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WO2005019210A1 - Detecteurs a base de polythiophene - Google Patents

Detecteurs a base de polythiophene Download PDF

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Publication number
WO2005019210A1
WO2005019210A1 PCT/GB2004/003616 GB2004003616W WO2005019210A1 WO 2005019210 A1 WO2005019210 A1 WO 2005019210A1 GB 2004003616 W GB2004003616 W GB 2004003616W WO 2005019210 A1 WO2005019210 A1 WO 2005019210A1
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WO
WIPO (PCT)
Prior art keywords
receptor
terthiophene
copolymer
bearing
binding
Prior art date
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Ceased
Application number
PCT/GB2004/003616
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English (en)
Inventor
Simon Joseph Higgins
Stewart Jeffrey Brown
Fouzi Mouffouk
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UK Secretary of State for Defence
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UK Secretary of State for Defence
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Filing date
Publication date
Application filed by UK Secretary of State for Defence filed Critical UK Secretary of State for Defence
Publication of WO2005019210A1 publication Critical patent/WO2005019210A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms

Definitions

  • the present invention is concerned with the production and use of polymers based on terthiophene compounds for sensing molecules in solution. Changes in the properties of conductive terthiophene polymers as a result of binding of ligands to specific receptor sites on sidechains form the basis for sensitive biosensors.
  • Conductometric sensors function by detecting the change in conductivity of the polymers, bound to a suitable film. The resistance between two adjacent microelectrodes is measured as a function of the concentration of analyte.
  • a potentiometric system may be used, in which changes in the system's redox potential in response to analyte binding are recorded.
  • One advantage to this approach is that it requires only one recording electrode, which may be incorporated in to the substrate film onto which the conducting polymers are bound. Colorimetric methods (depending on changes in the polymer's absorption properties) and changes in fluorescence properties may also be used as the basis of detection techniques.
  • Polythiophenes are particularly suitable since they respond to binding events with measurable changes in their electrical, redox and optical properties. This is because they are semiconductors with a comparatively small bandgap, and they can be p- doped at modest positive potentials. Moreover, 3-functionalised thiophenes are readily prepared, polythiophenes are accessible both chemically and electrochemically (Roncali, 1999) and, unlike polypyrroles, polythiophenes are stable in both their neutral and p-doped states. The electrogeneration of polythiophene films from thiophenes often requires highly positive potentials, which may degrade delicate functional groups.
  • Such systems may be used for the detection of a wide range of molecules, but are particularly suitable for specific detection of soluble ligands by cognate receptors. Sequence-specific binding and detection of nucleic acids by complementary single- stranded oligonucleotides linked to a biosensing apparatus is a particularly important application, but a wide variety of polypeptide receptors, antibodies or fragments thereof, or entirely synthetic chemical receptors have been used.
  • WO 03/024954 discloses a 3'-carboxyl terthiophene compound and its polymerisation with the subsequent covalent attachment of a single-stranded oligonucleotide via the 3'-carboxyl side chain.
  • electrochemically polymerised chains are irregular and poorly-characterised, giving relatively poor and inconsistent performance as biosensors.
  • polymerisation from pure functionalised monomers is expensive and unnecessary, since the resulting poorly defined high density of receptor-bearing sidechains is inefficient.
  • the invention provides a novel compound, succinic acid mono-(2- [2,2';5',2"]terthiophen-3'-yl-ethyl) ester, and a functionalised conductive polythiophene polymer derived from this compound. Also provided is an improved method of synthesising derivatised polymers capable of specifically binding soluble ligands.
  • the method comprises the steps of covalently attaching a receptor moiety and suitable spacer to the carboxyl-terminated ester monomers, copolymerising such receptor-bearing monomers with varied proportions of underivatised monomers to produce defined polymers with a defined density of receptor side-chains.
  • the invention provides an improved method of polymerising regioregular polythiophene, so as to produce a defined mixture of receptor-bearing and underivatised monomers so as to produce a regioregular array of receptors in a conducting polymer, attached to a solid substrate by solvent casting, suitable for use as a biosensor.
  • Preferred receptor moieties include single-stranded oligonucleotides, antibodies or functional antigen-binding fragments of antibodies, recombinant polypeptide receptor molecules, such as growth factor receptors, immunoglobulin superfamily receptors, integrins or lectins or functional ligand-binding fragments thereof.
  • Non-peptide receptors based on carbohydrates may also be used.
