Biomedical subjects

Timothy P Lodge

Publications and source records attributed to Timothy P Lodge.

At least 19 recordsLinked to original sources

PubMed2006

Morphologies of multicompartment micelles formed by ABC miktoarm star terpolymers.

Several new multicompartment micellar structures have been identified by cryogenic transmission electron microscopy (cryoTEM) from the aqueous self-assembly of mu-[poly(ethylethylene)][poly(ethylene oxide)][poly(perfluoropropylene oxide)] (mu-EOF) miktoarm star terpolymers. This work extends our previous studies, in which it was found that, upon decreasing the length of the hydrophilic block (O), the resulting micelles evolved from "hamburger" micelles to segmented worms and ultimately to nanostructured bilayers and vesicles. In the terpolymers examined here segmented ribbons and bilayers were found at an intermediate composition between segmented worms and nanostructured bilayers, provided that the fluoropolymer (F) was the minority component in the micelle core. On the other hand, when the F block exceeded the chain length of the hydrocarbon block (E), the superhydrophobic F block imposed a "double frustration" on the self-assembly of the mu-EOF(2-9-5) terpolymer; while F prefers to minimize its interfacial contact with the O corona, it must occupy the majority of the micellar core. Therefore, a richer variety of multicompartment micelles, including well-defined segmented worms, raspberry-like micelles, and multicompartmentalized worms, were formed from one terpolymer, as revealed by cryoTEM. Despite the complexity and variety of the observed aggregate morphologies, a small number of common structural elements can be invoked to interpret the observed micelles and to relate a given structure to the terpolymer composition.

Journal Article↗

PubMed2006

The micellar shuttle: thermoreversible, intact transfer of block copolymer micelles between an ionic liquid and water.

Poly(1,2-butadiene-block-ethylene oxide) (PB-PEO) block copolymer micelles are found to partition reversibly between an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) and water, thereby functioning as micellar shuttles controlled simply by temperature. The micelle size and structure are preserved during this reversible phase transfer. This phenomenon offers a simple means to transport chemicals back and forth between two immiscible phases.

Journal Article↗

PubMed2006

Superlattice formation in a binary mixture of block copolymer micelles.

A binary solution mixture of distinct block copolymer micelles is found to adopt a superlattice. The larger micelles, formed from polystyrene-polyisoprene diblocks, have a nominal radius of 29 nm; the smaller micelles, formed from polystyrene-polydimethylsiloxane diblocks, have a nominal radius of 16 nm. The superlattice unit cell dimension is 156 nm and is assigned to space group Fm3c; it corresponds to the AB13 structure. As these diblocks are uncharged, the driving force for superlattice formation is primarily free volume entropy, as in sterically stabilized colloidal hard spheres.

Colloids↗

PubMed2006

Transient solidlike behavior near the cylinder/disorder transition in block copolymer solutions.

A nearly symmetric polystyrene-block-polyisoprene diblock copolymer dissolved at a concentration of 40% in styrene-selective solvents exhibited a cylinder-to-disorder transition upon heating. The solvents used were diethyl phthalate (DEP) and 75:25 and 50:50 mixtures of DEP with di-n-butyl phthalate (DBP). In DEP, the most styrene-selective of the three solvents, rheological measurements indicated a distinct plateau in the temperature-dependent elastic modulus across the 8 degrees C interval above the order-disorder transition temperature, T(ODT) = 116 degrees C. Previous small-angle neutron scattering measurements in this regime indicated the equilibrium phase to be a liquidlike solution of approximately spherical micelles. An isothermal frequency sweep in this regime indicated a very long relaxation time. Annealing eventually led to the recovery of liquidlike rheological response, over a time scale of hours. Qualitatively similar phenomena were also observed in 75:25 DEP/DBP and 50:50 DEP/DBP solutions, except the fact that the temperature window of the transient response is narrow and the time scale for the recovery diminishes significantly. Neither small-angle X-ray scattering nor static birefringence gave any clear signature of the transient structure. The structure that leads to the transient rheological response is attributed to micellar congestion due to the slow relaxation of anisotropic micelles into an equilibrium distribution of micelles. Possible origins of the remarkable solvent selectivity dependence are also discussed.

