WO1999047570A1 - Auto-assemblage macromolecuilaire de microstructures, nanostructures, objets et solides mesoporeux - Google Patents

Auto-assemblage macromolecuilaire de microstructures, nanostructures, objets et solides mesoporeux Download PDF

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WO1999047570A1
WO1999047570A1 PCT/US1999/005940 US9905940W WO9947570A1 WO 1999047570 A1 WO1999047570 A1 WO 1999047570A1 US 9905940 W US9905940 W US 9905940W WO 9947570 A1 WO9947570 A1 WO 9947570A1
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poly
rod
coil block
block copolymer
group
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PCT/US1999/005940
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English (en)
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Samson A. Jenekhe
X. Linda Chen
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University Of Rochester
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Priority to CA002324140A priority Critical patent/CA2324140A1/fr
Priority to EP99913954A priority patent/EP1064310A1/fr
Priority to AU31913/99A priority patent/AU742976B2/en
Publication of WO1999047570A1 publication Critical patent/WO1999047570A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to microstructures, nanostructures, objects, or mesoporous solids formed from rod-coil block copolymers.
  • the present invention also relates to methods of making microstructures, nanostructures, objects, or mesoporous solids.
  • Such mesostructures (1-10 5 nm) are of broad fundamental and applied interests not only in chemistry but also biology, physics, materials science, colloid science, and surface science, while also addressing societal concerns in health care, the environment, energy needs, and national security (Whitesides, Angew. Chem. Int. Ed. Engl.. 29:1209-1218 (1990)).
  • nanostructured assemblies of current block copolymers lack functionality and control of size, interfaces, order, and 3-D shape due to the inability to control the underlying non-covalent intermolecular interactions between the macromolecular building blocks (Whitesides et al., Science, 254: 1312-1319 (1991)).
  • Block copolymers can produce numerous phase-separated microstructures and nanostructures that are of wide scientific and technological interest (Muthukumar et al., Science. 277:1225-1232 (1997); Chen et al., Science. 277:1248-1253 (1997); Park et al., Science, 276:1401-1404 (1997); Bates, Science. 251 :898-905 (1991); Milner, Science. 251 :905-914 (1991); Fredrickson et al.. Annu. Rev. Mater. Sci.. 26:501-550 (1996); Halperin et al.. Adv. Polvm. Sci.. 100:31-71 (1992); Tirrell. Ace. Chem.
  • ordered mesoporous solids with nanoscale pore sizes are of interest in areas such as catalysis, sensors, size- and shape-selective separation media, adsorbents, and scaffolds for composite materials synthesis (Kresge et al., Nature. 359:710-712 (1992); Sayari, Chem. Mater.. 8:1840-1852 (1996); Huo et al., Chem. Mater.. 8: 1 147-1160 (1996); Zhao et al., Science. 279:548-552 (1998); Kramer et al., Langmuir, 14:2027-2031 ( 1998); Wiinhoven et al.. Science, 281 :802-804 (1998)).
  • photonic crystals or photonic band gap materials i.e., structures that can create and manipulate light signals precisely, transmitting certain wavelengths while blocking others.
  • Photonic crystals were first envisioned by Eli Yablonovitch more than a decade ago (Yablonovitch, J. Opt. Soc Am. B., 10:283-295 (1993)). In these crystals, composite materials are ordered so that light traveling through them is modulated in a highly controlled fashion.
  • Micelles of coil-coil block copolymers in a selective solvent for one of the blocks are spheres consisting of a dense core of the insoluble block and a diffuse corona of the solvated block (McConnell et al.. Phvs Rev. Lett., 71 :2102-2105 (1993); McConnell et al., Macromolecules, 28:6754-6764 (1995); McConnell et al,
  • Micellar crystallization into either an fee or a bec lattice is determined by the length scale and steepness of repulsive interactions that can be controlled by the ratio of the coronal layer thickness to the core radius (McConnell et al., Phvs Rev. Lett.. 71 :2102-2105 (1993); McConnell et al., Macromolecules. 28:6754-6764 (1995); McConnell et al..
  • the present invention relates to a method for producing microstructures, nanostructures. or objects. This method involves providing a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, mixing the rod-coil block copolymer and a selective solvent for one of the blocks which solubilizes that block, and permitting the rod-coil block copolymer to self-assemble into organized mesostructures with a region of the unsolubilized block and a region of the solubilized block.
  • the present invention also relates to a microstructure, nanostructure.
  • rod-coil block copolymer which includes a rigid-rod block and a flexible-coil block, wherein the rod-coil block copolymer forms an organized mesostructure with a region of one block and a region of the other block.
  • Another aspect of the present invention is a method for producing a mesoporous solid.
  • This method involves providing a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, mixing the rod-coil block copolymer and a selective solvent for the flexible-coil block which solubilizes that block, permitting the rod-coil block copolymer to self-assemble into organized mesostructures with a region of the unsolubilized block and a region of the solubilized block, evaporating the solvent, and permitting the organized mesostructures to self-organize into a mesoporous solid.
  • the present invention also relates to a method for producing a polymer adsorption layer on a substrate.
  • This method involves providing a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, mixing the rod-coil block copolymer and a selective solvent for one of the blocks to form a solution of rod-coil block copolymer and solvent, inserting a substrate into the solution, permitting the rod- coil block copolymer to adsorb to the substrate, and removing the substrate from the solution under conditions effective to form an adsorption layer of a polymer on the substrate.
  • Another aspect of the present invention is a substrate with a polymeric adsorption layer, wherein the adsorption layer is a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, wherein one of the blocks of the rod-coil block copolymer is adsorbed to the substrate.
  • the adsorption layer is a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, wherein one of the blocks of the rod-coil block copolymer is adsorbed to the substrate.
  • the present invention also relates to an optical article including a substrate, a transparent conductor foimed as a coating on the substrate, a polymeric adsorption layer including a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, wherein one of the blocks of the rod-coil block copolymer is adsorbed to the transparent conductor, and a coating formed on the surface of the adsorption layer, wherein the adsorption layer allows the emission of polarized light.
  • Another aspect of the present invention is a method for encapsulating guest molecules, macromolecules, or nanoparticles.
  • This method involves providing a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, mixing the rod-coil block copolymer with a selective solvent for one of the blocks which solubilizes that block to form a solution of rod-coil block copolymer and solvent, adding guest molecules, macromolecules, or nanoparticles to the solution, and permitting the rod-coil block copolymer to self-assemble into organized mesostructures with a region of the unsolubilized block and a region of the solubilized block under conditions effective to encapsulate the guest molecules, macromolecules, or nanoparticles within the mesostructure.
  • Yet another aspect of the present invention is an organized mesostructure with an encapsulated guest molecule, macromolecule, or nanoparticle which includes a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, wherein 10
  • the rod-coil block copolymer forms an organized mesostructure with a region of one block and a region of the other block and a guest molecule, macromolecule. or nanoparticle. wherein the guest molecule, macromolecule, or nanoparticle is encapsulated within the mesostructure.
  • the present invention also relates to a method for solubilizing guest molecules, macromolecules, or nanoparticles.
  • This method involves providing a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, mixing the rod-coil block copolymer with a selective solvent for one of the blocks which solubilizes that block to form a solution of rod-coil block copolymer and solvent, adding guest molecules, macromolecules. or nanoparticles to the solution, and permitting the rod-coil block copolymer to self-assemble into organized mesostructures with a region of the unsolubilized block and a region of the solubilized block under conditions effective to solubilize the guest molecules, macromolecules. or nanoparticles.
  • the rod-coil block copolymers of the present invention form robust, functional, structurally well-defined, three-dimensional nanostructures, microstructures, and objects.
  • the nanostructures. microstructures, and objects may be used for encapsulating guest molecules, macromolecules, or nanoparticles.
  • the nanostructures, microstructures, and objects may be used to form mesoporous solids, without a template, for use in various optical applications, tissue engineering and biomaterials. molecular electronic devices, optically tunable and responsive coatings, and the processing of "soft" colloidal materials.
  • the rod-coil block copolymers of the present invention may be used to form an adsorption layer of a polymer.
  • Figure 1 shows preferred rod-coil block copolymer architectures of the present invention.
  • Figure 2 shows preferred rigid-rod blocks for the rod-coil block copolymers of the present invention.
  • Figure 3 shows additional preferred rigid-rod blocks for the rod-coil block copolymers of the present invention.
  • Figure 4 shows preferred flexible-coil blocks for the rod-coil block copolymers of the present invention.
  • Figure 5 shows the synthetic scheme for the diblock copolymers PPQso-b-
  • PS 2 ooo PPQ 50 -b-PS 100 o, PPQ 5 o-b-PS 300 , PPQ ⁇ o-b-PS 130 , PPQ 10 -b-PS,ooo, PPQ ⁇ 0 -b-PS 30 o, and PPQ,o-b-PS, 30 (54a-g).
  • Figure 6 shows the synthetic scheme for the triblock copolymers PPQ 50 -b- PS 5 oo-b-PPQ 5 o, PPQ 50 -b-PS 25 o-b-PPQ 50 , and PPQ 50 -b-PS 12 o-b-PPQ 5 o (55a-c).
  • Figure 7 shows the chemical structure and schematic illustration of the self-assembly of poly (phenylquinoline)-Woc,* -polystyrene ("PPQ-b-PS”) rod-coil block copolymers into hollow aggregates.
  • PPQ-b-PS polystyrene
  • Figure 8 shows some relevant hydrogen-bonded structural motifs for influencing molecular packing and 3-D structure.
  • Figure 9 shows hydrogen-bonded layers and bilayers of AB rod-coil block copolymers which are structural motifs for self-assembly of 3-D structures.
  • Figure 10 shows hydrogen-bonded tapes for self-assembly of 3-D structures by ABA and BAB rod-coil block copolymers.
  • Figure 11 shows examples of rod-coil block copolymers.
  • Figure 12 shows the molecular structure of the rod-coil block copolymer
  • Figure 13 shows examples of self-assembly of rod-coil block copolymers at surfaces of substrates to form adsorption layers.
  • Figure 14 shows schematic illustrations of the self-assembly of rod-coil
  • Figures 15A-D show the optical ( Figures 15A to C) and scanning electron ( Figure 15D) micrographs of the typical morphologies of PPQ 5 o-b-PS 3 oo. Drops of dilute solutions (0.5 to 1.0 mg/ml) of the rod-coil block copolymers were spread and dried on glass slides and aluminum substrates, respectively.
  • FIG. 15 A spherical aggregates (1 : 1 TFA:DCM, v/v, 95 °C);
  • Figure 15B lamellae (1:1 TFA:DCM, 25 °C);
  • Figure 15C cylinders (9:1 TFA:DCM, 25 °C);
  • Figure 15D vesicles (1 :1 - 1 :4 TFA:DCM, 25 °C).
  • Figures 16A-F show optical ( Figure 16A and Figure 16C) and fluorescence (Figure 16B, Figure 16D-F) micrographs of the typical morphologies of PPQ 50 -b-PS 0 o (54c). Drops of dilute solutions (0.5 to 1.0 mg/ml) of the diblock copolymers were spread and dried on glass slides. Spherical aggregates (Figure 16A) under cross-polarizers, ( Figure 16B) fluorescence lamp (7:1 TFA:DCM.
  • Figures 17A-F show optical ( Figure 17A and Figure 17C-F) and fluorescence (Figure 17B) micrographs of the typical morphologies of diblock copolymer
  • FIGS 19A-B show photoluminescence (“PL”) emission and excitation
  • PL emission spectra are for 380- nm excitation, and PLE spectra were obtained by monitoring the emission peaks.
  • PL decay data are for 380-nm laser excitation in time-correlated single-photon counting experiments.
