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WO1999026729A1 - Assemblage de derive de polythiophene sur une monocouche assemblee automatiquement (sam) - Google Patents

Assemblage de derive de polythiophene sur une monocouche assemblee automatiquement (sam) Download PDF

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Publication number
WO1999026729A1
WO1999026729A1 PCT/CA1998/001082 CA9801082W WO9926729A1 WO 1999026729 A1 WO1999026729 A1 WO 1999026729A1 CA 9801082 W CA9801082 W CA 9801082W WO 9926729 A1 WO9926729 A1 WO 9926729A1
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Prior art keywords
poly
methyl
thienyloxy
polymer
absorption
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PCT/CA1998/001082
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English (en)
Inventor
Karim Faid
Mario Leclerc
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Universite Laval
Universite de Montreal
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Universite Laval
Universite de Montreal
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Priority to AU13280/99A priority Critical patent/AU1328099A/en
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Anticipated expiration legal-status Critical
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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
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • 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

Definitions

  • the present invention relates to a methodology based on supramolecular polymeric assemblies for use in the areas of sensors, diagnostics, therapeutics and drug screening.
  • these polymers bearing adequately designed side chains, can undergo striking conformational changes when exposed to heat, light or various chemical and biochemical moieties giving rise to thermochromism, photochromism, ionochromism, or even biochromism.
  • optical transitions from deep violet to (maximum of absorption around 550 nm) to bright yellow (maximum of absorption near 400 nm) are believed to be related to a planar to non-planar (from highly conjugated to less conjugated) conformational transition of the backbone.
  • An object of the present invention is therefore to introduce the required side chains on the polymers through the use of acid-base interactions.
  • a further object of the present invention is to open the way to a whole novel area of surface modification through the use of electrostatic interactions.
  • a further object of the present invention is to provide a novel and simple way to create potential building blocks for supramolecular assemblies with new engineered chemical and optical properties
  • the present invention takes advantage of the fact that poly(2-(4-methyl-3-thienyloxy)ethanesulfonic acid) can react with various basic molecules to yield tunable, functionalized (through electrostatic interactions), and chromic polymers. New responsive polymers, both in solution and in the solid state, can then be easily prepared and utilized to detect a large number of different and targeted external stimuli.
  • aqueous solutions of sodium poly(2-(4- methyl-3-thienyloxy)-ethanesulfonate) undergo a thermally induced violet- to-yellow color (a shift of the absorption maximum from 540 nm to 400 nm) transition, which is believed to be related to a rod-to-coil (planar to non planar) conformational transition of the conjugated backbone.
  • thermochromic behavior observed upon heating of the neutral solutions revealed a decrease of the 540 nm absorption band and the apparition of a new band around 400 nm with the accompanying color changes from violet to yellow.
  • thermochromic feature is similar to that observed for the polymeric sodium salt, but the temperature range of the chromic transition was found to be strongly dependent on the nature of the substituents. Indeed, the increase of the bulkiness of the electrostatically bound substituents seems to disrupt more easily the planar polythiophene assemblies (Figure 2, inset).
