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WO2006001774A1 - Procedes mettant en application l'auto-assemblage/agregation de biomolecules pour construire des dispositifs electroniques bases sur des polymeres conjugues - Google Patents

Procedes mettant en application l'auto-assemblage/agregation de biomolecules pour construire des dispositifs electroniques bases sur des polymeres conjugues Download PDF

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Publication number
WO2006001774A1
WO2006001774A1 PCT/SE2005/001021 SE2005001021W WO2006001774A1 WO 2006001774 A1 WO2006001774 A1 WO 2006001774A1 SE 2005001021 W SE2005001021 W SE 2005001021W WO 2006001774 A1 WO2006001774 A1 WO 2006001774A1
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Prior art keywords
conjugated polymer
complex
biomolecule
biomolecules
polymer
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PCT/SE2005/001021
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English (en)
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Olle Werner INGANÄS
Peter K. R. Nilsson
Anna Herland
Per HAMMARSTRÖM
Per Björk
Original Assignee
Inganaes Olle Werner
Nilsson Peter K R
Anna Herland
Hammarstroem Per
Bjoerk Per
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Application filed by Inganaes Olle Werner, Nilsson Peter K R, Anna Herland, Hammarstroem Per, Bjoerk Per filed Critical Inganaes Olle Werner
Publication of WO2006001774A1 publication Critical patent/WO2006001774A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/761—Biomolecules or bio-macromolecules, e.g. proteins, chlorophyl, lipids or enzymes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene

Definitions

  • the present invention relates to the construction of electronic materials and devices based on self-assembly/aggregation of biomolecules and conjugated polymers.
  • biopolymers such as proteins and DNA
  • ordered conformations such as alfa-helix and beta-sheets
  • Well-ordered conformations of biomolecules are very important in biological systems, as a part of the cell signalling pathways and enzymatic reactions. If self-assembly/aggregation of three dimensional ordered structures of biomolecules can be used as construction elements for the assembly of molecular electronic systems based on conjugated polymers, the assembly and the addressing of molecular size electronic elements on the nano scale dimension will be fulfilled.
  • the electronic materials are all conjugated polymers and oligomers in metallic and in semiconducting states.
  • conjugated polymer useful as the functional material in electronic devices and wires.
  • conjugated polymer is a polyelectrolyte, and comprises copolymers or homopolymers of thiophene, pyrrole, aniline, furan, phenylene, vinylene, fluorene or their substituted forms, with one or more ionic side chain functionalities.
  • a further aspect of the invention provides a electronic device constructed with the self- assembly/aggregation of biomolecules, useful as rectifying elements (diodes, with subgroups in photodiodes and light emitting diodes), electrochemically operated transistors and diodes, field effect transistors, field effect transistors driven by electrolytic gates. These in turn may be assembled into digital circuits, operated in digital logic.
  • the assembly of more complex structures may include logical functions implemented in digital logic (AND, OR, NOR, NAND logical gates, oscillators, memory shift registers).
  • Devices for electronic processing and storage may also include systems based on analog operations, say in variable resistors and connectors, suitable for neural network type systems.
  • Figure 1 shows the chemical structure of polythiophene acetic acid (PTAA), an anionic polythiophene derivative, poly (3- [ (S)-5-AMINO-5-CARBOXYL-3-] [OXAPENTYL]-2,] 5-thiophenylene hydrochloride) (POWT), a zwitterionic polythiophene derivative, and poly((3,3"-di[(S)-5-amino-5-carbonyl-3-oxapentyl]-[2,2 1 ;5',2"])-5,5"-terthiophenylene, PONT a zwitterionic oligomer of thiophene derivatives.
  • PTAA polythiophene acetic acid
  • POWT 5-thiophenylene hydrochloride
  • PONT 5-thiophenylene hydrochloride
  • Figure 2 shows the absorption spectra of 40 ⁇ M PTAA (on a monomer basis) with 0 ⁇ M insulin, 5 ⁇ M native bovine insulin, or 5 ⁇ M amyloid bovine insulin, respectively after 5 minutes of incubation in 20 mM Na-phosphate buffer pH 7.0. Insertion showing microtiter plate wells containing PTAA/native bovine insulin (left) and PTAA/amyloid bovine insulin (right).