Butadienes↗

PubMed2006

Kinetics of disorder-to-fcc phase transition via an intermediate bcc state.

Time-resolved small-angle x-ray scattering measurements reveal that a long-lived intermediate bcc state forms when a poly(styrene-b-isoprene) diblock copolymer solution in an isoprene selective solvent is rapidly cooled from the disordered micellar fluid at high temperature to an equilibrium fcc state. The kinetics of the epitaxial growth of the [111] fcc peak from the [110] bcc peak was obtained by fitting the scattering data to a simple model of the transformation. The growth of the [111] fcc peak agrees with the Avrami model of nucleation and growth kinetics with an exponent n=1.4, as does the initial decay of the [110] bcc peak, with an exponent n=1.3. The data were also found to be in good agreement with the Cahn model of grain boundary nucleation and growth.

Journal Article↗

PubMed2006

Influence of conformational asymmetry on the phase behavior of ternary homopolymer/block copolymer blends around the bicontinuous microemulsion channel.

We have developed a new ternary polymeric system, poly(ethylene-alt-propylene) (PEP)/poly(butylene oxide) (PBO)/PEP-PBO, to study the complex phase behavior near the bicontinuous microemulsion phase channel. The molecular weights of the PEP and PBO homopolymers are 2600 and 3050 g/mol, respectively, and the copolymer is 23.4 kg/mol with volume fraction composition fPBO=0.49. A combination of small-angle neutron scattering, small-angle X-ray scattering, rheology, optical microscopy, and visual oil bath measurements was employed to map out the phase diagrams at five fixed homopolymer PBO/PEP ratios, ranging from 40/60 to 60/40 by volume, with copolymer concentrations ranging from 0 to 100%. It was found that the bicontinuous microemulsion channel is consistently cut off at low temperature by a hexagonal phase. We attribute this phenomenon to the effect of the conformational asymmetry between the PEP and PBO species, whereby the more flexible PBO component induces a spontaneous curvature toward the PBO domains. These findings complement previous descriptions of the isopleth phase diagrams for A/B/A-B systems and identify a new design variable for preparing bicontinuous phases.

Journal Article↗

PubMed2006

Self-assembly of block copolymer micelles in an ionic liquid.

Four amphiphilic poly((1,2-butadiene)-block-ethylene oxide) (PB-PEO) diblock copolymers were shown to aggregate strongly and form micelles in an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]). The universal micellar structures (spherical micelle, wormlike micelle, and bilayered vesicle) were all accessed by varying the length of the corona block while holding the core block constant. The nanostructures of the PB-PEO micelles formed in an ionic liquid were directly visualized by cryogenic transmission electron microscopy (cryo-TEM). Detailed micelle structural information was extracted from both cryo-TEM and dynamic light scattering measurements, with excellent agreement between the two techniques. Compared to aqueous solutions of the same copolymers, [BMIM][PF(6)] solutions exhibit some distinct features, such as temperature-independent micellar morphologies between 25 and 100 degrees C. As in aqueous solutions, significant nonergodicity effects were also observed. This work demonstrates the flexibility of amphiphilic block copolymers for controlling nanostructure in an ionic liquid, with potential applications in many arenas.

Butadienes↗

PubMed2006

Laterally nanostructured vesicles, polygonal bilayer sheets, and segmented wormlike micelles.

We report the formation of vesicles with a laterally nanostructured membrane by self-assembly of "miktoarm" star terpolymers, that is, macromolecules with three chemically distinct arms. The lateral structure consists of approximately hexagonally packed fluorocarbon channels with 4.1 nm radii, immersed in a continuous, two-dimensional hydrocarbon bilayer. We also show that the assembly of these vesicles proceeds via metastable polygonal, faceted bilayer sheets.

Colloids↗

PubMed2006

Mesoporous membrane templated by a polymeric bicontinuous microemulsion.

We demonstrate a facile method for preparing a novel nanoporous material with an isotropic, three-dimensionally continuous pore structure from a polymeric bicontinuous microemulsion precursor, which consists of two immiscible homopolymers and the corresponding diblock copolymer. The protocol for the generation of nanopores is selective cross-linking of one domain with the subsequent removal of the other domain by solvent dissolution.

