cebe, Peggy; Kaplan, David

    2011-03-01

    Block copolymers provide an attractive venue to study well-defined nano-structures that self-assemble to generate functionalized nano- and mesoporous materials. In the present study, a novel family of spider silk-like block copolymers was designed, bioengineered and characterized to study the impact of sequence chemistry, secondary structure and block length on assembled morphology. Genetic variants of native spider dragline silk (major ampullate spidroin I, Nephila clavipes) were used as polymer building blocks. Characterization by FTIR revealed increased ?-sheet content with increasing hydrophobic A blocks; SEM revealed spheres, rod-like structures, bowl-shaped and giant compound micelles. Langmuir Blodgett monolayers were prepared at the air-water interface at different surface pressures and monolayer films analyzed by AFM revealed oblate to prolate structures. Circular micelles, rod-like, densely packed circular structures were observed for HBA6 at increasing surface pressure. Exploiting hierarchical assembly provide a promising approach to rationale designs of protein block copolymer systems, allowing comparison to traditional synthetic systems.

  9. Controlling Miscibility in Polyethylene-Polynorbornene Block Copolymers via Side-Group Chemistry

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    Block copolymers containing a crystallizable block, such as polyethylene (PE), and an amorphous block with high glass transition temperature (Tg) are an interesting class of materials since the rigid glassy block can improve the mechanical response of the article under strain by reinforcing the crystal fold surface. However, to prepare an easily processable PE-containing block copolymer it is necessary to avoid microphase separation in the melt by selection of amorphous blocks with weak repulsive interactions against PE (low Flory interaction parameter χ or interaction energy density X) . Most such low- χ polymers are chemically similar to PE, such as copolymers of ethylene and a small amount of an α-olefin, and therefore exhibit similarly low glass transition temperatures. This work investigates a series of low- and high-Tg polymers based on substituted norbornene monomers, polymerized via ring-opening metathesis polymerization (ROMP). Hydrogenated polynorbornene derivatives possess a wide range of glass transition temperatures, and miscibility with PE can be readily tuned by the choice of substituents on the monomers (e.g. aromatic vs. aliphatic groups). Two species investigated, hydrogenated poly(cyclohexyl norbornene) and hydrogenated poly(norbornyl norbornene), have high Tg and also remain miscible with polyethylene to high molecular weight. Furthermore, we develop a set of mixing rules to qualitatively predict the solubility behavior of substituted ROMP polynorbornenes as a function of their side-groups.

  10. Surface Modification for Controlling the Orientation of Block Copolymers in thin film and in Cylindrical Nanopores

    NASA Astrophysics Data System (ADS)

    Lin, Xin-Guan; Lin, Feng-Cheng; Tung, Shih-Huang

    2012-02-01

    A series of benzocyclobutene-functionalized random copolymers of styrene and 4-vinylpyridine were synthesized by nitroxide-mediated controlled radical polymerization with BPO and TEMPO. Our research was to use these random copolymers of P(S-r-BCB-r-4VP) to control the orientation of microdomains in block copolymers(BCPs) of poly(styrene-b-4-vinylpyridine)(PS-b-P4VP) thin films and in cylindrical nanopores of anodized aluminum oxide (AAO) membranes. On P(S-r-BCB-r-4VP)-modified substrate,we found that in some particular compositions of random copolymer ,the parallel orientation of the microdomains is switched to be perpendicular in PS-b-P4VP thin film. We also introduced P(S-r-BCB-r-4VP) solution into the nanopores of the AAO and nanotubes formed after solvent evaporation and pyrolysis. And then BCPs of PS-b-P4VP were drawn into the P(S-r-BCB-r-4VP)-modified nanopores in the melt via capillary action to form P(S-r-BCB-r-4VP) coated nanorods of PS-b-P4VP.Similarly,in some particular compositions of random copolymer, we observed that the interactions of the blocks with the walls are not strong or if the interactions are balanced, then the orientation of the microdomains will change from being parallel to being perpendicular to the confining walls.

