Giant Wormlike Rubber Micelles
12 Feb 1999-Science (American Association for the Advancement of Science)-Vol. 283, Iss: 5404, pp 960-963
TL;DR: A low molecular weight poly(ethyleneoxide)-poly(butadiene) (PEO-PB) diblock copolymer containing 50 weight percent PEO forms gigantic wormlike micelles at low concentrations (<5 percent by weight) in water.
Abstract: A low molecular weight poly(ethyleneoxide)-poly(butadiene) (PEO-PB) diblock copolymer containing 50 weight percent PEO forms gigantic wormlike micelles at low concentrations (<5 percent by weight) in water. Subsequent generation of free radicals with a conventional water-based redox reaction leads to chemical cross-linking of the PB cores without disruption of the cylindrical morphology, as evidenced by cryotransmission electron microscopy and small-angle neutron scattering experiments. These wormlike rubber micelles exhibit unusual viscoelastic properties in water.
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TL;DR: In this paper, pH-induced self-assembly of a peptide-amphiphile was used to make a nanostructured fibrous scaffold reminiscent of extracellular matrix.
Abstract: We have used the pH-induced self-assembly of a peptide-amphiphile to make a nanostructured fibrous scaffold reminiscent of extracellular matrix. The design of this peptide-amphiphile allows the nanofibers to be reversibly cross-linked to enhance or decrease their structural integrity. After cross-linking, the fibers are able to direct mineralization of hydroxyapatite to form a composite material in which the crystallographic c axes of hydroxyapatite are aligned with the long axes of the fibers. This alignment is the same as that observed between collagen fibrils and hydroxyapatite crystals in bone.
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TL;DR: The results suggest a new class of synthetic thin-shelled capsules based on block copolymer chemistry, and both the membrane bending and area expansion moduli of electroformed polymersomes (polymer-based liposomes) fell within the range of lipid membrane measurements.
Abstract: Vesicles were made from amphiphilic diblock copolymers and characterized by micromanipulation. The average molecular weight of the specific polymer studied, polyethyleneoxide-polyethylethylene (EO40-EE37), is several times greater than that of typical phospholipids in natural membranes. Both the membrane bending and area expansion moduli of electroformed polymersomes (polymer-based liposomes) fell within the range of lipid membrane measurements, but the giant polymersomes proved to be almost an order of magnitude tougher and sustained far greater areal strain before rupture. The polymersome membrane was also at least 10 times less permeable to water than common phospholipid bilayers. The results suggest a new class of synthetic thin-shelled capsules based on block copolymer chemistry.
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TL;DR: This review is focused on the inherent advantages in using polymer vesicles over their small molecule lipid counterparts and the potential applications in biology for both drug delivery and synthetic cellular reactors.
Abstract: The ability of amphiphilic block copolymers to self-assemble in selective solvents has been widely studied in academia and utilized for various commercial products. The self-assembled polymer vesicle is at the forefront of this nanotechnological revolution with seemingly endless possible uses, ranging from biomedical to nanometer-scale enzymatic reactors. This review is focused on the inherent advantages in using polymer vesicles over their small molecule lipid counterparts and the potential applications in biology for both drug delivery and synthetic cellular reactors.
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TL;DR: The scope of amino acid selection and alkyl tail modification in the peptide-amphiphile molecules are investigated, yielding nanofibers varying in morphology, surface chemistry, and potential bioactivity, demonstrating the chemically versatile nature of this supramolecular system.
Abstract: Twelve derivatives of peptide-amphiphile molecules, designed to self-assemble into nanofibers, are described. The scope of amino acid selection and alkyl tail modification in the peptide-amphiphile molecules are investigated, yielding nanofibers varying in morphology, surface chemistry, and potential bioactivity. The results demonstrate the chemically versatile nature of this supramolecular system and its high potential for manufacturing nanomaterials. In addition, three different modes of self-assembly resulting in nanofibers are described, including pH control, divalent ion induction, and concentration.
1,266 citations
References
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TL;DR: The Part and the Whole as discussed by the authors principle of self-organization for the creation of functional units is not an invention of modern natural sciences; it was already a basic idea of the ancient philosophies in Asia and Europe: only the mutuality of the parts creates the whole and its ability to function.