  • Figures 20A-F show optical and fluorescence micrographs of hollow spherical vesicles from triblock copolymers PPQ 5 o-b-PS 5 oo-b-PPQ 5 o (55a) ( Figure 20A, Figure 20B); PPQ 5 o-b-PS 25 o-b-PPQ 5 o (55b) ( Figure 20C, Figure 20D); PPQ 50 -b-PS 120 -b-
  • Figures 20E, Figure 20F Figures 20A. 20C and 20E were taken under cross-polarizers. The samples were prepared by allowing drops of dilute solutions (0.5 to
  • Figures 21A-F show optical and fluorescence micrographs of vesicles from diblock and triblock copolymers PPQ 5 o-b-PS o 0 -b-PPQ 5 o (55a) ( Figures 21A-D) and
  • Figures 21 A. 2 IE, and 21F were take under bright field.
  • Figure 21 C was taken under cross-polarizers.
  • Figures 21B and 2 ID were taken when excited with 400-nm light.
  • Figures 22 A shows schematic illustrations of the H-aggregates (Figure
  • FIG. 22A and J-aggregates (Figure 22B) formed by rod-coil block copolymers.
  • Figures 23A-B show Photoluminescence (PL) emission and excitation
  • PL emission spectra are for 380-nm excitation, and PLE spectra were obtained by monitoring the emission peaks.
  • PL decay data are for 380-nm laser excitation in time-correlated single-photon counting experiments.
  • Figures 24A-F show scanning electron micrographs of the spherical aggregates self-assembled from PPQ 50 -b-PS oo ( Figure 24A, Figure 24B, Figure 24E, Figure 24F) and PPQ ⁇ o-b-PS 3 oo ( Figure 24C, Figure 24D). All these aggregates were prepared by spreading dilute solution (0.1 wt%) with a solvent ratio TFA:DCM of 7/1 onto aluminum substrates (25°C).
  • Figures 25A-D show fluorescence photomicrographs of PPQ 50 -b-PS 3 oo aggregates as described in Figure 10: (Figure 25A) Spherical, ( Figure 25B) lamellar, (Figure 25C) cylindrical, and ( Figure 25D) vesicular aggregates.
  • Figures 26A-C show a fluorescence photomicrograph of PPQ-b-PS showing spheres (Figure 26A), lamellae (Figure 26B), and cylinders (Figure 26C).
  • Figure 27 shows examples of 3-D shaped objects that could be prepared by molecular self-assembly.
  • Figures 28A-F show scanning electron micrographs of the typical morphologies of triblock copolymers PPQ o-b-PS 0 o-b-PPQ 5 o (55a) ( Figure 28A, Figure 28B, Figure 28E); PPQ 5 o-b-PS 25 o-b-PPQ 5 o (55b) ( Figure 28C. Figure 28F); PPQ 50 -b- PS,2o-b-PPQ 5 o (55c) ( Figure 28D). Drops of dilute solutions (0.5 to 1.0 mg/ml) of the triblock copolymers (6:4 TFA:DCM, 25°C) were spread and dried on aluminum substrates ( Figures 28A-E) or a copper grid ( Figure 28F), respectively.
  • Figures 29A-D show TEM images of aggregates prepared from 5:5 TFA:DCM solutions at 20 °C.
  • Figure 29A PPQ, 0 -b-PS 30 o (54f);
  • Figure 29B PPQ 50 -b- PS 300 (54c);
  • Figure 29C PPQ 5 o-b-PS 500 -b-PPQ 5 o (55a);
  • Figure 29D PPQ 5 o-b-PS 250 -b- PPQ 50 (55b).
  • Figures 30A-C show optical micrographs of aggregates of PPQ 5 o-b-PS 3 o 0 containing 5 wt.% solubilized C 6 o.
  • Figure 30A shows a sample from 1 :1 TFA:DCM under bright field.
  • Figure 30B shows a sample from 1 :1 TFA:toluene under cross- polarizers.
  • Figure 30C shows a schematic illustration of the cross-section of a spherical block copolymer aggregate with encapsulated fullerene-C 6 o.
  • Figure 31 shows TGA thermograms of homopolymer PPQ and PS, diblock copolymers 54a-g, and triblock copolymers 55a-c obtained in flowing nitrogen with a heating rate of 10 °c/min.
  • Figure 32 shows ⁇ NMR shifts in ⁇ (ppm) of PPQ 50 -b-PS 50 o-b-PPQ 50 (55a) in deuterated nitrobenzene/GaCl 3 .
  • Figure 33 shows the FTIR spectrum of PPQ 10 -b-PS 300 (541) in NaCl disk.
  • Figure 34 shows the micellar solubilization of C 6 o and C 70 in TFA DCM or TF A/toluene when PPQ 5 o-b-PS 3 oo (54c) or PPQ ⁇ 0 -b-PS 300 (54f) was present.
  • Figures 35A-C show optical absorption spectra of solutions of (Figure 35A) pure PPQ 50 -b-PS 300 (1 : 1 TFA:DCM. 0.05 wt.%), (Figure 35B) 5 wt % C 60 / PPQso- b-PS 300 (1 :1 TFA:DCM, 0.05 wt.%), and (Figure 35C) C 60 in CS 2 (0.05 wt.%). Inset is the magnified spectrum of the 5 wt.% C 6 o/ PPQ 5 o-b-PS 3 oo in the region of 450-700 nm.
  • Figure 35 shows the optical abso ⁇ tion spectra of solutions of 5 wt.% C 7 o PPQ 5 o-b-PS 300 and 5 wt.% C 7 o/PPQ ⁇ o-b-PS 30 o (1 :1 TFA:DCM. 0.05 wt.%). Also shown for comparison are the spectra of C ⁇ o in CS 2 (0.05 wt.%) and pure PPQ 50 -b-PS 3 oo (l :l TFA:DCM, 0.05 wt.%).
  • Figure 37 show the normalized absorbance of fullerene-PPQ-PS solutions as a function of fullerene loading: ( Figure 37A) C 6 o-PPQ-PS system and ( Figure 37B) C 70 -PPQ-PS system.
  • the solvent is TFA/DCM (1/1, v/v).
  • Figure 38 shows fluorescence ( Figures 38A and B) and polarized optical (Figure 38C) micrographs of aggregates of PPQ o-b-PS 3 oo containing 0.1 wt.%) solubilized C70 and (Figure 38D) fluorescence optical micrograph of 0.1 wt.% C 60 in PPQ 5 o-b-PS 30 o.
  • Figure 39 shows Fluorescence ( Figures 39A and B) and polarized optical (Figure 39C) micrographs of aggregates of PPQ 50 -b-PS 3 oo containing 1 wt.% solubilized C 6 o prepared from 4: 1 TFA:toluene.
  • Figure 40 shows fluorescence ( Figures 40A and C) bright field ( Figure
  • Figure 41 shows bright field optical micrographs of films of PPQ 5 o-b-PS oo aggregates dried from solutions containing 8 wt.% ( Figure 41 A) and 10 wt.% (Figure 41B) C 60 .
  • Figure 42 shows the average diameters of spherical fullerene/PPQ-PS aggregates as a function of fullerene loading and block copolymer composition. The line is only a guide to eyes.
  • Figure 43 A shows DSC scans of PS homopolymer (1), pure C 6 o (2), and 3 wt.%) C 6 o/PPQ 5 o-b-PS 3 oo aggregates.
  • Figure 43 B shows DSC scans of 1 wt.% C 6 o dispersed in PS homopolymer. The inset is the scan magnified in the region 250K to 290K.
  • Figures 44A-C show PL and PLE spectra of spherical PPQ 5 o-b-PS 3 oo aggregates containing no C 60 (a), 1 wt.% C 60 ( Figure 44B) and 5 wt.% C 6 o ( Figure 44C).
  • the excitation wavelength for the PL spectra were 380 nm ( Figure 44A), 360 nm (curve 1) and 475 nm (curve 2) ( Figure 44B), and 475 nm ( Figure 44C).
  • the emission wavelengths monitored for the PLE spectra were 480 nm ( Figure 44A), 480 nm (curve 3) and 600 (curve 4) ( Figure 44B), and 600 nm ( Figure 44C).
  • Figure 45 shows a fullerene solubilization and encapsulation induced transformation of PPQ-PS rod-coil diblock copolymer chains in H-aggregates to J- aggregates.
  • Figures 46A-B shows TGA thermograms of block copolymer samples PPQ 50 -b-PS 30 o (54c) and PPQ ⁇ 0 -b-PS 300 (54f) and the PPQ and PS homopolymers at 10 °C/minute in N 2 .
  • Figures 47A-C show fluorescence photomicrographs of solution cast micellar films of PPQ*o-b-PS 3 oo obtained by ambient air drying of different rod-coil block solution concentrations in CS 2 : ( Figure 47A) 0.005 wt.%; ( Figure 47B) 0.01 wt.%; and ( Figure 47C) 0.05 wt.%. Arrows in B indicate regions of self-ordering.
  • Figures 48A-D show ( Figure 48A) Polarized optical and ( Figures 48B and C) SEM micrographs of microporous micellar films obtained from a 0.5 wt.% PPQso-b- PS 2 ooo rod-coil block copolymer solution by solution casting on a glass slide and an aluminum substrate, respectively. The SEM samples were coated with a 10 nm gold layer. The SEM image in 48B is the top view and that in 48C is of the same sample tilted 45° from the beam axis to reveal 3-D structure.
  • Figure 48D shows a variation of hole diameter (D), periodicity (p) and minimum wall thickness (h) of ordered microporous films with the number of PS repeat units in the rod-coil block copolymers.
  • Figures 49A-B show ( Figure 49 A) a polarized optical micrograph of a microporous micellar film of PPQ ⁇ 0 -b-PS 30 o obtained from a 0.5 wt % solution containing 16 -
  • FIG. 50A-B show the ( Figure 50A) PL emission (390-nm excitation) and PLE excitation (460-nm emission) spectra of a micellar film of PPQ ⁇ 0 -b-PS 30 o and of the same rod-coil block copolymer chains homogeneously dispersed (0.1 wt.%) in a poly(ethylene oxide) (PEO) film and ( Figure 50B) PL decay dynamics of the same samples in A when excited at 360 nm and monitored at 490 nm.
  • PEO poly(ethylene oxide)
  • the present invention relates to a method for producing microstructures, nanostructures. or objects.
  • This method involves providing a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, mixing the rod-coil block copolymer and a selective solvent for one of the blocks which solubilizes that block, and permitting the rod-coil block copolymer to self-assemble into organized mesostructures with a region of the unsolubilized block and a region of the solubilized block.
  • Preferred rod-coil block copolymer architectures for the present invention include AB rod-coil diblock and ABA rod-coil-rod triblock copolymers illustrated in Figure 1. where A denotes a rigid-rod block and B denotes a flexible-coil block.
  • Preferred rigid-rod blocks include polyquinolines (1) (Jenekhe et al., Science 279:1903-1907 (1998); Agrawal et al., Macromolecules 26:895-905 (1993), which are hereby incorporated by reference), polyquinoxahnes (2), poly(/?-phenylenes) (3, 4), poly(/ phenylene vinylenes) (5, 6), polypridines (7), poly(pyridine vinylenes) (8), poly(naphthylene vinylenes) (9, 10), polythiophenes (11), poly(thiophene vinylenes) (12), polypyrroles (13), polyanilines (14), polybenzimidazoles (15), polybenzothiazoles (16), polybenzoxazoles (17), and polybenzobisazoles (18-20) ( Figure 2).
  • Additional preferred rigid-rod blocks include aromatic polyamides (21-24), aromatic polyhydrazides (25-27), aromatic polyazomethines (28-30), aromatic polyesters (31-33), and aromatic polyimides (34) (Yang, Aromatic High Strength Fibers. Wiley-Interscience, New York, (1989), which is hereby inco ⁇ orated by reference) (Figure 3).
  • Preferred flexible-coil blocks include polystyrene (35, PS), poly( ⁇ -methyl styrene) (36, PMS), polyethylene oxide (37, PEO), polypropylene oxide) (38, PPO), poly(acrylic acid) (39, PAA), poly(methylacrylic acid) (40. PMAA), poly(2- vinylpyridine) (41, P2VP), poly(4-vinylpyridine) (42, P4VP), polyurethane (43. PU), - 17 -
  • poly(vinyl pyrrolidone) 44), poly(methyl methacrylate) (45, PMMA), poly(n-butyl methacrylate) (46. PBMA), polyisoprene (47, PI), poly(butadiene) (48, PB), poly(dimethylsiloxane) (49, PDMS), poly(styrene sulfonic acid) (50, PSSA), and sodium poly(styrene sulfonate) (51, PSSNa) (Webber et al., Solvents and Self-Organization of Polymers. Kluwer Academic, Dordrecht. (1996); Hamley, The Physics of Block Copolymers, Oxford University Press. Oxford, (1998), which is hereby inco ⁇ orated by reference) ( Figure 4).