  • a high-affinity but non-specific synthetic receptor may be used, for example avidin or streptavidin, enabling detection of experimentally biotinylated molecules to be detected. This may be of use both as a means of detecting and purifying such biotinylated molecules but also as a model system for characterising and developing biosensor systems.
  • a biotin-bearing receptor may be used to detect avidin or avidin-containing molecules or complexes.
  • said functional ligand-binding receptor moiety is selected from the list consisting of single-stranded oligonucleotides, antibodies or functional antigen- binding fragments of antibodies, recombinant polypeptide receptor molecules or functional ligand-binding fragments thereof, biotin, avidin and streptavidin.
  • the functional ligand-binding receptor moiety may be linked to the polythiophene backbone of the polymer by a linker of variable length.
  • the linker contains from 5 to 20 in-chain atoms.
  • the in-chain atoms may, by way of example, be C, O, N or S, e.g. C or O. Included is a class of formulations in which all the in-chain atoms are all carbon. In one class of compounds there are 0, 1 , 2 or 3 in-chain atoms which are not carbon, e.g. 1 such non-carbon atom, and in a sub-class of compounds all these non-carbon in-chain atoms are oxygen.
  • non-carbon atoms are directly bonded to carbon atoms on either side of them in the chain, e.g. to form an ether linkage (typically -CH2-O-
  • L may be an alkylene group; in some instances it is an alkenylene group.
  • the in-chain bonds of the linker are typically double or single bonds; included is a class of compounds in which all the in-chain bonds are single bonds or are all single except one double bond.
  • the linker is unsubstituted; alternatively the linker may be substituted, for example each in-chain atom may have at least one substituent or, more frequently, the linker contains fewer substituent groups than in-chain atoms. In one class of compounds, no in-chain atom contains more than one substituent. Included are compounds in which the linker has 1 , 2 or 3 substituents, e.g. 1 substituent. As substituents there may be mentioned halogen (e.g. F or Cl), alkyl (e.g.
  • 1C to 4C for example methyl
  • alkoxy e.g. 1C to 4C, for example methoxy
  • aklythio e.g. 1C to 4C
  • haloalkyl e.g. 1C to 4C, for example trifluoromethyl
  • linker groups are -CH2-, -(CH 2 )2-, -(CHt ⁇ t ⁇ -, -(CH2)4-, -( C 2)5". -( CH 2)6 _
  • the invention provides a copolymer of 2,2'; 5', 2"-terthiophene and a receptor-bearing terthiophene derivative as described above.
  • the molar ratio of 2,2'; 5', 2"-terthiophene and the receptor-bearing terthiophene derivative monomers is between 50:1 and 2:1. More preferably, it is between 10:1 and 2:1. Most preferably it is 5: 1.
  • the invention provides a regioregular copolymer of terthiophene derivatives as described above, in particular a copolymer of receptor-bearing and unfunctionalised terthiophene derivatives.
  • the regioregular copolymer comprises at least different two receptor- bearing terthiophene derivatives. These may carry the same functional ligand- binding receptor moieties on different lengths of linker, which may give advantages in obtaining an optimal array of receptor moieties, or may carry different functional ligand-binding receptor moieties.
  • the regioregular copolymer is a functionalised regioregular poly-(3-hexylthiophene)-copoly-( ⁇ thiophen-3-yl ⁇ -hexan 1- ol).
  • the total monomer concentration is between 20mM and 1 mM, more preferably between 10mM and
  • the invention provides a method of preparing a regioregular, receptor-bearing copolymer of 2, 2'; 5', 2"-terthiophene and the receptor-bearing terthiophene derivative as described above, comprising the steps of mixing the monomers at a molar ratio of between 100:1 and 2:1 , ideally 5:1 , to a total concentration of between 0.1 and 100 mM, ideally 5 mM, in an organic electrolyte solution, preferably 0.2 M tetraethylammonium tetrafluoroborate in acetonitrile, and polymerising by electrochemical potential cycling, preferably between 0 V and +1.15 V vs saturated calomel reference electrode, at a scan rate of between 1 and 1000 mV s ⁇ preferably 10 mV s ⁇ 1 .
  • the number of repetitive scans (1 to 100) could be used as a control of film thickness.
  • 10 scans were employed
  • the invention provides a method of preparing a regioregular poly-(3-alkylthiophene) copolymer in which a controlled number of alkyl substituents bear, at their terminal carbon, a substituent, to which receptors may subsequently be attached.