  • the highly conjugated (violet) form is believed to be associated with intermolecular and intramolecular (through chain folding) aggregates, while upon heating, side-chain disordering disrupts these assemblies to yield nonplanar (less conjugated) polymer chains.
  • a similar cation size-dependant chromaticity has been recently reported with salts involving regioregular poly(thiophene-3-propionic acid) and could be explained by a similar sterically induced disruption of the aggregated phase.
  • polyoxyethylene substituents give rise to ionochromism, while azobenzene result in photochromic materials and biotinylated derivatives were used to detect the well-known avidin molecule.
  • the neutralization of the acid form can be monitored optically in real time through the decrease of the 800 nm absorption band, characteristic of an oxidized sulfonic acid-bearing polymer. Successive additions of different amine-bearing molecules result in multi- functionalized polymeric chains.
  • self assembled monolayers (SAM) of amine functionalized alkanethiolates or alkanesiloxanes can be modified by polythiophenes through complexation with the side-chain acid moieties.
  • a complex is formed between the sulfonic acids of the polymer and the amine groups of the SAMs.
  • electrochemical techniques can also be advantageously employed.
  • the recognition or binding events, between the functionalized side chains and the external stimuli, could be detected and measured by taking advantage of the large difference in the electronic structure between the planar and non planar forms of the polymer backbone, which results in significative shift of the oxidation potentials, allowing the design of highly selective and efficient, versatile and tunable electrochemical devices.
  • the oxidation potential of poly((3-(2-methyl- 1-butoxy)-4-methylthiophene), a polythiophene derivative that is stable in both its coiled (yellow) and planar (violet) form is found to be drastically different depending on its conformational state.
  • a potential of +0.88 V vs SCE is obtained while the planar form is oxidized at around +0.70 V.
  • the cumbersome multi-step synthesis of functional polythiophene derivative can be advantageously replaced by electrostatically binding an adequately functionalized derivative.
  • Figure 1 is a UV visible absorption spectra of an aqueous solution of poly(2-(4-methyl-3-thienyloxy)ethanesulfonic acid) ( ⁇ -JO "4 M) upon addition of n-butylamine, at room temperature;
  • Figure 2 is a temperature-dependant UV-visible absorption spectra of the 1 :1 complex between n-butylamine and poly(2- (4-methyl-3-thienyloxy)ethanesulfonic acid) in water. Evolution of the relative absorbency at 540 nm as a function of the temperature for (a) sodium poly(2-(4-methyl-3-thienyloxy)ethane sulfonate), (b) butylammonium poly(2-(4-methyl-3-thienyloxy)ethanesulfonate) and (c) tetrabutylammonium poly(2-(4-methyl-3-thienyloxy)ethane sulfonate);
  • Figure 3 is a UV-visible absorption spectra of the 1 :1 complex between biocytinhydrazide and oly(2-(4-methyl-3- thienyloxy)ethanesulfonic acid) ( ⁇ 5 x 10 7 mol) as a function
  • Figure 4 is a schematic description of the modified electrode
  • Figure 5 is a cyclic voltammogram of a monolayer deposited on an aminosilane-treated ITO electrode of (a) poly(2-(4- methyl-3-thienyloxy)ethanesulfonic acid), (b) a 0.5:1 complex between biocytinhydrazide and poly(2-(4-methyl-3-thienyloxy)ethanesulfonic acid), and (c) a 0.5:1 complex between biocytin hydrazide and poly(2-(4-methyl- 3-thienyloxy)ethanesulfonic acid) dipped into an aqueous avidin solution.
  • Figure 6 is a cyclic voltammogram and UV-visible absorption spectrum of cast films of poly(3-(2-methyl-1-butoxy)-4- methylthiophene in (1) a highly conjugated form and (2) a less conjugated form. All cyclovoltammograms have been recorded in acetonitrile with 0JM of tetrabutylammonium tetrafluoroborate at a scan rate of 100mV/s vs Ag/AgCI.
  • the absorption bands at 540 and 580 nm are still visible, even at 100°C, in the case of the polymer neutralized by sodium hydroxide while in the two other cases these bands have almost disappeared around 70-80°C.