Abstract: The Part and the Whole. The principle of self-organization for the creation of functional units is not an invention of modern natural sciences. It was already a basic idea of the ancient philosophies in Asia and Europe: only the mutuality of the parts creates the whole and its ability to function. Translated into the language of chemistry this means: the self-organization of molecules leads to supramolecular systems and is responsible for their functions. Thermotropic and lyotropic liquid crystals are such functional units, formed by self-organization. As highly oriented systems, they exhibit new properties. The importance of lyotropic liquid crystals for the life sciences has been known for a long time. They are a prerequisite for the development of life and the ability of cells to function. In materials sciences this concept of function through organization led to the development of new liquid-crystalline materials. From the point of view of macromolecular chemistry, this review tries to combine these two different fields and especially hopes to stimulate their interaction and joint treatment. To exemplify this, the molecular architecture of polymeric organized systems will be discussed. Polymeric liquid crystals combine the ability to undergo spontaneous self-organization–typical of liquid-crystalline phases–with the polymer-specific property of stabilizing these ordered states. As new materials, polymeric liquid crystals have already been investigated intensively. As model systems for biomembranes as well as for the simulation of biomembrane processes, they so far have been little discussed. The intention of this review article is to show that polymer science is able to contribute to the simulation of cellular processes such as the stabilization of biomembranes, specific surface recognition, or even the “uncorking” of cells. Polymer science, having an old tradition as an inter-disciplinary field, can no longer restrict itself to common plastics. Attempts to reach new horizons have already begun. The borderland between liquid crystals and cells will certainly play an important role. Basic requirements to work in this frontier area between organic chemistry, membrane biology, life science, and materials science will be the delight in scientific adventures as well as the courage to go ahead. The most important prerequisite will be the willingness to cooperate with disciplines which so far have not really accepted each other. From this point of view, this review does not aim at giving defined answers. It wants instead to encourage the scientific venture: too often we cling to painfully acquired knowledge, fearing adventures.
1,276 citations
TL;DR: Etude theorique de la dynamique de the relaxation de contrainte dans un systeme dense de polymeres vivants as mentioned in this paper, e.g.
Abstract: Etude theorique de la dynamique de la relaxation de contrainte dans un systeme dense de polymeres vivants
884 citations
TL;DR: The molecular constitution of viscoelastic gels is customarily described in terms of networks, which may have a transient or permanent character as discussed by the authors, depending on the ionic strength of the solution, these particles may be completely stiff or semiflexible.
Abstract: The molecular constitution of viscoelastic gels is customarily described in terms of networks, which may have a transient or permanent character. Such supermolecular structures are often observed in biological or macromolecular systems, but can even occur in dilute solutions of some detergents. Surfactant molecules in solution, under suitable conditions, assemble reversibly into large aggregates of rod-like geometry. Depending on the ionic strength of the solution, these particles may be completely stiff or semiflexible. At low concentrations, when the lengths of the rods are much smaller than their mean distance of separation, there exists a sol state which is highly sensitive to shear forces. At higher surfactant concentrations, where the lengths of the rod shaped micelles become comparable to their mean distance, one observes gel formation and the solutions exhibit pronounced elastic properties. In analogy to polymer systems, these elongated, rod shaped micelles are strongly entangled; this leads to co...
745 citations
TL;DR: The typical phase behavior of microemulsion systems undergoing phase inversion is briefly reviewed in this article, where the mean and Gaussian curvatures of the interfacial film with temperature are determined.
Abstract: The typical phase behavior of microemulsion systems undergoing phase inversion is briefly reviewed. As a model system H2O-n-octane-C12E5 is studied with various experimental techniques. The occurring microstructures are visualized by freeze fracture electron microscopy and the corresponding domain sizes are quantified by small-angle neutron scattering. From the variations of the domain sizes the mean and Gaussian curvatures of the interfacial film with temperature are determined. It is found that the mean interfacial curvatureH changes gradually and nearly linearly with temperature from positive (Winsor I) to negative (Winsor II), passing through zero for bicontinuous microemulsions where these contain exactly equal volume fractions of water and oil. There the interfacial tension between bulk water-and oil-rich phases passes through an extreme minimum. Quantitative knowledge of the curvatures permits the measurements of interfacial tensions between the bulk phases to be discussed in terms of the relative contributions of bending energy and entropy of dispersion.
486 citations
TL;DR: In this paper, the properties of aqueous solutions of cetyltrimethylammonium chloride (CTAC) with salicylate (from NaSal) as the binding counterion are presented as a function of counterion concentration.
Abstract: Artifact-free electron micrographs and rheological properties of aqueous solutions of cetyltrimethylammonium chloride (CTAC) with salicylate (from NaSal) as the binding counterion, are presented as a function of counterion concentration.
352 citations