  11. Theory for dynamical self arrest and gelation in microemulsions and the block copolymer systems

    SciTech Connect

    Wu, Sangwook

    2005-01-01

    The main purpose of this work is to investigate the glassy behavior of microemulsions and block copolymers. The origin of glassy behavior in microemulsions and block copolymers is frustration due to a competition between short-range interaction and long range interaction. According to the charge frustrated Ising model, the competition between ferromagnetic interaction and antiferromagnetic interaction is the origin of frustration in microemulsions. The competition between entropic effects and stoichiometric constraints responsible for the formation of micelles in microemulsions can lead to the emergence of a self generated glassy behavior in these systems. In the block copolymer, the competition between the repulsive short range interaction between monomers in polymer chains and the long range interaction by chemical bonds can lead to the emergence of a self generated glassy behavior. The criteria for the fluctuation induced first order transition and our microemulsion and block copolymer glasses are essentially the same. Both are a consequence of the large phase space of low energy excitations (14) (62) (all states with momenta q which fulfill |q| = qm) and are of at the most a moderate supercooling of the liquid state is required. This is strongly supported by the observation in Ref. (14) that the metastable states which are first to appear at a fluctuation induced first order transition are the ones build by a superposition of large amplitude waves of wavenumber qm, but with random orientations and phases, i.e. just the ones which form the metastable states of our microemulsion and block copolymer glass. (38)

  12. Characterization of a Poly(styrene-block-methylacrylate-random-octadecylacrylate-block-styrene) Shape Memory ABA Triblock Copolymer

    NASA Astrophysics Data System (ADS)

    Fei, Pengzhan; Cavicchi, Kevin

    2011-03-01

    A new ABA triblock copolymer of poly(styrene-block- methylacrylate-random-octadecylacrylate-block-styrene) (PS-b- PMA-r-PODA-b-PS) was synthesized by reversible addition fragmentation chain transfer polymerization. The triblock copolymer can generate a three-dimensional, physically crosslinked network by self-assembly, where the glassy PS domains physically crosslink the midblock chains. The side chain crystallization of the polyoctadecylacrylare (PODA) side chain generates a second reversible network enabling shape memory properties. Shape memory tests by uniaxial deformation and recovery of molded dog-bone shape samples demonstrate that shape fixities above 96% and shape recoveries above 98% were obtained for extensional strains up to 300%. An outstanding advantage of this shape memory material is that it can be very easily shaped and remolded by elevating the temperature to 140circ; C, and after remolding the initial shape memory properties are totally recovered by eliminating the defects introduced by the previous deformation cycling.

  13. The structure of nanochannels formed by block copolymer solutions confined in nanotubes.

    PubMed

    Chen, Houyang; Ruckenstein, Eli

    2009-09-21

    Monte Carlo simulations are employed to obtain information about the radius and the roughness of the inner surface of the channels, which are generated by a family of block copolymer solutions confined in nanotubes. The fluctuations of the above quantities also have been calculated. The simulations have been carried out by varying the interactions between various kinds of segments and those between segments and the wall of the nanotubes, as well as the chemical structure of the copolymer and the nanotube diameter. The present simulations provide insight regarding the structure of ionic and water channels formed by protein in the phospholipid bilayers of the cell membrane.

  14. The use of cholesterol-containing biodegradable block copolymers to exploit hydrophobic interactions for the delivery of anticancer drugs.

    PubMed

    Lee, Ashlynn L Z; Venkataraman, Shrinivas; Sirat, Syamilah B M; Gao, Shujun; Hedrick, James L; Yang, Yi Yan