  • Figure 3 shows the changes of the intensity of the absorbed light at 434nm and 463 nm of 40 ⁇ M PTAA (on a monomer basis) with an aliquot of 5 ⁇ M bovine insulin in 20 mM Na- phosphate buffer pH 7.O., during amyloid formation in the bovine insulin (0.3 mM, pH 1.6 65°C).
  • Figure 4 shows the emission spectra of 40 ⁇ M PTAA (on a monomer basis) with 0 ⁇ M insulin, 5 ⁇ M native bovine insulin, or 5 ⁇ M amyloid bovine insulin, respectively after 5 minutes of incubation in 20 mM Na-phosphate buffer pH 7.0. All of the emission spectra were recorded with excitation at 400 nm.
  • Figure 5 shows the changes of the ratio of the intensity of the emitted light at 550nm and 58Onm of 40 ⁇ M PTAA (on a monomer basis) with an aliquot of 5 ⁇ M insulin in 20 mM Na- phosphate buffer pH 7.O., during amyloid formation in the bovine insulin (0.3 mM, pH 1.6 65°C).
  • Figure 6 shows the emission spectra of 6.5 ⁇ M PONT with 0 ⁇ M insulin, 5 ⁇ M native bovine insulin, or 5 ⁇ M amyloid bovine insulin, respectively after 5 minutes of incubation in 25 mM HCl.. The emission spectra were recorded with excitation at 400 nm.
  • Figure 7 shows the changes of the ratio of the intensity of the emitted light at 560nm and 600nm of 6,5 ⁇ M PONT (on a monomer basis) with an aliquot of 5 ⁇ M insulin in 25 mM pH 1.6, during amyloid formation in the bovine insulin (0.3 mM, pH 1.6 65 0 C).
  • Figure 8 shows the changes of the ratio of the intensity of the emitted light at 540nm and 670nm of 30 ⁇ M POWT (on a monomer basis) with an aliquot of 5 ⁇ M insulin in 20 mM Na- phosphate buffer pH 1.6, during amyloid formation in the bovine insulin (0.3 mM, pH 1.6 65 0 C).
  • Figure 9 shows the fluorescence images of POWT/bovine insulin complexes. Hydrogels of POWT/native bovine insulin (left) and POWT/amyloid bovine insulin (right). The fluorescence was recorded with an epifluorescence microscope (Zeiss Axiovert inverted microscope A200 Mot) equipped with a CCD camera (Axiocam HR).
  • Figure 10 shows the fluorescence images (top) and transmission images (bottom) of PONT/bovine insulin complexes. Hydrogels of PONT/native bovine insulin (left) and PONT/amyloid bovine insulin (right).
  • the fluorescence and transmission images were recorded with an epifluorescence microscope (Zeiss Axiovert inverted microscope A200 Mot) equipped with a CCD camera (Axiocam HR).
  • Figure 11 shows the fluorescence images of PTAA/bovine insulin complexes. Hydrogels of PTAA/native bovine insulin (left) and PTAA/amyloid bovine insulin (right).
  • the fluorescence was recorded with an epifluorescence microscope (Zeiss Axiovert inverted microscope A200 Mot) equipped with a CCD camera (Axiocam HR).
  • Figure 12 shows emission spectra of 6.5 ⁇ M PONT-HCl (on a chain basis) with 5 ⁇ M bovine insulin in 25 mM HCl, when PONT was present during amyloid fibrillation.
  • the amyloid formation occurred at 0.3 mM bovine insulin, 0,39 mM PONT in 25 mM HCl heated to 65° C for different periods of time; 0 h, 5 h and 25 h.
  • the emission spectra were recorded with excitation at 400 run.
  • Figure 13 shows the changes of the ratio of the intensity of the emitted light at 540nm and 650 nm of 6.5 ⁇ M PONT-HCl (on a chain basis) with 5 ⁇ M bovine insulin in 25 mM HCl, when PONT was present during amyloid fibrillation.
  • the amyloid formation occurred at 0.3 mM bovine insulin, 0,39 mM PONT in 25 mM HCl heated to 65° C for different periods of time; 0 h, 5 h and 25 h.
  • the emission spectra were recorded with excitation at 400 nm.
  • Figure 14 shows a negative staining transmission electron micrograph of a PONT/bovine insulin amyloid fibril complex.
  • the amyloid formation occurred at 0.3 mM bovine insulin, 0,39 mM PONT in 25 mM HCl heated to 65° C for 25 h.