  • Preferred selective solvents include those solvents or mixtures of solvents which are selective for only the parent rigid-rod polymer, only the parent flexible-coil polymer, and solvents or mixtures of solvents which dissolve only one block in a block copolymer.
  • a selective solvent is chosen by selecting a solvent from the list of solvents known in the art and commonly tabulated for the parent rigid-rod polymer and for the parent flexible-coil polymer (Brandrup et al., Polymer Handbook. 3 rd ed., Wiley-Interscience, New York, (1989), which is hereby inco ⁇ orated by reference) or mixtures of such known solvents for respectively the rigid-rod and flexible-coil polymers.
  • PPQ-PS-PPQ triblock copolymers poly(phenylquinoline) (PPQ)-W(9c ⁇ polystyrene (PS) (PPQ-PS) diblock copolymers
  • PQx-PS-PPQ triblock copolymers polyquinoxaline (?Qx)-block- polystyrene (PQx-PS) diblock copolymers.
  • preferred selective solvents for the rigid-rod block include trifluoroacetic acid ("TFA"), mixtures of TFA and dichloromethane, and mixtures of TFA and toluene.
  • Preferred selective solvents for rod-coil block copolymers comprising PS or PMS blocks include carbon disulfide (CS 2 ), 1 -nitropropane, ethylbenzene. cyclohexanone, and mixtures thereof.
  • Preferred selective solvents for rod-coil block copolymers comprising PEO, PAA, PMAA, PSSA, or PSSNa blocks include water, dioxane/water, formamide, N,N- dimethyl-formamide (“DMF”), ethanol, methanol, and mixtures thereof.
  • Preferred temperatures of the solution or surface where self-organization of the rod-coil block copolymer is to take place varies from 20 °C up to about 5-25 °C above the boiling point of the solvent. Typically, the self-assembly temperature is between room temperature (about 22-25 °C) and 100 °C.
  • Preferred concentrations of rod-coil block copolymer in solution at room temperature for self-assembly of nanostructures, microstructures, or objects include concentrations greater than the critical micelle concentration (cmc) or the critical vesiculation concentration (cvc).
  • the cmc (or cvc) of a block copolymer is the concentration below which the copolymer exists as individual molecules or chains in solution and above which it exists primarily as aggregated species, and typically has values of about 10 "8 to 10 "4 Molar or less (Tuzar et al.. Surface and Colloid Science. 15:1- 83 (1993); Weber et al.. Solvents and Self-Organization of Polymers. Kluwer Academic, Dordrecht (1996).
  • a preferred solution concentration for self-assembly of the rod-coil block copolymers of the invention is between 10 ⁇ 4 wt.% (0.0001 wt.%) to 10.0 wt.%> at room temperature. Evaporation of solvent from solutions initially at room temperature by ambient air drying or by the application of heat necessarily changes the initial solution concentration.
  • the rod-coil block copolymer has the diblock architecture: rod block m coil block n .
  • the rod-coil block copolymer has the triblock architecture: rod block m coil block n rod block m .
  • Preferred rod-coil block copolymers for use in the present invention are poly(phenylquinoline)- ⁇ /o -polystyrene ("PPQ-b-PS") (54a-g, Figure 5) and poly(phenylquinoline)-WocA polystyrene-6/oeA:-poly(phenylquinoline) ("PPQ-b-PS-b- PPQ”) (55a-c, Figure 6).
  • the poly (phenylquinoline) (1, PPQ) homopolymer is a conjugated polymer with high modulus and thermal stability, and found to exhibit liquid crystalline ordered phases in solution (Sybert et al., Macromolecules.
  • the polystyrene (35, PS) is a well-known non-photoactive and non-electroactive polymer, soluble in common organic solvents such as tetrahydrofiiran (THF), dichloromethane, carbon disulfide (CS 2 ), and chloroform.
  • PPQ-b-PS (54) and PPQ-b-PS-b-PPQ (55) represent amphiphilic rod-coil diblock ( Figure 5) and rod-coil-rod triblock copolymers ( Figure 6).
  • Amphiphilic PPQ-b-PS ( Figure 7) rod-coil block copolymers self-organize into robust, micrometer-scale, spherical, vesicular, cylindrical, and lamellar aggregates from solution.
  • the heterocyclic rigid-rod polyquinoline block of the rod-coil block copolymers allows tuning of their amphiphilicity. For example, through protonation or quarternization of the imine nitrogen (Sybert et al., Macromolecules. 14:493-502 (1981); Agrawal et al., Macromolecules, 26:895-905 (1993); Agrawal et al., Chem. Mater..
  • the rod-like block can be turned into a polyelectrolyte.
  • the ⁇ -conjugated nature of the rigid-rod block confers electroactive and photoactive properties (Sybert et al., Macromolecules, 14:493-502 (1981); Agrawal et al., Macromolecules. 26:895-905 (1993); Agrawal et al., Chem. Mater.. 8:579-589 (1996); Jenekhe et al.. Photonic and Optoelectronic Polymers.
  • the PPQ-b-PS copolymers in selective solvents for PPQ, form large aggregates with various mo ⁇ hologies (spheres, vesicles, cylinders, and lamellae) that can be observed by optical microscopy (OM).
  • the amide linkage at the rod-coil interface in each block copolymer chain provides a means of strong intermolecular interactions, through hydrogen bonding, that enhance the stability of self-organized structures. More specifically, secondary amide linkages (-NH-CO-) and their associated hydrogen bonding, when strategically placed, can limit the number of possible arrangement of molecules in space with respect to one another as has been successfully done in the field of crystal engineering of hydrogen- bonded solid state structures ( Figure 8) (MacDonald et al., Chem. Rev., 94:2383-2420 (1994), which is hereby inco ⁇ orated by reference). Amide linkages may be inco ⁇ orated at the interfaces in AB and ABA block copolymers as shown in Figures 1, 9, and 10.
  • the rod-coil block copolymers of the present invention are novel types of ultralarge micelles. colloids, microemulsions and macroemulsions that are thermodynamically stable, polymer surface modification, photoregulation of surface properties, novel molecular containers for encapsulation of large molecules or nanoparticles. novel self-assembled nanoporous/microporous materials for photonic band gap applications, separation membranes, scaffolds for tissue engineering, and photonic and optoelectronic materials.
  • the present invention further includes evaporating the solvent after permitting the rod-coil block copolymer to self-assemble into organized mesostructures with a region of the unsolubilized block and a region of the solublized block.
  • the rod-coil block copolymers of the present invention may be also be used as a compatibilizer in a method of making molecular composites and nanocomposites of flexible-coil polymers and rigid-rod polymers.
  • This method involves providing a solution of flexible-coil polymer and rigid- rod polymer and adding a rod-coil block copolymer of the present invention to the solution under conditions effective to form a substantially fine dispersion of the flexible- coil polymer and rigid-rod polymer.
  • the rod-coil block copolymers of the present invention function as compatibilizers of mixtures of rod-like and coil-like polymers by segregating to the - 21 -
  • rod-coil block copolymers of the present invention in this way to compatibilize mixtures of rigid-rod and flexible-coil polymers, blends, nanocomposites, and molecular composites with fine dispersion (smaller phase sizes) are obtained, leading to improved mechanical properties for structural applications and improved optical and transport (barrier) properties.
  • the present rod-coil block copolymers are thus useful means to control and stabilize the mo ⁇ hology and properties of blends, nanocomposites. and molecular composites of rodlike and coil-like polymers.
  • the present invention also relates to a microstructure, nanostructure, or object including a rod-coil block copolymer which includes a rigid-rod block and a flexible-coil block, wherein the rod-coil block copolymer forms an organized mesostructure with a region of one block and a region of the other block.
  • Another aspect of the present invention is an optical article including a microstructure, nanostructure or object which includes a rigid-rod block and a flexible- coil block, wherein the rod-coil block copolymer forms an organized mesostructure with a region of one block and a region of the other block and an optical component, wherein the microstructure, nanostructure or object is formed as a coating on the optical component.
  • the present invention also relates to a method for producing a mesoporous solid.
  • This method involves providing a rod-coil block copolymer comprising a rigid-rod block and a flexible coil block, mixing the rod-coil block copolymer and a selective solvent for the flexible coil block which solubilizes that block, permitting the rod-coil block copolymer to self-assemble into organized mesostructures with a region of the unsolubilized block and a region of the solubilized block, evaporating the solvent, and permitting the organized mesostructures to self-organize into a mesoporous solid.
  • Rod-coil block copolymers in a selective solvent for the coil-like polymer self-organize into hollow spherical micelles having diameters depending on the molecular weight and composition.
  • Long-range, self-ordering of the micelles produces highly iridescent periodic mesoporous materials (i.e., photonic crystals- structures that can create and manipulate light signals precisely, transmitting certain wavelengths while blocking others).
  • aggregation in a selective solvent for the flexible-coil block induces spontaneous micellization, forming thermodynamically stable large micelles (> 1 OOnm) which after solvent evaporation produce mesoporous membrane films (Figure 12).
  • the underlying mechanism which produces the periodic (ordered) mesoporous solid film appears to be a type of colloidal crystallization as the micellar particle density increases with increasing concentration due to evaporation. Further solvent evaporation after colloidal crystallization and lattice formation appears to be followed by interdigitation of the flexible coil chains of the corona layer. Investigation of the influence of composition and architecture on the properties of the micellar suspensions and of the mesoporous solids allows the tuning of the geometric and physical properties of these self-assembled periodic mesoporous materials which may find applications such as photonic crystals, separation membranes, drug delivery vehicles, and scaffold for tissue engineering.
  • Solution cast micellar films consist of multilayers of hexagonally ordered arrays of spherical holes whose diameter, periodicity, and wall thickness depend on copolymer molecular weight and composition. Addition of guest molecules, such as fullerenes. into the copolymer solutions in a selective solvent for the flexible-coil block also regulates the microstructure and optical properties of the mesoporous films.
  • micellar building blocks can be tailored through copolymer architecture and composition as well as the solution chemistry (McConnell et al., Phvs Rev. Lett.. 71 :2102-2105 (1993); McConnell et al., Macromolecules. 28:6754-6764 (1995); McConnell et al., Macromolecules. 30:435-444 (1997); McConnell et al., Phvs. Rev. E.. 54:5447-5455 (1996); Webber et al.. Solvents and Self-Organization of Polymers, Kluwer Academic. Dordrecht (1996); Webber, JL Phvs. Chem.
  • micellar building blocks and other colloidal particles By combining different micellar building blocks and other colloidal particles, self-assembly of very unusual periodic mesoscopic structures with tailorable functions is possible.
  • different micellar building blocks and colloidal particles can be inco ⁇ orated into the walls of the mesoporous solids produced by rod-coil block copolymers.
  • Suitable micellar building blocks include micelles from different rod-coil block copolymers and colloidal particles which include dendrimers, polymer lattices, inorganic semiconductor nanocrystals. such as TiO 2 , CdS, CdSe, GaAs, and PbS, silver colloids, gold colloids, and peizoelectric ceramic particles.
  • photonic band gap materials and their associated applications Yablonovitch, J.
  • micellar films and their self-assembly process may have uses in tissue engineering and biomaterials (Fendler, Membrane Mimetic Chemistry, Wiley, New York (1982), which is hereby inco ⁇ orated by reference), fabrication of molecular electronic devices (Carter, Ed.. Molecular Electronics II, Marcel Dekker, New York (1987), which is hereby inco ⁇ orated by reference), separation media, sensors, optically tunable and responsive coatings, and processing of "soft" colloidal materials.