Crystallization↗

PubMed2005

Simultaneous, segregated storage of two agents in a multicompartment micelle.

The simultaneous, segregated storage of two different chromophores in a multicompartment micelle, which is formed from self-assembly of (polyethylethylene)(polyethylene oxide)(polyperfluoropropylene oxide) mikto-arm star terpolymers in water, was investigated by spectrophotometry. The multicompartment micelles, with segregated micellar cores composed of fluorocarbon and hydrocarbon compartments, can simultaneously absorb two chemically different molecules. These two molecules were confined into their preferred compartments with high selectivity.

Micelles↗

PubMed2005

Dynamics of a poly(ethylene oxide) tracer in a poly(methyl methacrylate) matrix: remarkable decoupling of local and global motions.

The tracer diffusion coefficient of unentangled poly(ethylene oxide) (PEO, M=1000 gmol) in a matrix of poly(methyl methacrylate) (PMMA, M=10 000 gmol) has been measured over a temperature range from 125 to 220 degrees C with forced Rayleigh scattering. The dynamic viscosities of blends of two different high molecular weight PEO tracers (M=440 000 and 900 000 gmol) in the same PMMA matrix were also measured at temperatures ranging from 160 to 220 degrees C; failure of time-temperature superposition was observed for these systems. The monomeric friction factors for the PEO tracers were extracted from the diffusion coefficients and the rheological relaxation times using the Rouse model. The friction factors determined by diffusion and rheology were in good agreement, even though the molecular weights of the tracers differed by about three orders of magnitude. The PEO monomeric friction factors were compared with literature data for PEO segmental relaxation times measured directly with NMR. The monomeric friction factors of the PEO tracer in the PMMA matrix were found to be from two to six orders of magnitude greater than anticipated based on direct measurements of segmental dynamics. Additionally, the PEO tracer terminal dynamics are a much stronger function of temperature than the corresponding PEO segmental dynamics. These results indicate that the fastest PEO Rouse mode, inferred from diffusion and rheology, is completely separated from the bond reorientation of PEO detected by NMR. This result is unlike other blend systems in which global and local motions have been compared.

Journal Article↗

PubMed2005

Interplay between cubic and hexagonal phases in block copolymer solutions.

The phase behavior of a symmetric styrene-isoprene (SI) diblock copolymer in a styrene-selective solvent, diethylphthalate, was investigated by in situ small-angle X-ray scattering on isotropic and shear-oriented solutions and by rheology and birefringence. A remarkable new feature in this phase diagram is the coexistence of both body-centered cubic (bcc) and hexagonally close-packed (hcp) sphere phases, in a region between close-packed spheres (cps) and hexagonally packed cylinders (hex) over the concentration range phi approximately 0.33-0.45. By focusing on the transitions among these various ordered phases during heating and cooling cycles, we observed a strong hysteresis: supercooled cylinders persisted upon cooling. The stability of these supercooled cylinders is quite dependent on concentration, and for phi > or = 0.40, the supercooled cylinders do not revert to spheres even after quiescent annealing for 1 month. The spontaneous formation of spheres due to the dissociation of cylinders is kinetically hindered in this case, and the system is apparently not amenable to any pretransitional fluctuations of cylinders prior to the cylinder-to-sphere transition. This contrasts with the case of cylinders transforming to spheres upon heating in the melt. The application of large amplitude shear to the supercooled cylinders is effective in restoring the equilibrium sphere phases.

Journal Article↗

PubMed2004

Temperature-dependent micellar structures in poly(styrene-b-isoprene) diblock copolymer solutions near the critical micelle temperature.