  • the scale bar represents 200 nm.
  • Figure 15 shows a fluorescent image of PONT/bovine insulin amyloid fibril complex. (left) and a transmission image of PONT/bovine insulin amyloid fibril complex.(right). The scale bars represents 20 ⁇ m.
  • Figure 16 shows a scanning electron micrograph of PONT/bovine insulin amyloid fibril complex . The complex is deposited on a silicon substrate and sputtered with a thin layer of gold.
  • Figure 17 a shows an fluorescent image of a PONT/bovine insulin amyloid fibril complex (top) deposited on a indium doped tin oxide coated glass substrate and embedded in a PEDOT/PSS matrix.
  • the substrate is in a three electrode setup an immersed in 0.1 M LiClO 4 in methanol, no voltage is applied, b) First doping of the doping of the complex (0.9 V vs. Ag/ AgCl). c) First de-doping of the complex (-0.3 V vs. Ag/ AgCl). d) Second doping of the complex (0.9 V vs. Ag/ AgCl). e) Second de-doping of the complex (-0.3 V vs. Ag/ AgCl).
  • the fluorescence images were recorded with an epifluorescence microscope (Zeiss Axiovert inverted microscope A200 Mot) equipped with a CCD camera (Axiocam HR).
  • the scale bars represents 20 ⁇ m.
  • This device is therefore an optoelectronic element, but also demonstrates that reversible doping of the conjugated polymer in the fibre is feasible, as well as that electronic conductivity in the fibre is sufficiently high for electronic transport transverse to the fibre axis.
  • Figure 18 shows YOYO-I stained ⁇ DNA(48,5 kbp) that is stretched on polystyrene substrate (top) and POWT/ ⁇ DNA(48,5 kbp) complexes stretched on polystyrene substrate (bottom).
  • the fluorescence images were recorded with an epifluorescence microscope (Zeiss Axiovert inverted microscope A200 Mot) equipped with a CCD camera (Axiocam HR). Te scale bares represents 25 ⁇ m.
  • the present invention relates to novel methods using self- assembly/aggregation of biomolecules for the construction of electronic devices based on conjugated polymers.
  • the conjugated polymer is exposed to the biomolecules whereby the polymer and the biomolecule of interest interact, and the biomolecules will self- assemble/aggregate with the conjugated polymer and thereby form conducting wires, electronic fibers and junctions useful in electronic devices.
  • the invention is based on conjugated polymers interacting with said biomolecule.
  • the interaction occurs without covalent bonding and is based on hydrogen bonding, electrostatic- and non-polar interactions between the conjugated polymer and the biomolecule, herein referred to as non-covalent bonding, which further includes any type of bonding that is not covalent in nature.
  • the present invention utilizes self-assembly/aggregation of the biomolecule, which act as construction workers on the molecular level for the assembly of electronic devices based on conjugated polymers.
  • the conjugated polymer is suitably implemented as an active part of an electronic device, e. g. by immobilizing the conjugated polymer on a substrate in an electronic device.
  • the electronic device comprises a suitable receptacle for said substrate, and a complex between the conjugated polymer and the biomolecule is formed on the substrate.
  • the assembly method is also suitable for assembly in three dimension, out of aqueous environments. While this assembly method does not require a substrate, there is a need to anchor the network onto a patterned substrate with some of the wires which form part of the network.
  • polymers exhibiting the above discussed characteristics poly (3- [[ (S)-5- AMINO-5-CARBOXYL-3-OXAPENTYL]-2,] 5-thiophenylene hydrochloride) (POWT), poly((3,3"-di[(S)-5-amino-5-carbonyl-3-oxa ⁇ entyl]-[2,2 l ;5',2"])-5,5"-terthiophenylene hydrochloride) (PONT) and poythiophene acetic acid (PTAA) (see Figure 1) can be mentioned. Studies of these polymers (see Andersson, M.; Ekeblad, P. O.
  • Especially the aggregation of polymer chains induce novel intra-and inter chain processes.
  • the intra-chain processes are related to optical and electronic processes within a polymer chain and the inter-chain processes are related to optical and electronic processes between adjacent polymer chains. This cause novel optical absorption and emission properties, due to the novel intra-and inter chain processes.
  • the ionic groups create versatile hydrogen bonding patterns with different molecules.
