We develop a range of various approaches to fabrication of polymer membranes and templates from
polymers, copolymers, block-copolymers and composite materials.
Thin films of block-copolymers undergo phase segregation, resulting in various regular structures
of lamellar, cylindrical, spherical, or even more complicated shapes. Dimensions of the structures
can be determined by the molecular dimensions of the block-copolymers and are of the order of
between 5 and 100 nm. This size range is of special interest as for the fabrication of polymer membranes
and templates. Using different approaches, including lithographical ones, those structures may be
transformed into regular arrays of submicron channels, pores, or domains of electroconductive,
light-emitting, magnetic materials, and so forth. Coordination of the particular block with low
molecular weight molecules on the first step allows fabrication of organized structures such as a
comb-like block copolymer. This morphology is then frozen by cooling the systems below the glass
transition temperature. The low molecular weight component is then removed by dissolving in a
selective solvent leaving voids and channels. The materials with a regular array of nano-pores
fabricated in this way can then be used as membranes or templates. The templates are filled with
metals or electroconductive polymers that yield thin films of practical interest for nano-devices
and sensors.
We developed a novel method for the fabrication of flexible stimulus-responsive polymer gel
membranes (PG-membranes). These membranes are thin porous films made of a cross-linked
polyelectrolyte. In our approach, the porous films are formed by the phase separation of
polyelectrolyte and a volatile additive. This approach provides the broad possibility of
regulating pore sizes and membrane responsiveness.
Video 1. Stimuli responsive membrane swelling-deswelling. Based on a series of real AFM images.
The PG-membranes can be prepared on any flat substrate with a low surface roughness (e.g.,
Si-wafer). Afterwards, the membrane can be transferred (and attached chemically, if necessary)
onto various porous or non-porous supports with flat, profiled, and even curved surfaces (e.g.,
membrane filter, fabrics, chemical sensor, or human skin) for the fabrication of devices with
pH-controllable permeability.
Video 2. Application of responsive membrane for filtration processes.
Major Directions:
Fabrication of combi-like block-copolymer thin films with the ordered arrays of cylindrical domains;
Fabrication of non-selective surfaces for orientation and switching of orientation of the block-copolymer films;
Fabrication of polymer membranes with nanoscopic pores;
Fabrication of polymer membranes with gradient properties;
Fabrication of ordered arrays of nanoscopic metallic nanoparticles of various shapes: round clusters, cylinders, lamellas;
Fabrication of responsive gel membranes.
Figure 1. Stimuli responsive polymer membranes and templates.
Publications on Topic (review titles are marked blue):
Koestner, R.; Roiter, Y.; Kozhinova, I.; Minko, S. AFM Imaging of Adsorbed Nafion Polymer on Mica and Graphite at Molecular Level.Langmuir2011, ACS Just Accepted Manuscript (Published on Web: July 7, 2011).
Details
Koestner, R.; Roiter, Y.; Kozhinova, I.; Minko, S. The Effect of Local Charge Distribution on Graphite Surface on Nafion Polymer Adsorption as Visualized at Molecular Level.Journal of Physical Chemistry C2011, ACS Just Accepted Manuscript (Published on Web: July 1, 2011).
Details
Tokarev, I.; Minko, S. Stimuli-Responsive Porous Hydrogels at Interfaces for Molecular Filtration, Separation, Controlled Release, and Gating in Capsules and Membranes.Advanced Materials2010, 22(31), 3446-3462.
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Tokarev, I.; Tokareva, I.; Gopishetty, V.; Katz, E.; Minko, S. Specific Biochemical-to-Optical Signal Transduction by Responsive Thin Hydrogel Films Loaded with Noble Metal Nanoparticles.Advanced Materials2010, 22(12), 1412-1416.
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Stuart, M. A. C.; Huck, W. T. S.; Genzer, J.; Müller, M.; Ober, C.; Stamm, M.; Sukhorukov, G. B.; Szleifer, I.; Tsukruk, V. V.; Urban, M.; Winnik, F.; Zauscher, S.; Luzinov, I.; Minko, S. Emerging applications of stimuli-responsive polymer materials.Nature Materials2010, 9(2), 101-113.