The temperature dependence of the micelle structures formed by poly(styrene-b-isoprene) (SI) diblock copolymers in the selective solvents diethyl phthalate (DEP) and tetradecane (C14), which are selective for the PS and PI blocks, respectively, have been investigated by small angle neutron scattering (SANS). Two nearly symmetric SI diblock copolymers, one with a perdeuterated PS block and the other with a perdeuterated PI block, were examined in both DEP and C14. The SANS scattering length density of the solvent was matched closely to either the core or the corona block. The resulting core and corona contrast data were fitted with a detailed model developed by Pedersen and co-workers. The fits provide quantitative information on micellar characteristics such as aggregation number, core size, overall size, solvent fraction in the core, and corona thickness. As temperature increases, the solvent selectivity decreases, leading to substantial solvent swelling of the core and a decrease in the aggregation number and core size. Both core and corona chains are able to relax their conformations near the critical micelle temperature due to a decrease in the interfacial tension, even though the corona chains are always under good solvent conditions.

Journal Article↗

PubMed2004

Long-lived metastable bcc phase during ordering of micelles.

We report a metastable bcc phase that intervenes between a disordered micellar suspension and an fcc crystal in a block copolymer solution. Upon heating, the metastable bcc phase nucleates first, and then transforms over the course of hours to the stable fcc phase. At still higher temperatures, the fcc phase transforms to an equilibrium bcc phase. These results constitute an interesting experimental manifestation of Ostwald's step rule, and also support recent theory and simulation results whereby bcc nucleates more readily from a melt of spheres.

Journal Article↗

PubMed2004

Multicompartment micelles from ABC miktoarm stars in water.

By combining three mutually immiscible polymeric components in a mixed-arm star block terpolymer architecture, we have observed the formation of a previously unknown class of multicompartment micelles in dilute aqueous solution. Connection of water-soluble poly(ethylene oxide) and two hydrophobic but immiscible components (a polymeric hydrocarbon and a perfluorinated polyether) at a common junction leads to molecular frustration when dispersed in aqueous solution. The incompatible hydrophobic blocks form cores that are protected from the water by the poly(ethylene oxide) blocks, but both are forced to make contact with the poly(ethylene oxide) by virtue of the chain architecture. The structures that emerge depend on the relative lengths of the blocks and can be tuned from discrete multicompartment micelles to extended wormlike structures with segmented cores.

Butadienes↗

PubMed2004

Origin of the thermoreversible fcc-bcc transition in block copolymer solutions.

The thermoreversible fcc-bcc transition in concentrated block copolymer micellar solutions is shown to be driven by decreases in the aggregation number as the solvent penetrates the core, leading to a softer intermicelle potential. Small-angle neutron scattering measurements in a dilute solution are used to quantify the temperature-dependent micellar characteristics. The observed phase boundary is in excellent agreement with recent simulations of highly branched star polymers.

Journal Article↗

PubMed2003

Micellar shape change and internal segregation induced by chemical modification of a tryptych block copolymer surfactant.

We report the detailed characterization of micelles formed by two nonionic, amphiphilic ABC triblock copolymers. Poly(ethylene oxide)-b-poly(styrene)-b-1,2-poly(butadiene) (PEO-b-PS-b-PB) triblock copolymer "OSB" forms core-corona spherical micelles in aqueous solution, and the two hydrophobic blocks S and B are mixed homogeneously within the micelle core. PEO-b-PS-b-PB:C6F13I triblock copolymer "OSF" was prepared by selective fluorination of the B block in OSB with n-perfluorohexyl iodide. Fluorination of the B block induces internal segregation into an inner F core and an intermediate S shell. Furthermore, the strong incompatibility that results from fluorination drives a shape change into an oblate ellipsoid. These micellar morphologies are confirmed by combined light, neutron, and X-ray scattering measurements, as well as TEM imaging.

Journal Article↗

PubMed2002

Thermoreversible, epitaxial fcc<-->bcc transitions in block copolymer solutions.

Uncharged block copolymer micelles display thermoreversible transitions between close-packed and bcc lattices for a range of concentration, solvent selectivity, and copolymer composition. Using small-angle x-ray scattering on shear-oriented solutions, highly aligned fcc crystals are seen to transform epitaxially to bcc crystals, with fcc/bcc orientational relationships that are well established in martensitic transformations in metals. The transition is driven by decreasing solvent selectivity with increasing temperature, inducing solvent penetration of the micellar core.

Journal Article↗