  • the detailed description of the invention that follows will deal separately with the conjugated polymers, biomolecules, methods of construction and electronic devices. The invention is finally exemplified with a number of experiments demonstrating the utility thereof.
  • the present invention relates to a variety of conjugated polymers, with a minimum of 5 mers, consisting of mers derived from the monomers thiophene, pyrrole, aniline, furan, phenylene, vinylene, fluorine, acetylene or their substituted forms, forming homopolymers and copolymers thereof.
  • the conjugated polymer can be mono dispersed, consist of polymer chains with a well-define chain length, or poly dispersed, comprised of polymer chains with different chain length.
  • monomers with anionic-, cationic-, zwitterionic- or hydrophobic side chain functionalities are included within the scope of the invention.
  • the side chain functionalities is derived from, but not limited to, amino acids, amino acid derivatives, neurotransmitters, monosaccharides, nucleic acids, or combinations and chemically modified derivatives thereof.
  • the conjugated polymers of the present invention may contain a single side chain functionality or may comprise two or more different side chain functionalities.
  • the functional groups of the conjugated polymers make these polymer derivatives suitable for forming strong polymer complexes with biomolecules.
  • the presence of a hydrophobic main chain in these polymers add the possibility of hydrophobic interactions to biomolecules .
  • the conjugated polymers of the present invention form a complex with a biomolecule of interest. This complex is formed without covalent bonding and based on hydrogen bonding, electrostatic-and non-polar interactions between the conjugated polymer and the biomolecule.
  • the molecule will have the ability to self-assemble/aggregate, or adopt a well-order three dimensional structure. The self-assembly/aggregation of the biomolecules can occur prior to the complexation of the conjugated polymer and the biomolecule, or within the conjugated polymer-biomolecule complex.
  • a wide variety of biomolecule can be used and the choice of biomolecule is only limited by the affinity to the conjugated polymer.
  • biomolecules include, but are not limited to, peptides, carbohydrates, nucleic acids and DNA, lipids, pharmaceuticals, antigens, antibodies, proteins, amyloid fibrils, enzymes, toxins, any organic polymers or combination of these molecules.
  • the biomolecules can be chemically modified to interact with the conjugated polymer of interest. Methods of derivatizing a diverse range of proteins and DNA are well known. For example, amino acid side chains can easily be modified to contain polar and non-polar groups, or groups with hydrogen bonding abilities.
  • the present invention relates to methods of constructing electronic devices based on self-assembly/aggregation of biomolecules and conjugated polymers. It includes free-form assembly in three dimensional space, as well as surface directed assembly onto micropatterned substrates. Both procedures use liquid environments for the assembly process, but cues for this assembly may be supplied through localised stimulus, and growth may be occurring in confined geometries. Adress tags for assembly, both to surface and in 3D, can be supplied through molecules such as DNA and oligonucleotides, which act to create assembly during hybridisation, which is sequence specific.
  • the conjugated polymers, the biomolecules or the conjugated polymer-biomolecule complexes can be immobilized on a variety of solid supports, including, but not limited to silicon wafers, glass (e. g. glass slides, glass beads, glass [WAFERS ETC. ), SILICON RUBBER, POLYSTYRENE, POLYETHYLENE, TEFLON, SILICA GEL BEADS,] gold, indium tin oxide (ITO coated materials, e. g. glass or plastics), filter paper (e. g. nylon, cellulose and nitrocellulose), standard copy paper or variants and separation media or other chromatographic media.
  • solid supports including, but not limited to silicon wafers, glass (e. g. glass slides, glass beads, glass [WAFERS ETC. ), SILICON RUBBER, POLYSTYRENE, POLYETHYLENE, TEFLON, SILICA GEL BEADS,] gold, indium tin oxide (ITO coated materials, e.
  • Transfer of the conjugated polymer, the biomolecule or the conjugated polymer-biomolecule complexes to the solid support can be achieved by using, but not limited to, dip coating, spin-coating, microcontact printing, screen printing, ink jet technologies, spraying, dispensing and microfluidic printing by the use of soft lithography.
  • Immobilization of the conjugated polymer, the biomolecule or the conjugated polymer- biomolecule complexes are achieved by physical adhesion to the solid support by entrapment in a hydrogel matrix, or possible by treatment to create crosslinking at elevated temperatures,
  • Solvents for the conjugated polymers, the biomolecules or the conjugated polymer- biomolecule complexes of the present invention during the immobilization to the solid support can be, but are not limited to, water, buffered water solutions, methanol, ethanol, chloroform and combinations thereof. Supporting polymers of other kinds can also be added in this step.