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Tokarev, I.; Motornov, M.; Minko, S. Molecular-engineered stimuli-responsive thin polymer film: a platform for the development of integrated multifunctional intelligent materials.Journal of Materials Chemistry2009, 19(38), 6932-6948.
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Tokarev, I.; Gopishetty, V.; Zhou, J.; Pita, M.; Motornov, M.; Katz, E.; Minko, S. Stimuli-Responsive Hydrogel Membranes Coupled with Biocatalytic Processes.ACS Applied Materials & Interfaces2009, 3(1), 532-536.
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Tokarev, I.; Tokareva, I.; Minko, S. Gold-Nanoparticle-Enhanced Plasmonic Effects in a Responsive Polymer Gel.Advanced Materials2008, 20(14), 2730-2734.
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Gopishetty, V.; Tokarev, I.; Minko, S. 'Smart' membranes from stimuli-sensitive biopolymer hydrogel.PMSE Preprints2008, 99, 719-720.
Tokarev, I.; Orlov, M.; Katz, E.; Minko, S. Chemical and electrochemical gating using a responsive thin film gel membrane.PMSE Preprints2008, 99, 715-716.
Katz, E.; Kin, T. T.; Jean, Z.; Gopishetty, V.; Ornatska, M.; Pita, M.; Minko, S. Switchabe polymer-modified interfaces and membranes for bioelectronic applications.PMSE Preprints2008, 99, 711.
Tokarev, I.; Tokareva, I.; Minko, S. Surface plasmon resonance effects in stimuli-sensitive polyelectrolyte/gold nanoparticle hybrid membranes.PMSE Preprints2008, 99, 160-161.
Gopishetty, V.; Tokarev, I.; Minko, S. Multifunctional nanostructured hybrid membranes from biopolymer hydrogel.Polymer Preprints2008, 49(2), 885-886.
Tokarev, I.; Orlov, M.; Katz, E.; Minko, S. An Electrochemical Gate Based on a Stimuli-Responsive Membrane Associated with an Electrode Surface.Journal of Physical Chemistry B2007, 111(42), 12141-12145.
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Orlov, M.; Tokarev, I.; Scholl, A.; Doran, A.; Minko, S. pH-Responsive Thin Film Membranes from Poly(2-vinylpyridine): Water Vapor-Induced Formation of a Microporous Structure.Macromolecules2007, 40(6), 2086-2091.
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Orlov, M.; Tokarev, I.; Minko, S. Responsive polyelectrolyte membranes.Polymer Preprints2007, 48(1), 248-249.
Tokarev, I.; Orlov, M.; Minko, S. Microporous thin film membranes from pH-responsive polymer.Polymer Preprints2007, 48(1), 723-724.
Tokarev, I.; Orlov, M.; Minko, S. Responsive Polyelectrolyte Gel Membranes.Advanced Materials2006, 18(18), 2458-2460.
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Tokarev, I.; Krenek, R.; Burkov, Y.; Schmeisser, D.; Sidorenko, A.; Minko, S.; Stamm, M. Microphase Separation in Thin Films of Poly(styrene-block-4-vinylpyridine) Copolymer-2-(4'-Hydroxybenzeneazo)benzoic Acid Assembly.Macromolecules 2005,38(2), 507-516.
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Minko, S. Responsive nanostructured polymer materials for lithography.PMSE Preprints2005,92, 143.
Tokarev, I.; Sidorenko, A.; Minko, S. Fabrication of ordered arrays of copper nanorods using thin block copolymer templates.Polymer Preprints2005, 46(2), 740-741.
Tokarev, I.; Sidorenko, A.; Minko, S.; Stamm, M. Switching nanotemplates.PMSE Preprints2004, 90, 292-293.
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Tokarev, I.; Sydorenko, A.; Minko, S.; Stamm, M. Novel supramolecular approach to periodic nanostructures in thin polymer films.PMSE Preprints2003, 89, 115-116.
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Sidorenko, A.; Tokarev, I.; Minko, S.; Stamm, M. Ordered Reactive Nanomembranes/Nanotemplates from Thin Films of Block Copolymer Supramolecular Assembly.Journal of the American Chemical Society2003, 125(40), 12211-12216.
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Tokarev, I.; Minko, S.; Stamm, M. "Hairy tube" polymer templates from diblock copolymer thin films.Materials Research Society Symposium Proceedings2002, 728, 11-16.