  • the evolution of the absorption at 540 nm as a function of temperature reveals a significant difference between the behavior of the different polymers, with a very significant and rapid depletion of the 540 nm band in the case of the tetrabutylammonium substituents.
  • the introduction of such a bulky substituents induces a more facile disruption of the planar conformation compared to the two other cases.
  • Self-acid doped poly(2-(3-thienyloxy)ethane sulfonate)s and poly(2-(4-methyl-3-thienyloxy)ethanesulfonic acid) exhibits a large absorption band around 800 nm, characteristic of an oxidized and conducting (S S/cm) form.
  • This self-acid-doping process is fully reversible by the neutralization of the acid moieties by sodium hydroxide solution.
  • the absorption at 800 nm is decreasing with the addition of increasing amount of sodium hydroxide allowing real time monitoring of the neutralization process and hence modulation of the properties and characteristics of the resulting polymers.
  • thermochromic characteristics of polythiophenes In addition to the modulation of the thermochromic characteristics of polythiophenes through the tuning of the electrostatically attached substituents, various functional substituents can be easily attached to the polythiophene backbone combining the inherent chromic properties of the latter species with the affinity and/or recognition properties of adequately selected substituents, opening the way to the fabrication of integrated chemical systems which incorporate both a trigger and a transducer.
  • biotinylated polythiophene derivative can be advantageously replaced by the electrostatic binding of an adequately functionalized biotin derivative (i.e. biocytin hydrazide, an amine functionalized biotin derivative) to poly(2-(4-methyl-3-thienyloxy)- ethanesulfonic acid).
  • biocytin hydrazide an amine functionalized biotin derivative
  • water-soluble polythiophene derivative bearing a biotin molecule
  • water-soluble polythiophene derivative bearing a biotin molecule
  • biocytin an amine-terminated and highly water-soluble biotin derivative
  • poly(2-(4- methyl-3-thienyloxy)ethanesulfonic acid) A deep purple solution was obtained with its main absorption around 530 nm and, by adding a few percent of a co-solvent (methanol, ethanol, tetrahydrofuran,...), the main absorption can be tuned at will.
  • the solution composition is adjusted in such a way that the main absorption is around 400 nm, indicating that the main chains are predominantly in the coiled form (a similar effect can be obtained in pure water by increasing the temperature).
  • the difference between these two systems may be due to the different density and distribution of the binding moieties, multiple bindings to avidin creating a rigidification of the polythiophene backbone and a single binding leading to a coil conformation.
  • regioregular polythiophene derivatives bearing covalently attached oxyethylene oligomers can detect optically the presence of several alkali metal ions.
  • This characteristic can be duplicated with the electrostatic complexation of amino-oligo(oxyethylene) to the sulfonic acid polythiophene derivative.
  • amino- polyoxyethylene is electrostatically complexed to sulfonic acid-bearing polythiophenes to chromically detect the presence of several alkali metal ions.
  • KSCN potassium thiocyanate
  • photochromic polythiophenes is obtained through acid-base complexation with 4- phenylazolaniline.
  • the predominantly frans-azobenzene side chains undergo an isomerization forcing the main polymeric chains to a rod-to-coil transition, in a manner similar to what has been observed in regioeregular polythiophenes covalently modified by azobenzene moieties.
  • diaminated molecules permits to obtain positively charged polythiophenes derivatives, allowing the design of supramolecular assemblies through the alternate binding of oppositely charged moieties.