    2012-02-01

    A series of biodegradable amphiphilic block copolymers with controlled composition and relatively low polydispersity index were synthesized from monomethoxy polyethylene glycol (mPEG-OH, 5 kDa) via organocatalytic ring opening polymerization of aliphatic cyclic carbonate monomers - trimethylene carbonate (TMC) or cholesteryl 2-(5-methyl-2-oxo-1,3-dioxane-5-carboxyloyloxy)ethyl carbamate (MTC-Chol) or a copolymer of both the monomers (TMC and MTC-Chol): mPEG(113)-b-PTMC(67), mPEG(113)-b-P(MTC-Chol(11)) and mPEG(113)-b-P(MTC-Chol(x)-co-TMC(y))(x+y). These well-defined polymers were employed to study the role of molecular weight and composition of the hydrophobic block of the polymers in loading paclitaxel (PTX), an extremely hydrophobic anticancer drug with rigid structure and strong tendency of self-association to form long fibers. The PTX-loaded micelles were fabricated by simple self-assembly without sonication or homogenization procedures. The results demonstrated that the presence of both MTC-Chol and TMC in the hydrophobic block significantly increased PTX loading levels, and the micelles formed from the polymer with the optimized composition (i.e. mPEG(113)-b-P(MTC-Chol(11)-co-TMC(30))) were in nanosize (36 nm) with narrow size distribution (PDI: 0.07) and high PTX loading capacity (15 wt.%). In vitro treatment of human liver hepatocellular carcinoma HepG2 cells with blank micelles showed that these polymeric carriers were non-cytotoxic with cell viability greater than 90% at ~2400 mg/L. Importantly, PTX-loaded micelles were able to kill cancer cells much more effectively compared to free PTX. In addition, these nanocarriers also possessed exceptional kinetic stability. The results from non-invasive near-infrared fluorescence (NIRF) imaging studies showed that these micelles allowed effective passive targeting, and were preferably accumulated in tumor tissue with limited distribution to healthy organs. PMID:22137125

  15. The use of cholesterol-containing biodegradable block copolymers to exploit hydrophobic interactions for the delivery of anticancer drugs.

    PubMed

    Lee, Ashlynn L Z; Venkataraman, Shrinivas; Sirat, Syamilah B M; Gao, Shujun; Hedrick, James L; Yang, Yi Yan

    2012-02-01

    A series of biodegradable amphiphilic block copolymers with controlled composition and relatively low polydispersity index were synthesized from monomethoxy polyethylene glycol (mPEG-OH, 5 kDa) via organocatalytic ring opening polymerization of aliphatic cyclic carbonate monomers - trimethylene carbonate (TMC) or cholesteryl 2-(5-methyl-2-oxo-1,3-dioxane-5-carboxyloyloxy)ethyl carbamate (MTC-Chol) or a copolymer of both the monomers (TMC and MTC-Chol): mPEG(113)-b-PTMC(67), mPEG(113)-b-P(MTC-Chol(11)) and mPEG(113)-b-P(MTC-Chol(x)-co-TMC(y))(x+y). These well-defined polymers were employed to study the role of molecular weight and composition of the hydrophobic block of the polymers in loading paclitaxel (PTX), an extremely hydrophobic anticancer drug with rigid structure and strong tendency of self-association to form long fibers. The PTX-loaded micelles were fabricated by simple self-assembly without sonication or homogenization procedures. The results demonstrated that the presence of both MTC-Chol and TMC in the hydrophobic block significantly increased PTX loading levels, and the micelles formed from the polymer with the optimized composition (i.e. mPEG(113)-b-P(MTC-Chol(11)-co-TMC(30))) were in nanosize (36 nm) with narrow size distribution (PDI: 0.07) and high PTX loading capacity (15 wt.%). In vitro treatment of human liver hepatocellular carcinoma HepG2 cells with blank micelles showed that these polymeric carriers were non-cytotoxic with cell viability greater than 90% at ~2400 mg/L. Importantly, PTX-loaded micelles were able to kill cancer cells much more effectively compared to free PTX. In addition, these nanocarriers also possessed exceptional kinetic stability. The results from non-invasive near-infrared fluorescence (NIRF) imaging studies showed that these micelles allowed effective passive targeting, and were preferably accumulated in tumor tissue with limited distribution to healthy organs.