  • Yet another aspect of the present invention is a method for tissue engineering. This method includes providing a mesoporous solid, adding a cell culture to the mesoporous solid, and allowing the cells to grow on the mesoporous solid under conditions effective to produce an organized tissue layer.
  • the present invention also relates to a method for producing a polymer adso ⁇ tion layer or "brush" on a substrate.
  • This method involves providing a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, mixing the rod-coil block copolymer and a selective solvent for one of the blocks to form a solution of rod- coil block copolymer and solvent, inserting a substrate into the solution, permitting the rod-coil block copolymer to adsorb to the substrate, and removing the substrate from the solution under conditions effective to form an adso ⁇ tion layer of a polymer on the substrate.
  • Preferred substrates include glass, plastics, metals, semiconductors (e.g., Si wafers with or without an oxide layer) glass coated with indium-tin-oxide (ITO) or aluminum or other metal, glass or plastic with a plasma treated surface, mica, patterned substrates, and chemical functionalized substrates.
  • the adso ⁇ tion layer of a polymer is an adso ⁇ tion layer of a rigid-rod polymer block of a rod-coil block copolymer ( Figure 13).
  • Another aspect of the present invention is a substrate with a polymeric adso ⁇ tion layer, wherein the adso ⁇ tion layer is a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, wherein one of the blocks of the rod-coil block copolymer is adsorbed to the substrate.
  • the adso ⁇ tion layer is a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, wherein one of the blocks of the rod-coil block copolymer is adsorbed to the substrate.
  • the present invention also relates to an optical article including a substrate, a transparent conductor formed as a coating on the substrate, an adsorption layer of a polymer including a rod-coil block copolymer including a rigid-rod block and a flexible-coil block formed on the transparent conductor, and a coating formed on the surface of the adso ⁇ tion layer, wherein the adso ⁇ tion layer allows the emission of polarized light.
  • Another aspect of the present invention is a method for encapsulating guest molecules, macromolecules, or nanoparticles.
  • This method involves providing a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, mixing the rod-coil block copolymer with a selective solvent for one of the blocks which solubilizes that block to form a solution of rod-coil block copolymer and solvent, adding guest molecules, macromolecules, or nanoparticles to the solution, and permitting the rod-coil block copolymer to self-assemble into mesostructures with a region of the unsolubilized block and a region of the solubilized block under conditions effective to encapsulate the guest molecules, macromolecules, or nanoparticles.
  • guest molecules are defined as molecules deliberately added that are not a solvent or the self-assembling rod-coil block copolymer.
  • Guest molecules may include oligomers which are defined as polymers including from about 2 to about 20 repeat units.
  • macromolecules are defined as polymers other than the self-assembling rod-coil block copolymer. Macromolecules are defined as polymers including from about 20 to about 5000 repeat units.
  • nanoparticles are defined as particles ranging from about 1 nm to about 100 nm.
  • Preferred guest molecules, macromolecules, or nanoparticles include fullerenes, carbon nanotubes, drug formulations, cosmetic formulations, metal particles, semiconductor particles, and magnetic particles.
  • the guest molecule is a fullerene, most preferably C 6 o or C 70 .
  • Spherical fullerenes i.e., C 6 o, C7 0
  • micellar aggregates Encapsulating phenomena associated with micellar aggregates (Halperin et al.. Adv. Polvm. Sci.. 100:31-71 (1992); Tuzar et al.. Surface and Colloid Science. 15: 1- 83 (1993); Weber et al., Ed., Solvents and Self-Organization of Polymers. Kluwer Academic. Dordrecht (1996); which are hereby inco ⁇ orated by reference) are enhanced in amphiphilic rod-coil block copolymers. In particular, it is possible to package guest molecules, macromolecules, or even nanoparticles. The reason for this is the large size, stability, and hollow cavity of these aggregates self-organized from rod-coil block copolymer systems.
  • Yet another aspect of the present invention is an organized mesostructure with an encapsulated guest molecule, macromolecule. or nanoparticle which includes a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, wherein the rod-coil block copolymer forms an organized mesostructure and a guest molecule, macromolecule, or nanoparticle. wherein the guest molecule, macromolecule, or nanoparticle is encapsulated within the mesostructure.
  • Another aspect of the present invention is a method for solubilizing guest molecules, macromolecules, or nanoparticles.
  • This method involves providing a rod-coil block copolymer including a rigid-rod block and a flexible-coil block, mixing the rod-coil block copolymer with a selective solvent for one of the blocks which solubilizes that block to form a solution of rod-coil block copolymer and solvent, adding guest molecules, macromolecules, or nanoparticles to the solution, and permitting the rod-coil block copolymer to self-assemble into mesostructures with a region of the unsolubilized block and a region of the solubilized block under conditions effective to solubilize the guest molecules, macromolecules, or nanoparticles.
  • Polystyrenes with mono- or di- carboxylic acid-terminated functional group (PS-COOH, HOOC-PS-COOH), which had a molecular weight (M w ) of 218400, 109200, 32760, 14200, respectively, for PS-COOH, and 54600, 27600, and 13100 for HOOC-PS-COOH, and a polydispersity (M w /M n ) of 1.05 (Scientific Polymer Products, Inc., Ontario), were used without further purification.
  • M w molecular weight
  • M w polydispersity
  • Reagents and solvents such as 4- aminoacetophenone, dichloromethane, toluene, trifluoroacetic acid, triethylamine, ethanol, ethyl acetate, diphenyl phosphate were purchased from Aldrich (Milwaukee, WI) and were used as received. m-Cresol was distilled under vacuum before use for the polymerization. 5-Acetyl-2-aminobenzophenone (52) was synthesized according to the method disclosed in Sybert. et al., Macromolecules, 14:493-502 (1981), which is hereby inco ⁇ orated by reference.
  • Polyethylene oxide) (PEO) (M vv of 5.000.000, M, v /M n -2.8) and polystyrene (M w of 6,000,000, M w /M n -1.2) were purchased from Polysciences, Inc. (Warrington. PA) and were used as received.
  • Mono-ketone methylene-terminated polystyrene (53a).
  • the end group modification reactions are exemplified by the experiment for the carboxylic acid-terminated PS with a M w of 32760.
  • a rapidly stirred solution of 100 g (3.18 mmol) of carboxylic acid terminated PS (PS-COOH) and 1.74 g (12.84 mmol) of 4-aminoacetophenone in 500 ml of toluene was heated at reflux for 24 hours in a 2-L flask equipped with a Dean-Stark trap. The solution was diluted with 500 ml of toluene and 100 ml of 5 % aqueous HCl solution was added.
  • the organic toluene layer was extracted twice with 100 ml 5 %> aqueous HCl solution, washed with water, and dried with anhydrous magnesium sulfate. The toluene was then removed and the functionalized polystyrene was dried in a vacuum oven at 60 °C for 12 hours.
  • the functionalized polystyrene (53a) was purified by twice redissolving in chloroform and precipitating into methanol. The yield was 85%>.
  • the end groups of mono-functionalized PS (PS-COOH) with a M w of 218400, 109200, and 14200, were similarly converted to ketone methylene functional units.
  • Diketone methylene-terminated polystyrene (53b).
  • the end group modification reactions are exemplified by the experiment for the dicarboxylic acid-terminated PS with M w of 54,600.
  • a rapidly stirred solution of 100 g (1.83 mmol) of dicarboxylic acid-terminated PS (HOOC-PS-COOH, M w 54,600) and 2.0 g (7.33 mmol) of 4-aminoacetophenone in 500 mL of toluene was heated at reflux for 24 hours in a 2-L flask equipped with a Dean-Stark trap.
  • the reaction solution was diluted with 500 mL of toluene and 100 mL of 5 % aqueous HCl solution was added.
  • the organic toluene layer was extracted twice with 100 mL of 5 % aqueous HCl solution, washed with water, and dried with anhydrous magnesium sulfate. The toluene was then removed by rotary evaporator and the functionalized polystyrene was dried in a vacuum oven at 60 °C for 12 hours.
  • the functionalized polystyrene (53) was purified by twice redissolving in chloroform and precipitating into methanol. The yield was 85 %.
  • the end groups of di-functionalized PS (HOOC-PS-COOH) with M w of 27600 and 13100 were similarly converted to diketone methylene functional units.
  • PPQ-Z>-PS block copolymers (PPQ 50 -b-PS 2 ooo, PPQ 50 -b-PS ⁇ 00 o, PPQso-b- PS 300 , PPQ 50 -b-PS 130 , PPQ,o-b-PS 10 oo, PPQ 10 -b-PS 30 o, and PPQ 10 -b-PS 130 (54a-54 )) were synthesized by copolymerization of 5-acetyl-2-aminobenzophenone (52) with PS-CONH- Ph-COCH 3 (53a) as shown in Figure 5.
  • 52 5-acetyl-2-aminobenzophenone
  • the copolymerization is exemplified by the preparation of PPQ 5 o-b-PS 3 oo (54c), as follows. 2.39 g (10 mmol) of 5-acetyl-2- aminobenzophenone (52) and 6.31 g (0.2 mmol) of PS-CONH-Ph-COCH 3 (53a) were added to a solution of 5 g of diphenyl phosphate (DPP) and 20 g of freshly distilled m- cresol in a cylindrical glass flask fitted with a mechanical stirrer, two gas inlets, and a side arm. The reactor was purged with argon for 10 minutes before the temperature was raised slowly to 140 °C in 2-3 hours.
  • DPP diphenyl phosphate
  • the degree of polymerization of the PPQ block (N A ) in the rod-coil diblock (A A B B ) was controlled by the stoichiometric method. Because the condensation reaction yields of copolymerization were 100%, the polydispersity (M w /M n ) of the PPQ blocks was estimated to be around the theoretically expected value of 2 (Odian, Principles of Polymerization. 2nd ed.. Wiley. New York,
  • the diblock copolymers of PPQ 50 -b-PS 2 ooo (54a), PPQ 50 -b-PS ⁇ ooo (54b), PPQ 50 -b- PS 130 (54d), PPQ 10 -b-PS 10 oo (54e), PPQ 10 -b-PS 30 o (54f), and PPQ 10 -b-PS 130 (54g) were similarly prepared.
  • Poly (phenylquinoline)-b-polystyrene-b-poly(phenylquinoline) triblock copolymers 55.
  • PPQ- ⁇ -PS- ⁇ -PS triblock copolymers PPQ 50 -b-PS 50 o-b-PPQ 5 o, PPQso-b-
  • PS 25 o-b-PPQ 5 o, and PPQ 50 -b-PS ⁇ 2 o-b-PPQ 5 o (55a-c)) were synthesized by block copolymerization of 5-acetyl-2-aminobenzophenone (52) with 53b (CH 3 CO-Ph-NHCO- PS-CONH-Ph-COCH 3 ), as shown in Figure 6.
  • the copolymerization is exemplified by the preparation of PPQ 5 o-b-PS 500 -b-PPQ 5 o (55a), as follows.
  • the bright orange solution product was cooled and precipitated into 500 mL of 10 % triethylamine/ethanol mixture to wash away the w-cresol and DPP.
  • the final product was purified by Soxlet extraction with 10 %> triethylamine/methanol for 48 hours to get rid of the residue w-cresol, DPP, and the un-reacted homopolymer PS, because homopolymer PS can dissolve in hot methanol.
  • the degree of polymerization of the PPQ block (N A ) in the rod-coil triblock copolymers (A NA B NB A NA ) was controlled by the stoichiometric method.
  • copolymers of PPQ 50 -b-PS 25 o-b-PPQ 5 o (55b) and PPQ 50 -b-PS, 2 o-b- PPQ 50 (55c) were similarly synthesized.
  • DSC DuPont Model 2100 Thermal Analyst based on an IBM PS/2 Model 60 computer and equipped with a Model 951 TGA unit and a Model 910 DSC unit.
  • the DSC thermograms were obtained in nitrogen at a heating rate of 5°C/minute.
  • the TGA data were obtained in flowing nitrogen at a heating rate of 10°C/minute.
  • ⁇ NMR spectra were taken at 300 MHz, using a General Electric Model QE 300 instrument.