  • poly(2-(4-methyl-3- thienyloxy)ethanesulfonic acid) can interact with silanized glass bearing terminal amine groups. Deposition of the polymer occurs with, as a direct consequence, the apparition of absorption bands in the range 450-500 nm. It has to be noticed that all the deposited polymer seems to be neutralized, with no more non-complexed sulfonic acid as evidenced by the complete disappearance of the 800 nm band. When a partially neutralized solution is used, a functionalized polythiophene monolayer electrostatically attached to the aminated substrate can be obtained .
  • the generality of the acid-base complexation reactions between poly(2-(4-methyl-3-thienyloxy)-ethanesulfonic acid) and amine- bearing molecules also opens the way to a novel area of surface modification through the use of electrostatic interactions.
  • a monolayer of the oxidized self-acid- doped polymer is then transferred onto the substrate.
  • An absorption band appears in the range of 500-550 nm, indicating an acid-base interaction (neutralization) between the amine-bearing substrate and the acidic polymer.
  • the deposition of monolayers is particularly critical for these solid state sensors since it is believed that the interaction between large biochemical species and binding sites will mainly occur at the interface, and therefore, it is important to maximize the surface/volume ratio for such applications.
  • any perturbation in the conformation of the main chain may result in a huge difference in the electronic structure of these materials and hence in their electrochemical properties.
  • /V-butylamine shows a marked pale grey-to-violet color transition with the decrease of the initial absorption band at 800 nm and the increase of a new band centered around 540 nm, indicating a progressive neutralization of the acidic and oxidized form with the concurrent formation of a neutral and amine-bearing polymeric material (Figure 1).
  • Amino-poly-(ethylene glycol) (amino-PEG)(Sherwater), n-butylamine, 4-phenyl-azolaniline, tetrabutylammonium tetrafluoroborate, tetrabutylammonium bromide, 3- aminopropyltrimethoxysilane (Aldrich), and biocytin and avidin (Pierce) were used as received.
  • Neutralization of the sulfonic acid polymeric solution was usually carried out by the stepwise addition of aliquots of the various amine bearing molecules.
  • Amino-functionalized silanized ITO- coated glass has been prepared following well established procedures.
  • an ITO-coated glass (Applied glass) plate was dipped in a 70-30 H 2 SO 4 -H 3 O 2 solution for 10 s in such a way as to enhance the hydrophilic nature of the surface to ensure the proper anchorage of the siloxane groups without destroying the conductive oxide layer.
  • the glass plates are silanized by dipping them in a 5% solution of aminopropyl trimethoxysilane in toluene for various periods of time.
  • a immersion time of 30 mn was found to be optimum in order to avoid the occurrence of multi layer deposition while obtaining an acceptable surface coverage.
  • the glass plates were heated to 105°C for 1 h to allow the condensation reaction of the siloxane to proceed.
  • the ITO electrodes were stored in dry argon prior to use.
  • the electrostatic transfer of poly(2-(4-methyl-3-thienyloxy)ethanesulfonic acid) onto the ITO-coated glass slides was carried out by dipping the slides in a 0.01 M aqueous solution of the polymer.
  • a 50 % pre-neutralization of the sulfonic acid polymer with biocytin hydrazide allows the transfer of biotinylated polythiophene onto amine-bearing silanized ITO-coated glass.
  • UV-visible absorption spectra were obtained with a Hewlett- Packard diode array spectrophotometer (Model 8452A). Cyclic voltammetry measurements were obtained with a EG&G potentiostat/galvanostat (Model 273). Ag/AgCI reference electrode and platinum electrodes were used. Electrochemical measurements were performed at 100 mV/s with use of an electrolyte made of 0J M tetrabutylammonium tetrafluoroborate dissolved in acetonitrile. The silanized ITO-coated glass electrodes are dipped for various periods of time in different polymeric solutions. After copious rinsing to remove unbound polymeric chains and drying with dry argon, it was found that an immersion time of 1 min is sufficient to obtain reproducible cyclic voltammograms.