  16. Disk-cylinder and disk-sphere nanoparticles from block copolymer blend solution construction

    SciTech Connect

    Zhu, Jiahua; Zhang, Shiyi; Zhang, Ke; Wang, Xiaojun; Mays, Jimmy; Wooley, Karen L; Pochan, Darrin

    2013-01-01

    Researchers strive to produce nanoparticles with complexity in composition and structure. Although traditional spherical, cylindrical and membranous, or planar, nanostructures are ubiquitous, scientists seek more complicated geometries for potential functionality. Here we report the simple solution construction of multigeometry nanoparticles, disk-sphere and diskcylinder, through a straightforward, molecular-level, blending strategy with binary mixtures of block copolymers. The multigeometry nanoparticles contain disk geometry in the core with either spherical patches along the disk periphery in the case of disk-sphere particles or cylindrical edges and handles in the case of the disk-cylinder particles. The portions of different geometry in the same nanoparticles contain different core block chemistry, thus also defining multicompartments in the nanoparticles. Although the block copolymers chosen for the blends are important for the definition of the final hybrid particles, the control of the kinetic pathway of assembly is critical for successful multigeometry particle construction.

  17. Liquid Crystalline Block Copolymers with Brush Type Architecture: Toward Functional Membranes by Magnetic Field Alignment

    NASA Astrophysics Data System (ADS)

    Choo, Youngwoo; Gopinadhan, Manesh; Mahajan, Lalit; Kasi, Rajeswari; Osuji, Chinedum

    2015-03-01

    We introduce a novel liquid crystalline block copolymer with brush type architecture for membrane applications by magnetic field directed self-assembly. Ring-opening metathesis of n-alkyloxy cyanobiphenyl and polylactide (PLA) functionalized norbornene monomers provides efficient polymerization yielding low polydispersity block copolymers. The molecular weight of the PLA side chains, spacer length of the cyanobiphenyl mesogens are systematically varied to form well-ordered BCP morphologies at varying volume fractions. Interestingly, the system features morphology dependent anchoring condition where mesogens adopt planar anchoring on cylindrical interface while homeotropic anchoring was preferred on a planar block interface. The minority PLA domains from highly aligned materials can be readily degraded by hydrolysis to produce vertically aligned nanoporous polymer films which exhibit reversible thermal switching behavior. The polymers introduced here provide a versatile platform for scalable fabrication of aligned membranes and further functional materials based on such templates. This work was supported by NSF(CCMI-1246804).

  18. Reconstitution of the membrane protein OmpF into biomimetic block copolymer-phospholipid hybrid membranes.

    PubMed

    Bieligmeyer, Matthias; Artukovic, Franjo; Nussberger, Stephan; Hirth, Thomas; Schiestel, Thomas; Müller, Michaela

    2016-01-01

    Structure and function of many transmembrane proteins are affected by their environment. In this respect, reconstitution of a membrane protein into a biomimetic polymer membrane can alter its function. To overcome this problem we used membranes formed by poly(1,4-isoprene-block-ethylene oxide) block copolymers blended with 1,2-diphytanoyl-sn-glycero-3-phosphocholine. By reconstituting the outer membrane protein OmpF from Escherichia coli into these membranes, we demonstrate functionality of this protein in biomimetic lipopolymer membranes, independent of the molecular weight of the block copolymers. At low voltages, the channel conductance of OmpF in 1 M KCl was around 2.3 nS. In line with these experiments, integration of OmpF was also revealed by impedance spectroscopy. Our results indicate that blending synthetic polymer membranes with phospholipids allows for the reconstitution of transmembrane proteins under preservation of protein function, independent of the membrane thickness. PMID:27547605

  19. SYNTHESIS AND CHARACTERIZATION OF SUBSTITUTED POLY(STYRENE)-b-POLY(ACRYLIC ACID) BLOCK COPOLYMER MICELLES

    SciTech Connect

    Pickel, Deanna L; Pickel, Joseph M; Devenyi, Jozsef; Britt, Phillip F

    2009-01-01

    Block copolymer micelle synthesis and characterization has been extensively studied. In particular, most studies have focused on the properties of the hydrophilic corona due to the micelle corona structure s impact on the biodistribution and biocompatibility. Unfortunately, less attention has been given to the effect of the core block on the micelle stability, morphology, and the rate of diffusion of small molecules from the core. This investigation is focused on the synthesis of block copolymers composed of meta-substituted styrenes and acrylic acid by Atom Transfer Radical Polymerization. Micelles with cores composed of substituted styrenes having Tgs ranging from -30 to 100 oC have been prepared and the size and shape of these micelles were characterized by Static and Dynamic Light Scattering and TEM. In addition, the critical micelle concentration and rate of diffusion of small molecules from the core were determined by fluorimetry using pyrene as the probe.