  • Block copolymer solutions for ⁇ NMR spectroscopy were prepared in a dry box, using deuterated nitrobenzene(C 6 D 5 NO?) containing gallium chloride.
  • FTIR Fourier transform infrared
  • Samples for observation by polarized optical microscopy (POM) and fluorescence microscopy (FM) were prepared by allowing several drops of a block copolymer solution in TFA:DCM or TFA:toluene to spread and dry on glass slides.
  • the various drying conditions explored are described below and were found not to influence the observed mo ⁇ hologies of aggregates (size, shape, and their distributions).
  • Observations were done on an Olympus Model BX60 Fluorescence Optical Microscope.
  • the glass slides were placed under an optical fluorescence microscope.
  • Optical (bright field, polarized light) and fluorescence images were recorded by a digital camera with 0.5 inches CCD chips. The images were stored and processed by a PC computer equipped with Image Pro. (Media Cybernetics, Silver Spring, MD) software.
  • Samples for scanning electron microscopy were prepared by allowing several drops of a copolymer solution to spread and dry on aluminum substrates. The samples were then coated with a thin layer of 100 A gold.
  • Photoluminescence (PL) and photoluminescence excitation (PLE) spectra were obtained on a Spex Fluorolog-2 spectrofluorimeter. Time -resolved fluorescence spectra were obtained by using a single-photon-counting technique.
  • the solutions of the aggregates were similarly sealed inside a 1 -mm-path-length quartz cuvet. Thin films and solutions of aggregates were measured by using the front face geometry in which samples were positioned such that the emission was detected at 22.5° from the incident radiation beam. Further details of the photophysical experimental techniques used here are similar to those we have described in detail elsewhere (Osaheni et al., J. Am. Chem. Soc, 1 17:7389-7398 (1995), which is hereby inco ⁇ orated by reference).
  • Example 1 was done using various ratios of trifluoroacetic acid (TF A)/dichloromethane (DCM) and TF A/toluene, which are good selective solvents for the rigid-rod block.
  • TF A trifluoroacetic acid
  • DCM dichloromethane
  • TF A/toluene good selective solvents for the rigid-rod block.
  • the rigid-rod PPQ block was protonated and solvated by the TFA. forming a rod-like polyelectrolyte block in solution. Drying drops of dilute solutions (0.5 to 1.0 mg/ml) of PPQ-b-PS on substrates produced micelle-like aggregates because DCM and toluene, which are selective solvents for the PS block, had faster evaporation rates than TFA which is a selective solvent for the rigid-rod block.
  • TFA Dilute solutions (0.5 to 1.0 mg/ml) of each rod-coil block copolymer in mixed solvents.
  • PPQ blocks essentially were transformed to polyelectrolytes with positive charges. The electrostatic forces between protonated PPQ blocks and the surrounding negative counter-ions were expected to help stabilize the colloidal structures, just as the charged protein helps stabilize the natural rubber latex.
  • Rod- coil-rod triblock copolymers can either fold to form single loop-layers, or they can form bilayer tape-like structures as shown in Figure 14. Therefore, in selective solvents for the rigid rod blocks, triblock copolymers are expected to either form micelles from single loop-layers as diblock copolymer did, or form vesicles from bilayer tape-like structures ( Figure 14).
  • the self-assembly of a rod-coil block copolymer in a selective solvent for the rigid-rod block has not been theoretically investigated (Semenov et al, Sov. Phys. JETP.
  • Spherical aggregates with a wide distribution of sizes were observed by rapid drying of solutions on a heated substrate at 95 °C and by preparing aggregates from solutions from a TFA/DCM ratio of 4/1. Further reducing the TFA DCM ratio resulted in two more phases.
  • Relatively flat (2D) lamellae with rough surfaces having diameters in the range of 5 to 30 ⁇ m together with minor phase-donut-shape rings ( ⁇ 20%>) were obtained from a solution with a solvent ratio of 1 : 1.
  • Aggregates prepared by drying solutions at room temperature had non-spherical mo ⁇ hologies, and each sample was predominantly (-70%) either lamellae, cylinders, or vesicles depending on the initial solvent composition; the minor phases in these mo ⁇ hologies were cylinders, lamellae, or spheres, respectively.
  • Lamellar aggregates had diameters in the 5 to 30 ⁇ m range, the cylinders were relatively uniform in diameter (1 to 3 ⁇ m) but highly polydisperse in length (5 to 25 ⁇ m), and vesicles had outer diameters of about 0.5 to 1.0 ⁇ m and wall thickness of about 200 nm. Similar multiple mo ⁇ hologies were observed in aggregates prepared from other diblock copolymers, with average sizes of the aggregates depending on the molecular weight of the block copolymers (Table 1). 35
  • the number inside bracket is the average sizes.
  • Figure 17 shows some representative mo ⁇ hologies self-assembled from copolymer 54b ( Figures 17A and 17B), 54e ( Figure 17C), 54f ( Figures 17D), and 54g ( Figures 17E and 17F).
  • Spherical aggregates with sizes ranging from 1 - 20 ⁇ m were obtained from PPQ 50 - b-PSiooo (54b, Figure 17A), which was bigger than those from PPQ 50 -b-PS 3 oo (54c) by a factor of about 2 ( Figures 16A and B).
  • Cylindrical aggregates prepared from PPQ 5 o-b- PSiooo (54b, Figure 17B) had a diameter of 2 ⁇ m. and length of 2-20 ⁇ m, with diameter - 36 -
  • the aggregation number, N 0 or number of rod-coil block copolymer chains per aggregate, was estimated to be 1.5 x 10 8 for a hollow sphere with diameter of 5 ⁇ m. assuming the density of the spherical aggregates is 0.14 g/cm 3 .
  • the aggregation number for cylindrical aggregates with diameter of 1 ⁇ m and length of 10 ⁇ m was similarly estimated to be 3x10 8 .
  • the aggregation number N 0 can also be estimated by the amount of the copolymers consumed for construction of various aggregates.
  • PL emission and excitation spectra were observed for spherical, lamellar, and cylindrical aggregates self-assembled from diblock copolymers 54a-54g (54c, Figure 19) and vesicles from triblock copolymer 55a-55c.
  • PLE and PL spectra of PPQ homogeneously dispersed in poly(ethyl oxide) (PEO) matrix were also obtained.
  • the PL spectrum of PPQ/PEO solid solution gave rise to an emission band centered at 460 nm, which was assigned to PPQ single-chain emission.
  • the corresponding PLE spectrum when monitored at 460 nm, gave rise to an abso ⁇ tion band centered at 390 nm, which was identical to the abso ⁇ tion spectrum obtained from UN -vis experiments.
  • Spherical aggregates from diblock copolymers exhibited a blue emission band centered at 454 nm, whereas the PLE spectrum showed an abso ⁇ tion band with a peak at 388 nm, slightly blue-shifted to the emission from the PPQ single chain.
  • both lamellar and cylindrical aggregates from diblock and vesicles from triblock copolymers had broad emission bands with peaks at 576, 594 nm, and 610nm. respectively, and PLE spectra of those when monitored at emission peaks gave rise to spectra which were totally different to the PLE spectrum of PPQ/PEO solid solution.
  • the PLE spectra showed a peak at 422 nm and a shoulder peak at 406 nm and -460 nm.
  • the extensive mo ⁇ hology studies of aggregates revealed that all the aggregates had highly ordered crystalline structures ( Figures 16. 17, 20. and 21), suggesting that in all these aggregates, a high degree of ordered packings of PPQ blocks took place.
  • the PL and PLE spectra showed that the PPQ blocks in spherical aggregates self-assembled from diblock copolymers formed H-aggregates, whereas the PPQ blocks in cylindrical, lamellar, donut-ringlike aggregates from diblock copolymers and vesicles from triblock copolymers formed J- aggregates (Shimomura et al., J. Am. Chem. Soc. 109:5175-5183 (1987), which is hereby inco ⁇ orated by reference).
  • the slight differences in PL and PLE spectra of the J- aggregates could be caused by the differences in tilted angles of the PPQ blocks ( Figure 22).
  • Figure 24 shows the SEM of the spherical aggregates from diblock copolymer 54c ( Figures 24A, 24B, 24E, 24F) and 54f ( Figures 24C. 24D) prepared from TFA/DCM (7/1, v/v) solutions with copolymer concentration of 0.5 wt.%o.
  • Spherical aggregates with wide size distribution, with size in the range of 1-10 ⁇ m were observed for copolymer 54c, whereas the spherical aggregates from 54f had typical sizes in the range of 0.5-5 ⁇ m.
  • Figure 24E shows a spherical aggregate prepared from copolymer 54c with a defect hole, and the magnified version of defect area of Figure 24E is shown in Figure 24F. That the spherical aggregate is indeed hollow inside and can be seen clearly, consistent with the proposed model for the spherical aggregates.
  • FIG. 20 shows the polarized optical micrographs and fluorescence micrographs of triblock copolymers (55a, 55b, and 55c) prepared from TFA/DCM solutions with triblock copolymer concentration of 0.1 wt.%o. All of the samples were prepared by spreading the solvents on hot glass substrates (90 °C).
  • Spherical aggregates self-assembled from triblock copolymer PPQ 5 o-b-PS2 5 o-b-PPQ 5 o (55b) had much narrower size distribution, with typical sizes in the range of 10 - 20 ⁇ m (90%)), and the minor phase was very small spherical aggregates with sizes from 1 ⁇ m to 5 ⁇ m (10%>), giving an average size of 16 ⁇ m.
  • Triblock copolymer PPQ 50 -b-PS ⁇ 2 o-b- PPQ 50 (55c) also arranged as spherical aggregates in solid state, with sizes ranging from 1 - 5 ⁇ m, with structures having severe defects with many holes developed in the micelles.
  • the spherical aggregates from copolymers PPQ 5 o-b-PS 5 oo-b-PPQ5o and PPQ 50 - b-PS 25 o-b-PPQ 5 o (55a and 55b) formed similar sizes arranged closed-packed in substrates in a hexagonal manner. All the spherical aggregates (with or without defects) had highly ordered structures, as indicated in images taken under cross polarizers ( Figures 20A, 20C, and 20E).
  • the aggregation number for each aggregate was also estimated. For 55a,
  • 0.5-g solution with copolymer concentration of 0.1 wt.% can cast a film with area of 2 cm " .
  • average density of the micelles with typical diameter of 30 ⁇ m was about 1.5 x 10 4 /cm 2 . Therefore the aggregation number was calculated to be 3.3 x 10 10 .
  • the aggregation number can also be estimated from density. Assuming the micelle has 90 %> porosity, the density of the micelles is close to 0.14 g/cm . As the volume for each micelle is 1.4 xlO ⁇ m J , aggregation number will be 1.5 xlO , very close to that estimated from the other method (see above).
  • FIG. 28 shows the SEM micrographs of triblock copolymers 55a, 55b and 55c prepared from TFA DCM solutions with triblock copolymer concentrations of 0.5 wt.%). All the samples were prepared by slowly evaporating the solvents at room temperature.
  • Triblock copolymer PPQso-b-PS ⁇ o-b-PPQso (55c) also arranged as spherical ' micelles in solid state; however, severe defects, such as holes with sizes ranging from 0.5 ⁇ m to 1 ⁇ m, developed all through the structures (Figure 28D).
  • Figures 28E and 28F show the SEM micrographs of broken spherical aggregates from copolymers 55a and 55b, respectively. The microcavity inside the spherical micelles was clearly revealed.
  • the wall thickness of the aggregate prepared from PPQ 5 o-b-PS 5 oo-b-PPQ 5 o (55a) varied from 340 nm to 1100 nm, whereas the wall thickness varied from 250 nm to 540 nm for copolymer PPQ 50 -b-PS 25 o-b-PPQ 5 o (55b). Because the extended lengths for copolymer 55a and 55b were 180 nm and 120 nm, respectively, it appeared that the wall of the aggregates needed to be at least 2 to 6 extended copolymer molecules in order to reach the necessary thickness.