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Abstract

Cette invention concerne un procédé permettant d'obtenir des dispositifs monolithiques, lequel consiste à appliquer des monocouches de polythiophènes en utilisant des monocouches assemblées automatiquement (SAM) et porteuses d'amine, un complexe solide étant formé entre les groupes acide sulfonique restants à l'aide substituants choisis judicieusement. Il est ainsi possible d'obtenir facilement des substrats électro-actifs fonctionnalisés qui peuvent servir à effectuer diverses réactions ultérieures et peuvent faire preuve d'une reconnaissance intéressante en ce qui concerne les caractéristiques de réponse aux champs. Cette méthodologie, qui fait appel à des ensembles polymères supramoléculaires, peut trouver de nombreuses applications dans les domaines des capteurs, des diagnostics, des procédés thérapeutiques et du criblage de médicaments.
PCT/CA1998/001082 1997-11-21 1998-11-20 Assemblage de derive de polythiophene sur une monocouche assemblee automatiquement (sam) Ceased WO1999026729A1 (fr)

Priority Applications (1)

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AU13280/99A AU1328099A (en) 1997-11-21 1998-11-20 Assembly of polythiophene derivative on a self-assembled monolayer (sam)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002025282A3 (fr) * 2000-09-22 2002-11-14 Motorola Inc Procede permettant de faire adherer des polymeres sur des substrats a revetement metallique
WO2002006407A3 (fr) * 2000-07-17 2003-02-13 Harvard College Surfaces resistant a l'adsorption d'especes biologiques
WO2002081735A3 (fr) * 2001-04-05 2003-04-17 Infectio Diagnostic Inc Detection de polymeres charges negativement au moyen de derives polythiophenes cationiques hydrosolubles
US6916506B2 (en) * 2001-10-10 2005-07-12 Seiko Epson Corporation Method for forming thin film and method for forming electronic device
US7138121B2 (en) 2003-01-23 2006-11-21 Spangler Brenda D Biosensors utilizing dendrimer-immobilized ligands and there use thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4992300A (en) * 1988-05-24 1991-02-12 Matsushita Electric Industrial Co., Ltd. Manufacturing method for a recording medium or a recording head
EP0511650A1 (fr) * 1991-04-30 1992-11-04 Matsushita Electric Industrial Co., Ltd. Film antistatique et méthode de fabrication
US5338571A (en) * 1993-02-10 1994-08-16 Northwestern University Method of forming self-assembled, mono- and multi-layer fullerene film and coated substrates produced thereby
WO1995002251A2 (fr) * 1993-07-01 1995-01-19 Massachusetts Institute Of Technology Auto-assemblage moleculaire de polymeres electroconducteurs
US5624711A (en) * 1995-04-27 1997-04-29 Affymax Technologies, N.V. Derivatization of solid supports and methods for oligomer synthesis

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4992300A (en) * 1988-05-24 1991-02-12 Matsushita Electric Industrial Co., Ltd. Manufacturing method for a recording medium or a recording head
EP0511650A1 (fr) * 1991-04-30 1992-11-04 Matsushita Electric Industrial Co., Ltd. Film antistatique et méthode de fabrication
US5338571A (en) * 1993-02-10 1994-08-16 Northwestern University Method of forming self-assembled, mono- and multi-layer fullerene film and coated substrates produced thereby
WO1995002251A2 (fr) * 1993-07-01 1995-01-19 Massachusetts Institute Of Technology Auto-assemblage moleculaire de polymeres electroconducteurs
US5624711A (en) * 1995-04-27 1997-04-29 Affymax Technologies, N.V. Derivatization of solid supports and methods for oligomer synthesis

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002006407A3 (fr) * 2000-07-17 2003-02-13 Harvard College Surfaces resistant a l'adsorption d'especes biologiques
US7276286B2 (en) 2000-07-17 2007-10-02 President & Fellows Of Harvard College Surfaces that resist the adsorption of biological species
US7494714B2 (en) 2000-07-17 2009-02-24 President & Fellows Of Harvard College Surfaces that resist the adsorption of biological species
WO2002025282A3 (fr) * 2000-09-22 2002-11-14 Motorola Inc Procede permettant de faire adherer des polymeres sur des substrats a revetement metallique
WO2002081735A3 (fr) * 2001-04-05 2003-04-17 Infectio Diagnostic Inc Detection de polymeres charges negativement au moyen de derives polythiophenes cationiques hydrosolubles
US7083928B2 (en) 2001-04-05 2006-08-01 Infectio Diagnostic (I.D.I.), Inc. Detection of negatively charged polymers using water-soluble, cationic, polythiophene derivatives
US7446213B2 (en) 2001-04-05 2008-11-04 Geneohm Sciences Canada, Inc. Detection of negatively charged polymers using water-soluble, cationic, polythiophene derivatives
US7601503B2 (en) 2001-04-05 2009-10-13 Geneohm Sciences Canada, Inc. Detection of negatively charged polymers using water-soluble, cationic, polythiophene derivatives
EP2404915A1 (fr) * 2001-04-05 2012-01-11 Infectio Diagnostic (I.D.I.) Inc. Détection de polymères charges négativement au moyen de dérivés polythiophenes cationiques hydrosolubles
US6916506B2 (en) * 2001-10-10 2005-07-12 Seiko Epson Corporation Method for forming thin film and method for forming electronic device
US7138121B2 (en) 2003-01-23 2006-11-21 Spangler Brenda D Biosensors utilizing dendrimer-immobilized ligands and there use thereof

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Publication number Publication date
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