  • the biomolecules When the biomolecules are immobilized on the solid support underneath, on top of or together with the conjugated polymer of the present invention they form a complex with the polyelectrolyte through non- covalent interactions. This complex is formed without covalent chemistry and is based on hydrogen bonding, electrostatic-and non-polar interactions between the conjugated polymer and the biomolecule.
  • the class of electronic devices here considered include both classical polymer electronic devices usable as rectifying elements (junction diodes, with subgroups in photodiodes and light emitting diodes), and field effect transistors. These junctions may be created in the build up of a fiber, either along the fiber or transverse to the fibre length; they may also be created in the junction of two crossing fibres. Junctions may be built by sequential deposition of two different polymers onto a fiber, in concentric geometry.
  • junctions between two semiconducting wires form a heterojunction, if the polymers are of two different bandgaps, and give rise to rectification along the junction.
  • Junctions between a metallic layer and a semiconducting layer may likewise realize rectification.
  • Junctions between semiconducting/insulating and metallic/insulating layers are essential parts of field effect devices, field effect transistors.
  • Crossing of electronic fibres may be accomplished by microfluidic tools, to introduce or to form the wires insides the channels of a microstructured stamp. It may also be done by mechanical crossing of fibres carried on surfaces.
  • Electronic current may pass both along the fibre and transverse to the fibre. Ionic currents may also pass along the fibre and transverse to it. Electronic currents in one fibre may be gated by ionic processes in another fibre; likewise ionic currents in one fibre may be controlled by electronic processes in another fibre. Electronic transport in one fibre may be controlled by field effect from another fibre, where the fibres are separated by insulating layers on the fibre.
  • the class of devices also include electrochemically operated hybrid devices, such as electrochemical diodes, triodes and multigate devices, electrochemical transistors, and field effect transistors driven by electrolytic gates.
  • electrochemically operated hybrid devices such as electrochemical diodes, triodes and multigate devices, electrochemical transistors, and field effect transistors driven by electrolytic gates.
  • Such devices for electronic processing and storage may also be incorporated in systems based on analog operations, say in variable resistors and connectors, suitable for neural network type systems.
  • the assembly of more complex structures may include logical functions implemented in digital logic (AND, OR, NOR, NAND logical gates, oscillators, memory shift registers).
  • Experimental Example 1 Optical detection of amyloid formation of bovine insulin in solution, using PTAA.
  • a stock-solution containing 1.0 mg PTAA/ml in deionized water was prepared.
  • a stock solution containing 320 ⁇ M bovine insulin in 25 mM HCl was placed in a water bath (65°C) to induce the amyloid formation.
  • 10 ⁇ l of the polymer stock-solution was mixed with 25 ⁇ l of the insulin stock-solution, and diluted to a final volume of 1500 ⁇ l with 20 mM Na-phosphate pH 7.0. After 5 minutes of incubation, the absorption spectrum was recorded.
  • Example 2 Fluorescent detection of amyloid formation in bovine insulin in solution, using PTAA.
  • a stock-solution containing 1.0 mg PTAA/ml in deionized water was prepared.
  • a stock solution containing 320 ⁇ M bovine insulin in 25 mM HCl was placed in a water bath (65°C) to induce the amyloid formation.
  • 10 ⁇ l of the polymer stock- solution was mixed with 25 ⁇ l of the insulin stock-solution, and diluted to a final volume of 1500 ⁇ l with 20 mM Na-phosphate pH 7.0. After 5 minutes of incubation, the emission spectrum was recorded.
  • Emission spectra were recorded on a ISA Jobin-Yvon spex FluoroMax-2 apparatus and samples were analyzed during a time period of 10 hours. All of the spectra were recorded with excitation at 400 nm. Amyloid formation is detected by a decrease of the emitted light and a shift of the emission maximum to a longer wavelength (Figure 4). The ratio of the intensity of the emitted light at 550 nm and 580 nm can be used to detect amyloid formation of bovine insulin (Figure 5).
  • Example 3 Fluorescent detection of amyloid formation of bovine insulin in solution, using PONT.