  • Spherical aggregates from solutions with lower copolymer concentrations were also prepared. SEM studies of these samples revealed that spherical aggregates in the range of 200 nm to 1000 nm were also present, coexisting with the aggregates with sizes larger than 1 ⁇ m. About 5-10 % of the spheres whose sizes were in the range of 100 to 1000 nm were observed in the sample prepared from 0.1 and 0.5 wt.% solutions. In samples prepared from 0.01 wt.%> solution, the numbers of the spherical aggregates with sizes in the range of 200 to 1000 nm increased to almost 20 %>.
  • the spherical aggregates self-assembled from triblock copolymers could not be similarly explained as aggregates with inner-shell PS/outer-shell-PPQ as diblock copolymer could.
  • the main difficulty was in the discrepancy of the wall thickness. If the triblock copolymer folds over and forms a loop-single layer, because the lengths of the triblock copolymers were all less than 180 nm, spherical aggregates with at most 90-nm thick walls would be expected.
  • extensive studies revealed that the wall thickness varied from 250 nm to 1 100 nm. indicating several layers were present and constituted the wall.
  • the spherical aggregates self-assembled from triblock copolymers were vesicles which had one or several bilayer structures forming the wall.
  • a large portion of triblock copolymers may have folded to form a single layer, serving as the curvature-inducing factor to let bilayers form vesicles instead of lamellae (Szleifer et al.. Proc Natl. Acad. Sci. USA. 95:1032-1037 (1998); Safran et al.. Science, 248:354-356 (1990); Dan et al., Europhvs. Lett..
  • TEM Transmission electron microscopy
  • Figure 29 shows typical TEM images from diblock copolymer PPQ ⁇ o-b-PS 00 (54f) ( Figure 29A), PPQ 5 o-b-PS 300 (54c) ( Figure 29B) and triblock copolymer PPQ 50 -b- PS 250 -b-PPQ 5 o (55a) ( Figure 29C) and PPQ 50 -b-PS 50 o-b-PPQ 50 (55b) ( Figure 29D).
  • Spherical aggregates prepared from diblock PPQ ⁇ o-b-PS 3 oo (54f) and PPQ 5 o-b-PS 30 o (54c) in the range of 100 to 100 nm were clearly revealed in Figures 29A and 29B, whereas spherical aggregates with sizes varying from 150 nm to 800 nm were shown in Figures 29C and 29D. Based on this information, it seemed that the molecular packing in diblock and triblock copolymer was different, as evidenced from Figure 29A and Figure 29D. The spherical aggregates from triblock copolymers were more structured; a concentric ring-like image was revealed in TEM. It also seemed that folding did occur in triblock copolymers.
  • the smallest size of the vesicles shown in Figures 29C and 29D was about 150 nm. Because the fully extended length for triblock PPQ 0 -b-PS oo-b-PPQ 5 o (55a) and PPQ 5 o-b-PS 25 o-b-PPQ 5 o (55b) was about 180 nm and 120 nm, respectively, the results suggested that the folded loop-single layer (Figure 14) was the main building unit for the vesicles ( ⁇ 600 nm).
  • TGA thermograms of the rod-coil block samples are shown in Figures 30 and 31. TGA thermograms of the PPQ and PS homopolymers were also obtained for comparison. The decomposition temperatures of PPQ and PS were 600 °C and
  • thermograms of the block copolymers showed a two-step decomposition in flowing N 2 .
  • the onset of the first thermal decomposition of the rod-coil blocks was 420 °C for 54c and 54d, 400 °C for 54a, 54b, 54e-54g, and 410 °C for 55a- 55c, which was assigned to the decomposition of the flexible-coil PS block. ( Figures 31A and 3 IB).
  • the slightly improved thermal stability of the PS block in the rod-coil block copolymers compared to the parent PS homopolymer can be understood as a consequence of the tethering of the former chains onto rigid-rod chains.
  • the DSC thermograms of the rod-coil block copolymers, and those of the two parent homopolymers were also obtained.
  • PS homopolymer had a glass transition temperature (T g ) at 100 °C. No crystalline melting or T a was observed in PPQ before reaching its decomposition, consistent with the excellent thermal stability and high modulus of rigid rod-like conjugated polyquinolines.
  • the DSC thermograms of the diblock copolymers 54a-54g were essentially supe ⁇ ositions of those of the two parent homopolymers. exhibiting only a glass transition at 100 °C. However, the DSC thermograms of triblock copolymers 55a-c behaved quite differently.
  • the DSC thermograms of PPQ 5 o-b-PS 5 oo-b-PPQ 5 o (55a) and PPQ 50 -b-PS 25 o-b-PPQ 5 o (55b) in the first scan showed a second-order transition with temperature at 114 °C. and subsequent scans of the samples were identical to those of the initial scans.
  • the DSC thermogram of PPQ 5 o-b-PS ⁇ 2 o-b-PPQ 5 o (55c) showed a straight line from -50 to 400 °C; no discernible transition was observed. Compared to polystyrene homopolymer.
  • Protons of the side group phenyl ring appeared at 7.5 ppm, overlapping with the signals from the nitrobenzene solvent.
  • Protons of the PS block had resonances at 7.3-7.4 and 6.7-6.8 ppm, assigned to the phenyl ring, and at 1.5-1.6 and 2.2 ppm due to resonances of the protons of the methylene units.
  • FTIR spectra were also obtained as an independent check for the molecular structure of the rod-coil block copolymers.
  • Figure 33 The FTIR spectra of the rod-coil block copolymer samples were essentially supe ⁇ ositions of the spectra of the parent PS and PPQ homopolymers. There were significant differences between the vibrational spectra of PS and PPQ homopolymers and hence their contributions to the FTIR spectra of the block copolymers 54a-g and 55a-c. For example, the vibrational bands at 2922 and 2949 cm "1 , which can be assigned to aliphatic C-H stretching in PS, were absent in the FTIR spectrum of PPQ homopolymer.
  • Vesicles foimed from triblock copolymer PPQ 5 o-b-PS 5 o 0 -b-PPQ 5 o (55a) had size ranges of 5 ⁇ m to 120 ⁇ m ( Figures 21C, 2 ID, and 2 IE), whereas vesicles from copolymer PPQ 5 o-b-PS 25 o-b-PPQ 5 o (55b) ( Figure 2 IF) and PPQ 5 o-b-PSi2o-b-PPQ 5 o (55c) had sizes in the range of 1 to 100 ⁇ m. and 1 to 15 ⁇ m, respectively.
  • vesicles from triblock copolymers PPQ 5 o-b-PS 5 oo-b-PPQ 50 (55a) and PPQ 5 o-b-PS 25 o-b-PPQ 5 o (55b) were perfect; no flat or elongated shapes were observed.
  • vesicles from copolymer PPQso-b-PS ⁇ o-b-PPQso (55c) had severe deformities in the structures, with holes developed all through the structures. All the vesicles (with or without defects) seemed to have highly ordered structures, as evidenced by the images taken under cross polarizers ( Figure 21C). All these results were consistent with the observation from the samples in solid state.
  • the two copolymer compositions of poly(phenylquinoline)-W ⁇ cA- polystyrene used in this study, denoted here as PPQ 50 -b-PS 3 oo (54c) and PPQ ⁇ o-b-PS 30 o (54f). were synthesized by coupling functionalized polystyrene (PS) with the PPQ monomer.
  • PS polystyrene
  • 5-acetyl-2-aminobenzophenone Sybert et al., Macromolecules. 14:493-502 (1981). which is hereby inco ⁇ orated by reference
  • the starting monofunctionalized PS had a reported number average degree of polymerization of 300 and a polydispersity of 1.05 (Aldrich.
  • the number average degree of polymerization of the PPQ blocks was determined from ⁇ NMR spectra, thermal analysis, and other data.
  • Poly(ethylene oxide) (PEO) (M w of 5.000.000, M w /Mnch -2.8), poly(methyl methacrylate) (M w of 350,000, M w /M n -1.15) and polystyrene (M w of 6,000,000, M w /M n -1.2) were purchased from Polysciences, Inc. (Warrington, PA) and were used as received.
  • Copolymer solutions of PPQ-&-PS block copolymers (PPQ5o-b-PS 0 o (54c) and PPQ ⁇ o-b-PS 0 o (54f)) (0.5 to 1 mg/ml) used for the solubilization studies were prepared by dissolving each copolymer in various TFA/DCM or TF A/toluene mixtures of 9/1, 7/1, 1/1, and 1/4 solvent volume ratios. The resulting solutions had concentrations of 0.35 to 3.5 mg/ml (0.05 to 0.5 wt.%>) of diblock copolymers.
  • fullerene/copolymer solutions were prepared by adding know amounts of solid polymer and fullerene to the binary TFA DCM or TF A/toluene at the same time to achieve solutions with similar concentrations.
  • Fullerene/copolymer solutions were also prepared by mixing a solution of fullerene in DCM or in toluene with a pre-made copolymer solution. Different weight ratios of fullerene to copolymer were employed, ranging from 0.1 to 50 wt.%>.
  • fullerene/copolymer solutions were then stored for at least 2 days to equilibrate before assessment of solubilization and preparation of fullerene/block copolymer aggregates.
  • Films (-1 to 20 ⁇ m thick) resulting from drying the dilute solutions of block copolymer/solubilized fullerenes on glass slides at room temperature were investigated as made, or after treating them in 5 % triethylamine/ethanol (to remove any trace acids), and drying in a vacuum oven at 60 °C for 24 hours.
  • the films were investigated by polarized optical and fluorescence microscopies as well as by UN-Vis abso ⁇ tion and photoluminescence spectroscopies.
  • Abso ⁇ tion spectra of solutions (0.1 wt.%) of fullerene C 6 o and C7 0 in CS 2 were obtained using a quartz cuvet which was sealed by wax to prevent solvent evaporation. Abso ⁇ tion spectra of the pure PPQ 5 o-b-PS 3 oo (54c) and PPQ ⁇ o-b-PS 30 o (54f) were similarly obtained in 1 :1 TFA:DCM solutions at 0.1 wt.% which was orders of magnitude larger than their cmc. These were used as the reference spectra for comparing the abso ⁇ tion spectra of solubilized fullerene/block copolymer micelles.
  • the UV-Vis abso ⁇ tion spectra of all fullerene/PPQ-PS dispersions were obtained in a 1-mm cuvet at room temperature (25 °C) and were used to estimate the solubilization capacities of the fullerene/PPQ-PS systems.
  • the absorbance of each UV-Vis spectrum was normalized at a characteristic C 60 or C 70 abso ⁇ tion band.
  • the normalized absorbance was then plotted as a function of the amount of fullerene added to a dispersion.
  • the saturation of the normalized absorbance versus fullerene loading provided an estimate of the maximum amount that was solubilized.
  • Samples for observation by polarized optical microscopy (POM) and fluorescence microscopy (FM) were prepared by allowing several drops of a fullerene/block copolymer solution in TFA:DCM or TFA:toluene to spread and dry on glass slides.
  • the various drying conditions explored were described above and were found not to influence the observed mo ⁇ hologies of aggregates (size, shape, and their distributions). Observations were made on an Olympus Model BX60 Fluorescence Optical Microscope and optical (bright field, polarized light) and fluorescence images were recorded by a digital camera.
  • Photoluminescence (PL) and photoluminescence excitation (PLE) spectra were obtained on a Spex Fluorolog-2 spectrofluorimeter. Thin films of aggregates were measured by using the front face geometry in which samples were positioned such that the emission was detected at 22.5° from the incident radiation beam. Further details of - 54 -
  • the DSC thermograms were obtained on a Du Pont Model 2100 Thermal Analyst based on an IBM PS/2 Model 60 computer and equipped with a Model 910 DSC unit. The DSC thermograms of samples were obtained in nitrogen at a heating rate of 10 °C/min. Samples for DSC measurements were prepared by casting films of fullerene/PPQ 5 o-b-PS 30 o (54c) solutions in TFA/DCM (1/1, v/v) onto glass slides and carefully removing vacuum dried fullerene-containing aggregates from glass slides into DSC sample pans by using a sha ⁇ razor blade. Before the aggregates were removed from the glass slides, they were observed by an optical microscope to ascertain their spherical micellar mo ⁇ hology. In the case of fullerene/polystyrene and fullerene/poly(methyl methacrylate) samples, drops of solutions in CS 2 were dried directly in aluminum DSC pans.