  20. Molecular transport into and out of ionic-liquid filled block copolymer vesicles in water

    NASA Astrophysics Data System (ADS)

    Lodge, Timothy; Yao, Letitia; So, Soonyong

    We have developed a method to prepare stable, size-controlled block copolymer vesicles that contain ionic liquid in the interior, but that are dispersed in water. Such nanoemulsions are of interest as nanoreactors, because the mass transfer and cost limitations of ionic liquids are circumvented. However, a crucial question is whether target molecules (e . g ., reagents and products) can enter and leave the vesicles, respectively, on a useful time scale (i . e ., seconds or shorter). In this talk we will briefly describe methods to prepare such vesicles with narrow size distributions, using poly(styrene)-block-poly(ethylene oxide) and poly(butadiene)-block-poly(ethylene oxide) copolymers of various compositions. We will then present results of pulsed-field gradient NMR measurements of probe diffusion that yield independent measurements of the entry and escape rates for selected small molecules, as a function of membrane thickness and temperature.

  1. Self-Assembly of Rod-Coil Block Copolymers and Their Application in Electroluminescent Devices

    SciTech Connect

    Tao, Yuefei; Ma, Biwu; Segalman, Rachel A.

    2008-11-18

    The formation of alternating electron transporting and hole transporting 15 nm lamellae within the active layer of an organic light-emitting diode (OLED) is demonstrated to improve device performance. A new multifunctional bipolar rod-coil block copolymer containing a poly(alkoxy phenylenevinylene) (PPV) rod-shaped block as the hole transporting and emitting material and a poly(vinyloxadiazole) coil-shaped electron transporting block is synthesized. This new block copolymer is the active material of a self-assembling multicomponent electroluminescent device that can be deposited in a single step. In the thin film, grazing incidence X-ray scattering and transmission electron microscopy demonstrate that the layers form grains which are oriented bimodally: parallel and perpendicular from the anode. In this mixed orientation, the device demonstrates better performance than those with either pure PPV or a blend of the two analogous homopolymers as the active materials, i.e., higher external quantum efficiency (EQE) and brightness. This improved device performance is mainly attributed to the bipolar functionality and microphase separation of the block copolymer, which provide highly efficient hole and electron recombination at the nanodomain interfaces.

  2. Self-Assembly of Rod-Coil Block Copolymers And Their Application in Electroluminescent Devices

    SciTech Connect

    Tao, Y.; Ma, B.; Segalman, R.A.

    2009-05-26

    The formation of alternating electron transporting and hole transporting 15 nm lamellae within the active layer of an organic light-emitting diode (OLED) is demonstrated to improve device performance. A new multifunctional bipolar rod-coil block copolymer containing a poly(alkoxy phenylenevinylene) (PPV) rod-shaped block as the hole transporting and emitting material and a poly(vinyloxadiazole) coil-shaped electron transporting block is synthesized. This new block copolymer is the active material of a self-assembling multicomponent electroluminescent device that can be deposited in a single step. In the thin film, grazing incidence X-ray scattering and transmission electron microscopy demonstrate that the layers form grains which are oriented bimodally: parallel and perpendicular from the anode. In this mixed orientation, the device demonstrates better performance than those with either pure PPV or a blend of the two analogous homopolymers as the active materials, i.e., higher external quantum efficiency (EQE) and brightness. This improved device performance is mainly attributed to the bipolar functionality and microphase separation of the block copolymer, which provide highly efficient hole and electron recombination at the nanodomain interfaces.

  3. Morphology And Local Mechanical Properties Of A Block Copolymer Cell Substrate

    NASA Astrophys