  • a stock-solution containing 1.5 mg PONT/ml in deionized water was prepared.
  • a stock solution containing 320 ⁇ M bovine insulin in 25 mM HCl was placed in a water bath (65°C) to induce the amyloid formation.
  • 10 ⁇ l of the polymer stock- solution was mixed with 25 ⁇ l of the insulin stock-solution, and diluted to a final volume of 1500 ⁇ l with 25 mM HCl. After 5 minutes of incubation, the emission spectrum was recorded. Emission spectra were recorded on a ISA Jobin-Yvon spex FluoroMax-2 apparatus and samples were analyzed during a time period of 10 hours.
  • Example 5 Fluorescent detection of amyloid formation of bovine insulin in POWT hydrogel spots on a surface. 1.0 ⁇ l droplets of POWT (1.0 mg/ml) were placed on a polystyrene surface and left to dry for 10 min. The polymer droplets were cross-linked with 2.5 ⁇ l bovine insulin solution (25 mM HCl) containing 5 ⁇ M native bovine insulin or amyloid fibril insulin, respectively.
  • Example 6 Fluorescent detection of amyloid formation of bovine insulin in PONT hydrogel spots on a surface. 1.0 ⁇ l droplets of PONT (1.5 mg/ml) were placed on a polystyrene surface and left to dry for 10 min. The polymer droplets were cross-linked with 2.5 ⁇ l bovine insulin solution (25 mM HCl) containing 5 ⁇ M native bovine insulin or amyloid fibril insulin, respectively.
  • Example 7 Fluorescent detection of amyloid formation of bovine insulin in PTAA hydrogel spots on a surface. 1.0 ⁇ l droplets of PTAA (1.0 mg/ml) were placed on a polystyrene surface and left to dry for 10 min. The polymer droplets were cross-linked with 2.5 ⁇ l bovine insulin solution (25 mM HCl) containing 5 ⁇ M native bovine insulin or amyloid fibril insulin, respectively.
  • Example 8 Fluorescent detection of PONT/bovine insulin amyloid fibrils complexes and PONT.
  • a stock solution containing 320 ⁇ M bovine insulin bovine insulin and 390 ⁇ M PONT (on a chain basis) in 25 mM HCl was placed in a water bath (65 0 C) to induce the amyloid formation.
  • 25 ⁇ l of the polymer/insulin stock-solution was diluted to a final volume of 1500 ⁇ l with 25 mM HCl. After 5 minutes of incubation, the emission spectrum was recorded. Emission spectra were recorded on a ISA Jobin-Yvon spex FluoroMax-2 apparatus and samples were analyzed during a time period of 25 hours.
  • Example 9 Morphology studies of PONT/bovine insulin amyloid fibrils complexes
  • a stock solution containing 320 ⁇ M bovine insulin bovine insulin and 390 ⁇ M PONT (on a chain basis) in 25 mM HCl was placed in a water bath (65°C) to induce the amyloid formation.
  • For transmission electron micrographs aliquots were collected at different time points during wire formation were diluted in 25 mM HCl and applied to carbon coated grids for 2 min. The grids were washed and negatively stained with uranyl acetate 2% (wt/vol) in water and air-dried before examined in a Phillips EM400 transmission electron microscope (TEM) at an accelerating voltage of 120 kV.
  • TEM transmission electron microscope
  • Example 10 Electrochemical doping of PONT/bovine insulin amyloid fibrils complexes
  • a stock solution containing 320 ⁇ M bovine insulin bovine insulin and 390 ⁇ M PONT (on a chain basis) in 25 mM HCl was placed in a water bath (65°C) to induce the amyloid formation.
  • a insulin/PONT sample incubated for 25 h at 65° C was centrifuged at 130krpm for 30 min. The pellet was resuspended in 25 mM HCl and the sample was drop casted on a clean glass substrate coated with indium doped tin oxide (ITO) (Balzer, BaltracomTM having a sheet resistance of 10 ohm/square).
  • ITO indium doped tin oxide
  • PEDOT/PSS from Bayer AG, EL grade
  • the sample was let to dry and mounted in a three electrode cell in an epifluorescence microscope (Zeiss Axiovert inverted microscope A200 Mot).
  • a platinum probe was used to contact the sample surface
  • an Ag/ AgCl e:arelectrode was used as reference electrode
  • an ITO coated glass surface was used as counter electrode.