  • Figure 35 shows the abso ⁇ tion spectra of TFA DCM solutions of pure PPQ 5 o-b-PS 300 (54c) ( Figure 36A), PPQ 50 -b-PS 30 o (54c) with 5 wt % C 60 ( Figure 35B), together with the spectrum of pure C 6 o in CS 2 ( Figure 35C).
  • the spectrum of C 60 /PPQ 5 o- b-PS 3 oo blend solution showed abso ⁇ tion bands characteristic of the two components, C 6 o and the diblock copolymer PPQ 5 o-b-PS 3 oo (54c).
  • the abso ⁇ tion band in the 370-460 nm region with maxima at 405 nm was due to the PPQ block of the copolymer.
  • the sha ⁇ peak at 330 nm was due to the optical transition of C 6 o.
  • the magnified version of the blend spectrum in the 400-700 nm region is shown as the insert of Figure 35.
  • the abso ⁇ tion bands with ⁇ max at 540 and 600 nm were characteristic abso ⁇ tion bands of C 6 o.
  • Figure 36 shows the abso ⁇ tion spectra of 5 wt.%> C7o/PPQ o-b-PS 3 oo and 5.wt % C 70 /PPQ ⁇ o-b-PS 3 oo in TFA/DCM and C70 in CS 2 .
  • the characteristic C 70 abso ⁇ tions at 335, 383 and 473 nm and PPQ-PS abso ⁇ tion centered at 405 nm were observed in the C7 0 /PPQ-PS solution spectra which could be readily deconvoluted into the component spectra.
  • solubilized fullerene/block copolymer solutions illustrated in Figure 34 i.e., addition of solid fullerene to a pre-existing copolymer solution and addition of both fullerene and block copolymer to the solvent mixture.
  • fullerene/PPQ-PS solutions were also prepared by mixing a solution of fullerene in DCM with a pre-made copolymer solution. No discernible differences were observed between the three methods. Similar solution abso ⁇ tion spectra and, subsequently, similar aggregate mo ⁇ hologies were obtained. This suggested that the observed solubilization behavior was likely near equilibrium conditions.
  • FIG. 37A shows plots of normalized C 6 o absorbance at 330 nm versus C OO loading into the solution (mg C 6 o per g diblock copolymer in solution).
  • the relative amount of solubilized C 6 o increased linearly with the fullerene loading of the diblock copolymer solutions, reaching saturation at a loading of about 200 mg/g. This was taken as the solubilization capacity of the block copolymer solutions.
  • solubilization capacity of 200 mg/g translated to 1 1.8 and 9.2 solubilized C 6 o molecules per diblock chain for PPQ 5 o-b-PS 3 o (54c) and PPQ ⁇ o-b-PS 30 o (54f), respectively.
  • the maximum amount of solubilized C70 molecule per diblock chain of PPQ 5 o-b-PS 3 oo and PPQ ⁇ 0 -b-PS 3 oo were 10.1 and 7.9, respectively.
  • the measured solubilization capacity of 200 mg of solubilized fullerene (C 6 o or C 70 ) per gram of diblock copolymer represented a solubility enhancement by factors of 1040 and 63 compared to the solubilities in pure dichloromethane and toluene, respectively.
  • organic solvent for C 6 o was 1- chloronaphthalene which had a solubility limit of 42.7 mg/g at room temperature (22 °C) (Dresselhaus et al.. Science of Fullerenes and Carbon Nanotubes, Academic Press, San Diego, California (1996); Ruoff et al., J. Phys. Chem.. 97:3379 et seq.
  • PS micellar aggregates containing 1 and 5 wt.% fullerenes C 6 o and C 70 from TFA/DCM and TF A/toluene solutions were dried and then placed in pure DCM or toluene, which are good solvents for PS block, for several days. Release of any encapsulated fullerene was not observed by optical abso ⁇ tion spectroscopy which did not detect any abso ⁇ tion signals of fullerene in solution. Subsequent examination of these aggregates by optical microscopy showed that there was no change in the mo ⁇ hology, before and after their immersion in the aprotic organic solvents.
  • Figures 38-40 show the typical mo ⁇ hologies of PPQ 50 -b-PS 3 oo (54c) aggregates with encapsulated fullerenes revealed by optical and fluorescence microscopies.
  • Figure 38 shows the fluorescence ( Figure 38A-B) and polarized optical ( Figure 38C) micrographs of a 0.1 wt.% C 7 o/PPQ o-b-PS 3 oo copolymer sample. Only spherical aggregates, with a typical diameter of about 10 ⁇ m, were observed. The spherical aggregates had highly ordered structures as indicated by the polarized optical micrographs such as that shown in Figure 38C.
  • Figures 39 and 40 show the photomicrographs of 1%> C 6 o/PPQ o-b-PS 30 o and 6%> Ceo/PPQ 5 o-b-PS 3 oo samples, respectively.
  • the average diameter of the aggregates in Figure 39 was 20 ⁇ m. Fluorescence imaging showed the aggregates to be bright red in color ( Figures 39A, B). Under crossed polarizers, the same aggregates showed yellow- brown color ( Figure 39C).
  • Figure 39C At a loading of 6 wt.% C 6 o, the average diameter of the highly spherical aggregates of Figure 40 was 30 ⁇ m. These aggregates were relatively uniform in size distribution and they had highly ordered structures with deep reddish-brown color under crossed polarizers.
  • Figure 42 shows the average aggregate diameter, measured from the optical and fluorescence micrographs, as a function of fullerene loading in the four different fullerene/PPQ-PS systems.
  • One main feature of the data was that at all fullerene loadings, C7o/PPQ 50 -b-PS 3 oo aggregates had the largest sizes.
  • the apparent 70- mg/g transition point may be regarded as the encapsulation capacity of the fullerenes in the block copolymer assemblies: that is, the maximum fullerene loading level where complete sequestering inside the spherical block copolymer aggregates is ensured as evidence by the mo ⁇ hological observations ( Figures 38-41). Since this loading level (70 mg/g) was much smaller that the amount of fullerene that could be solubilized (200 mg/g) as determined by solution abso ⁇ tion spectroscopy, this raised questions about the origin for this difference. One possibility was that the excess fullerene molecules outside the spherical aggregates (see for example Figure 41) were originally solubilized inside the - 61 -
  • nonspherical aggregates tubules, lamellae, doughnuts which were distabihzed.
  • Another possibility was that some of the fullerene molecules in solution exhibited colloidal interactions with the block copolymer molecules and micelles.
  • the 6 wt.% C 6 o or 64 mg/g encapsulated was equivalent to 3.7 C 6 o molecules per PPQ 5 o-b-PS 3 oo diblock chain which in combination with N 0 meant that about 2.2xl ⁇ ' fullerene-Ceo molecules were encapsulated inside each aggregate of Figure 40.
  • Similar estimates of the number of C 6 o encapsulated in the PPQ 50 -b-PS 3 oo spherical micelles at 0.1 and 3 wt.% fullerene loading were 4x10 and 2xl0 9 . respectively.
  • the aggregation number of the present PPQ-PS rod-coil block copolymer micelles was about 6 to 7 orders of magnitude larger.
  • DSC differential scanning calorimetry
  • the PPQ homopolymer does not exhibit any DSC transitions below 673 K.
  • Figure 43 A is the first DSC scan of 3 wt.%> C 6 o/PPQ 5 o-b-PS 3 oo (curve 3) which revealed two second-order transitions with onset temperatures at 273 and 375 K, respectively. These two transition temperatures shifted slightly during subsequent scans, 269 and 374 K for the second run and 282 and 374 K for the third scan. It is noteworthy that the sc ⁇ fcc phase transition of pure C 6 o at 259 K was not observed in the DSC scan of C6o PPQso-b-PS 3 oo aggregates.
  • the aggregate transition at 374-375 can be easily inte ⁇ reted as the T a of the PS block (Polymer Handbook. Brandrup et al., Eds., 3 rd ed., Wiley, New York, Chapt. V, pp. 77-86 (1989), which is hereby inco ⁇ orated by reference). However, the aggregate second-order transition near 273 K was new and must be carefully assigned.
  • the DSC scan of a 1 wt.%> C 6 o/PS sample is shown in Figure 43B, revealing two second-order transitions at 274 and 373 K during the first run.
  • the 373-K transition corresponded to the T g of PS.
  • the transition at 274 K shifted slightly to 270 K in subsequent scans.
  • the repeated DSC scans of C 6 o dispersed in poly(methylmethacrylate) (PMMA) -1 wt % C 6 o
  • the focus was on the molecular packing of the conjugated rigid-rod PPQ block whose relative fluorescence quantum yield was orders of magnitude larger than those of the fullerenes (C 6 o, C 70 ). It was also noteworthy that the emission bands of the fullerenes were in the near infrared region, which was far away from where PPQ-PS aggregates emit, so that there was no possible interference from their fluorescence bands.
  • the photoluminescence emission (PL) and excitation (PLE) spectra of the isolated PPQ 50 -b-PS 30 o chain in the form of a dilute blend film [0.1 wt % PPQ 50 -b-PS 30 o in poly(ethylene oxide) (PEO)] was investigated.
  • PPQ 50 -b-PS 3 oo chain had a peak at 466 nm (when excited at 380 nm) and a PLE spectrum with an abso ⁇ tion maximum at 390 nm when monitoring emission at 460 nm.
  • Figure 44A shows the PL and PLE spectra of a film of spherical PPQ 50 -b- PS 3 oo aggregates without any fullerene. These spherical aggregate spectra were very similar to those of the isolated PPQ 0 -b-PS 3 oo single chain except that they were slightly blue shifted. The aggregate PL spectrum had a peak at 454 nm whereas the PLE spectrum had a peak at 388 nm.
  • the PLE spectrum monitored at 480 nm gave an abso ⁇ tion band centered at 388 nm, slightly narrower (full width at half maximum of 62 versus 72 nm) than the spectrum of the empty PPQ5o-b-PS 3 oo aggregates.
  • the PLE spectrum monitored at 600 nm showed entirely new abso ⁇ tion characteristics with peaks at 426 and 480 nm. These results suggested that the 430-nm and 600-nm emission bands come from different emitting species. Direct excitation of the fullerene-PPQso-b- PS 300 aggregate at 480 nm gave an emission band that was the same as the 600-nm PL band.
  • Figure 44C shows the PL and PLE spectra of aggregates of 5 wt.%> C 6 o/PPQ 5 o-b- PS 30 o- Only one emission band at 600 nm was observed regardless of the excitation wavelength. The corresponding PLE spectrum monitored at 600 nm showed abso ⁇ tion peaks at 429 and 506 nm. In fact, similar investigations of other compositions of encapsulated C 60 in PPQ 50 -b-PS 3 oo between 0.1 and 5 wt.%) of C 6 o showed a progressive evolution of the photophysical properties with fullerene loading.
  • micellar structure consisting of a hollow core, a rod-like inner shell, and a flexible-coil outer corona, had a diffuse corona characteristic of coil-coil block copolymer micelles (McConnell et al.. Phvs Rev. Lett., 71 :2102-2105 (1993); - 67 -
  • McConnell et al. Macromolecules. 28:6754-6764 (1995); McConnell et al..
  • micellar aggregates looked somewhat like red blood cells because of distortion and partial collapse of the hollow spheres due to drying. Additional microscopic observations under bright field and crossed polarizers confirmed that the micelles formed by all three copolymer samples had approximate diameters of 3 to 5 ⁇ m. Polarized optical microscopy indicated that the micelles were highly ordered. This ordering originated from orientationally ordered radial packing of the rigid, rod-like blocks; micellar aggregates of coil-coil block copolymers lack such order (Webber et al., Solvents and Self-Organization of Polymers, Kluwer Academic, Dordrecht (1996); Webber, J. Phvs. Chem. B.
  • micellar film of PPQio- b-PS 3 oo which revealed a 2-D hep structure when viewed from the top ( Figure 47C) and was visually highly iridescent at various reflection angles akin to a credit card hologram.