  • the electrochemical measurements were preformed with an Autolab Pgstat 10 (EcoChemie, The Netherlands). 0.1 M LiClO 4 in methanol was used as electrolyte solution. Doping/dedoping of PONT was preformed at 0.9 V and -0.3 V respectively.
  • the fluorescence quenching and enhancement following the doping processes were recorded with an epifluorescence microscope (Zeiss Axiovert inverted microscope A200 Mot) equipped with a CCD camera (Axiocam), using a 470/40nm filter (LP515).
  • Example 11 Stretching of ⁇ DNA stained with YOYO-I and construction of ⁇ DNA/POWT complex nanowires A 10 mg/ml polystyrene (PS) solution in toluene was prepared. The PS solution was spin- coated onto clean extra planar glass slides at 2000 rpm for 1 min. For DNA stretching, a stock-solution of 25 ⁇ g ⁇ DNA/ml in 50 mM MES pH 5.55 buffer and a stock-solution of 10 ⁇ M YOYO-I fluorescence dye in 50 mM MES pH 5.55 buffer was prepared.
  • PS polystyrene
  • 10 ⁇ l of ⁇ DNA stock-solution was mixed with 8 ⁇ l of the YOYO-I stock-solution and diluted in 50 mM MES pH 5,55 buffer to a final volume of 500 ⁇ l.
  • a stock-solution of 0.5 mg POWT/ml in deionized water and a stock-solution of 25 ⁇ g ⁇ DNA/ml in 50 mM MES pH 5.55 buffer were prepared.
  • 150 ⁇ l of ⁇ DNA stock- solution was mixed with 10 ⁇ l of the POWT stock-solution and diluted in 50 mM MES pH 5,55 buffer to a final volume of 1500 ⁇ l.

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Abstract

L'invention concerne des procédés servant à préparer des matériaux et des dispositifs électroniques au moyen de l'auto-assemblage/agrégation de biomolécules afin de construire des dispositifs électroniques basés sur des polymères conjugués. Le polymère conjugué est exposé à la protéine, ce qui permet au polyélectrolyte et à la biomolécule conjugués d'exercer une interaction réciproque et de s'assembler automatiquement en fibres formant des solides. Ces fils sont semi-conducteurs ou métalliques en fonction du choix du polymère et de leur état de dopage. Les jonctions entre deux fils semi-conducteurs créent une hétérojonction, si les polymères possèdent deux structures de bande différentes et donnent lieu à une rectification le long de la jonction. Des jonctions peuvent également être créées par assemblage consécutif de deux polymères différents le long du diamètre de la fibre, ainsi que par dépôt de deux polymères différents contigus l'un à l'autre sur une fibre.
PCT/SE2005/001021 2004-06-28 2005-06-27 Procedes mettant en application l'auto-assemblage/agregation de biomolecules pour construire des dispositifs electroniques bases sur des polymeres conjugues WO2006001774A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
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EP2236512A1 (fr) * 2007-04-18 2010-10-06 Biochromix AB Liaison de formes pathologiques de protéines utilisant des polyélectrolytes conjugués
CN110818863A (zh) * 2019-11-01 2020-02-21 中国科学院长春应用化学研究所 一种基于聚噻吩的两亲嵌段聚合物、其制备方法和电活性胶束
CN113571636A (zh) * 2021-07-27 2021-10-29 南京邮电大学 一种柔性忆阻器件及其制备方法

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CN111650267B (zh) * 2020-06-11 2023-02-28 南京师范大学 一种系列共轭芳香分子掺杂蛋白质的制备及调节蛋白质电子传输带隙的方法

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Publication number Priority date Publication date Assignee Title
EP2236512A1 (fr) * 2007-04-18 2010-10-06 Biochromix AB Liaison de formes pathologiques de protéines utilisant des polyélectrolytes conjugués
CN110818863A (zh) * 2019-11-01 2020-02-21 中国科学院长春应用化学研究所 一种基于聚噻吩的两亲嵌段聚合物、其制备方法和电活性胶束
CN110818863B (zh) * 2019-11-01 2021-08-17 中国科学院长春应用化学研究所 一种基于聚噻吩的两亲嵌段聚合物、其制备方法和电活性胶束
CN113571636A (zh) * 2021-07-27 2021-10-29 南京邮电大学 一种柔性忆阻器件及其制备方法

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