  • the air holes revealed by carefully peeling off part of the top layer with an adhesive tape largely reflected the original hollow spherical micelles.
  • the moderate mechanical properties of these self-ordered micellar films suggested that significant interdigitation of the polystyrene coronal chains occurred between the micellar building blocks of the microporous solid.
  • the present hole diameters and periodicities were comparable to infrared (IR) wavelengths. Reductions in D snap to sizes comparable to visible wavelengths are desirable for some photonic and optoelectronic applications (Yablonovitch, J. Opt. Soc Am. B..
  • micellar building blocks best explained the observed photophysical properties. H-aggregation of the rigid rod-like blocks implied that they were orientationally aligned close to the radial direction in the spherical micellar assemblies ( Figure 12). Such an H-aggregation of conjugated molecules can lead to novel cooperative optical and nonlinear optical properties (Kasha, Radiation Research. 20:55 et seq. (1963); Hochstrasser et al., Photochem. Photobiology. 3:317 et seq. (1964); Czikkely et al., Chem. Phvs.. 6:11-14 (1970); Chen et al., J. Am. Chem. Soc. 118:2584 et seq. (1996), which are hereby inco ⁇ orated by reference).

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Abstract

La présente invention porte sur un procédé de production de microstructures, nanostrucutres ou objets. Ce procédé consiste à produire un copolymère bloc de type barre-enroulement comprenant un bloc de type barre rigide et un bloc de type enroulement flexible; à mélanger le copolymère bloc de type barre-enroulement et un solvant sélectif destiné à l'un des blocs qui solubilise ce bloc, et permettre l'auto-assemblage du copolymère bloc de type barre-enroulement en nanostructures organisées avec une région du bloc insolubilisé et une région du bloc solubilisé. L'invention porte également sur des mésostructures organisées obtenues selon ce procédé. Selon une autre variante, l'invention permet de produire la mésostructure organisée sous forme d'un solide mésoporeux. Selon encore une autre variante, la présente invention permt de produire une couche d'adsorption du copolymère bloc de type barre-enroulement et un article optique formé avec cette couche d'adorption. La présente invention porte, d'autre part, sur de grosses molécules, macromolécules ou nanoparticules d'encapsidation et de solubilisation, ce procédé consistant à ajouter de grosses molécules, macromolécules ou nanoparticules à la solution de copolymère bloc et de solvant.
PCT/US1999/005940 1998-03-18 1999-03-18 Auto-assemblage macromolecuilaire de microstructures, nanostructures, objets et solides mesoporeux WO1999047570A1 (fr)

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CA002324140A CA2324140A1 (fr) 1998-03-18 1999-03-18 Auto-assemblage macromolecuilaire de microstructures, nanostructures, objets et solides mesoporeux
EP99913954A EP1064310A1 (fr) 1998-03-18 1999-03-18 Auto-assemblage macromolecuilaire de microstructures, nanostructures, objets et solides mesoporeux
AU31913/99A AU742976B2 (en) 1998-03-18 1999-03-18 Macromolecular self-assembly of microstructures, nanostructures, objects and mesoporous solids

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FR2857586A1 (fr) * 2003-07-16 2005-01-21 Oreal Composition comprenant au moins un polymere conducteur et au moins un colorant d'oxydation et procede la mettant en oeuvre
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FR2857583A1 (fr) * 2003-07-16 2005-01-21 Oreal Composition comprenant un polymere conducteur et au moins un polymere filmifiable, procede la mettant en oeuvre et utilisation
FR2857584A1 (fr) * 2003-07-16 2005-01-21 Oreal Composition comprenant au moins un polymere conducteur et des particules rigides non filmogenes, procede la mettant en oeuvre et utilisation
FR2857582A1 (fr) * 2003-07-16 2005-01-21 Oreal Composition comprenant un polymere conducteur et un agent reducteur, procede de deformation permanente la mettant en oeuvre
US6927201B2 (en) 2001-08-28 2005-08-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Capsules for incorporation into detergent or personal care compositions
FR2870121A1 (fr) * 2004-05-12 2005-11-18 Oreal Composition cosmetique comprenant au moins un copolymere bloc specifique.
FR2870120A1 (fr) * 2004-05-12 2005-11-18 Oreal Composition cosmetique comprenant au moins un copolymere bloc specifique.
DE10252032B4 (de) * 2002-11-06 2006-04-13 Teller, Joachim, Dr. Verfahren zur Herstellung von sphärischen Partikeln und sphärische Partikel
US7106938B2 (en) 2004-03-16 2006-09-12 Regents Of The University Of Minnesota Self assembled three-dimensional photonic crystal
US7211273B2 (en) 2001-08-28 2007-05-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent or personal care composition with oil capsules
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FR2951640A1 (fr) * 2009-10-22 2011-04-29 Oreal Composition cosmetique comportant un filtre uv
FR2951644A1 (fr) * 2009-10-22 2011-04-29 Oreal Composition cosmetique comportant des particules produisant une couleur visible.
FR2951643A1 (fr) * 2009-10-22 2011-04-29 Oreal Compositions et films photoprotecteurs et procede de preparation.
FR2951642A1 (fr) * 2009-10-22 2011-04-29 Oreal Composition cosmetique comportant un agent fluorescent.
US7981441B2 (en) 2004-02-18 2011-07-19 The Board Of Trustees Of The Leland Stanford Junior University Drug delivery systems using mesoporous oxide films
US8097269B2 (en) 2004-02-18 2012-01-17 Celonova Biosciences, Inc. Bioactive material delivery systems comprising sol-gel compositions
WO2011048570A3 (fr) * 2009-10-22 2012-03-01 L'oreal Compositions et films photoprotecteurs, et procédé de préparation
US8551808B2 (en) 2007-06-21 2013-10-08 Micron Technology, Inc. Methods of patterning a substrate including multilayer antireflection coatings
US8557128B2 (en) 2007-03-22 2013-10-15 Micron Technology, Inc. Sub-10 nm line features via rapid graphoepitaxial self-assembly of amphiphilic monolayers
US8785559B2 (en) 2007-06-19 2014-07-22 Micron Technology, Inc. Crosslinkable graft polymer non-preferentially wetted by polystyrene and polyethylene oxide
US8900963B2 (en) 2011-11-02 2014-12-02 Micron Technology, Inc. Methods of forming semiconductor device structures, and related structures
US8956713B2 (en) 2007-04-18 2015-02-17 Micron Technology, Inc. Methods of forming a stamp and a stamp
US8993088B2 (en) 2008-05-02 2015-03-31 Micron Technology, Inc. Polymeric materials in self-assembled arrays and semiconductor structures comprising polymeric materials
US8999492B2 (en) 2008-02-05 2015-04-07 Micron Technology, Inc. Method to produce nanometer-sized features with directed assembly of block copolymers
US9087699B2 (en) 2012-10-05 2015-07-21 Micron Technology, Inc. Methods of forming an array of openings in a substrate, and related methods of forming a semiconductor device structure
US9114125B2 (en) 2008-04-11 2015-08-25 Celonova Biosciences, Inc. Drug eluting expandable devices
US9142420B2 (en) 2007-04-20 2015-09-22 Micron Technology, Inc. Extensions of self-assembled structures to increased dimensions via a “bootstrap” self-templating method
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WO2000026157A1 (fr) * 1998-11-04 2000-05-11 The Regents Of The University Of California Oxydes poreux organises en hierarchie
WO2002041043A2 (fr) * 2000-11-14 2002-05-23 The Regents Of The University Of California Composites inorganiques/copolymere sequence-colorants et matieres mesoporeuses dopees par des colorants pour applications optiques et de detection
WO2002041043A3 (fr) * 2000-11-14 2003-03-27 Univ California Composites inorganiques/copolymere sequence-colorants et matieres mesoporeuses dopees par des colorants pour applications optiques et de detection
US6927201B2 (en) 2001-08-28 2005-08-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Capsules for incorporation into detergent or personal care compositions
US7211273B2 (en) 2001-08-28 2007-05-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent or personal care composition with oil capsules
WO2003063811A2 (fr) * 2002-01-31 2003-08-07 L'oreal Utilisation de polymeres conducteurs solubles pour le traitement des fibres keratiniques humaines
US7217295B2 (en) 2002-01-31 2007-05-15 L'oreal S.A. Use of soluble conductive polymers for treating human keratin fibers
WO2003063811A3 (fr) * 2002-01-31 2004-05-06 Oreal Utilisation de polymeres conducteurs solubles pour le traitement des fibres keratiniques humaines
WO2003068185A3 (fr) * 2002-02-14 2003-11-13 Sixty Inc C Utilisation de nanotubes de fullerene ou de carbone pour l'administration de medicaments
WO2003068185A2 (fr) * 2002-02-14 2003-08-21 C Sixty, Inc. Utilisation de nanotubes de fullerene ou de carbone pour l'administration de medicaments
US7070810B2 (en) 2002-02-14 2006-07-04 C Sixty Inc. Use of buckysome or carbon nanotube for drug delivery
WO2004015167A2 (fr) * 2002-08-09 2004-02-19 Canon Kabushiki Kaisha Film a mesostructure, film poreux et procede de fabrication
WO2004015167A3 (fr) * 2002-08-09 2004-05-27 Canon Kk Film a mesostructure, film poreux et procede de fabrication
DE10252032B4 (de) * 2002-11-06 2006-04-13 Teller, Joachim, Dr. Verfahren zur Herstellung von sphärischen Partikeln und sphärische Partikel
FR2857584A1 (fr) * 2003-07-16 2005-01-21 Oreal Composition comprenant au moins un polymere conducteur et des particules rigides non filmogenes, procede la mettant en oeuvre et utilisation
FR2857582A1 (fr) * 2003-07-16 2005-01-21 Oreal Composition comprenant un polymere conducteur et un agent reducteur, procede de deformation permanente la mettant en oeuvre
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US8097269B2 (en) 2004-02-18 2012-01-17 Celonova Biosciences, Inc. Bioactive material delivery systems comprising sol-gel compositions
US7981441B2 (en) 2004-02-18 2011-07-19 The Board Of Trustees Of The Leland Stanford Junior University Drug delivery systems using mesoporous oxide films
US7106938B2 (en) 2004-03-16 2006-09-12 Regents Of The University Of Minnesota Self assembled three-dimensional photonic crystal
FR2870121A1 (fr) * 2004-05-12 2005-11-18 Oreal Composition cosmetique comprenant au moins un copolymere bloc specifique.
FR2870120A1 (fr) * 2004-05-12 2005-11-18 Oreal Composition cosmetique comprenant au moins un copolymere bloc specifique.
WO2005110350A1 (fr) * 2004-05-12 2005-11-24 L'oreal Composition cosmétique comprenant au moins un copolymère spécifique séquencé
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WO2007081876A2 (fr) * 2006-01-04 2007-07-19 Liquidia Technologies, Inc. Surfaces nanostructurées pour applications biomédicales/biomatérielles et traitements à partir de celles-ci
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US9314548B2 (en) 2006-01-04 2016-04-19 Liquidia Technologies, Inc. Nanostructured surfaces for biomedical/biomaterial applications and processes thereof
US8944804B2 (en) 2006-01-04 2015-02-03 Liquidia Technologies, Inc. Nanostructured surfaces for biomedical/biomaterial applications and processes thereof
US8557128B2 (en) 2007-03-22 2013-10-15 Micron Technology, Inc. Sub-10 nm line features via rapid graphoepitaxial self-assembly of amphiphilic monolayers
US9768021B2 (en) 2007-04-18 2017-09-19 Micron Technology, Inc. Methods of forming semiconductor device structures including metal oxide structures
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US9257256B2 (en) 2007-06-12 2016-02-09 Micron Technology, Inc. Templates including self-assembled block copolymer films
US8785559B2 (en) 2007-06-19 2014-07-22 Micron Technology, Inc. Crosslinkable graft polymer non-preferentially wetted by polystyrene and polyethylene oxide
US8551808B2 (en) 2007-06-21 2013-10-08 Micron Technology, Inc. Methods of patterning a substrate including multilayer antireflection coatings
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