  • the proportion of functionalised monomer in the polymer can be varied from 1 per 1000 thiophene rings, to 1 per 2 thiophene rings. Preferably, it is 1 :100 - 1 :5 rings. Most preferably, it is 1 per 20 thiophene rings.
  • the invention provides the use of a terthiophene derivative, a receptor-bearing terthiophene derivative, or a copolymer as described above as a sensor to detect the binding of an analyte.
  • binding of an analyte is detected by mean of a change in electrochemical impedence.
  • binding of an analyte is detected by mean of a change in redox potential or by mean of a change in optical properties.
  • the invention provides an apparatus comprising an electrochemical sensing copolymer as described above.
  • the binding of an analyte is detected by means of a change in the electroactivity of the copolymer.
  • the analyte may be dissolved in an aqueous buffer.
  • This is advantageous for the analysis of a great many biological molecules and allows greater speed and convenience of processing.
  • Detection methods based on potentiometric methods of measuring redox potentials require non-aqueous buffer systems (using, for example, acetonitrile).
  • the binding of an analyte is detected by means of a change in the optical properties of the copolymer.
  • this is a change in optical absorbance.
  • it may be a change in fluorescence.
  • the apparatus comprises a functionalised regioregular poly-(3-hexylthiophene)-copoly-( ⁇ thiophen-3-yl ⁇ -hexan 1- ol). More preferably it comprisies biotinylated regioregular poly-(3-hexylthiophene)- copoly-( ⁇ thiophen-3-yl ⁇ -hexan 1 -ol).
  • Figure 1 shows the reaction scheme for the synthesis of 'terthiophene 1' (the carboxyl-terminated ester of 3'-(2-hydroxyethyl)-2,2'; 5',2"-terthiophene) and 'terthiophene 2', its biotinylated derivative.
  • Figure 2 shows cyclic voltammograms (30 mV s ⁇ 1 ) of a 1 :terthiophene copolymer film before and after incubation with avidin.
  • Figure 3 shows cyclic voltammograms (30 mV s _1 ) of a 2:terthiophene copolymer film before and after incubation with avidin.
  • Figure 4 shows electrochemical impedance spectra of a 2:terthiophene copolymer film at various applied potentials, prior to incubation with avidin.
  • Figure 5 (A) shows polymer 4 (Scheme 1) in 1 :1 CHCI 3 :dmso; (B) after addition of 1 drop aqueous buffer containing excess BSA; (C) after addition of 1 drop aqueous buffer containing excess avidin.
  • Figure 7 shows IV characteristics of a spin-coated film of polymer 4 (Scheme 1) prior to buffer exposure (full line), after exposure to BSA in 0.1 M aq. NaCI/10 mM edta buffer (broken line), and after exposure to avidin in buffer (crosses).
  • Figure 8 shows a simple solid-state device comprising polymer 4 (Scheme 1) spin- coated onto gold finger electrodes deposited onto a glass substrate
  • Terthiophenes 1 and 2 were prepared by the sequence shown in Figure 1.
  • the 3'- (2-hydroxyethyl)-2,2':5',2 , '-terthiophene was prepared by a modified literature method (Scheib and Bauerle, 1999; Higgins et al, 2001), and esterified with excess succinyl chloride to give 1 after workup.
  • Terthiophene 1 was activated with 1 ,2,2,2- tetrachloroethyl- ⁇ /-succinimidyl carbonate (Jaouadi et al, 1987), then reacted with commercially-available biotin hydrazide to give 2.
  • Copolymers of 1 with 2,2':5',2"-terthiophene, and of 2 with 2,2':5',2"-terthiophene were grown by repetitive scan cyclic voltammetry (10 scans) on Pt disc electrodes, using a 5:1 mole ratio of 2,2':5',2"-terthiophene:1 (or 2), and a 5 mM total monomer concentration.
  • the cyclic voltammograms of the two copolymers in pure 0.2 M TEAT / CH 3 CN are shown in Figures 1 and 2.
  • a SNIFTIRS spectrum of a neutral terthiophene: 2 copolymer film (on a gold electrode) showed bands at 3180 and 3120 cm “1 (v NH ), 1730 cm “1 (sh; ester v C o), 1685 cm -1 (hydrazido v C o) (Asorga et al, 1993) and 1664 cm -1 (biotin v C o) (Sato and Machida, 1977) consistent with the presence of intact biotin moieties.
  • the change in electroactivity is consistent with the presence of an avidin adlayer which greatly slows the uptake of anions on electrooxidation of the polyterthiophene to its cationic (conducting) form, so that its rate is comparable with the voltammetric timescale.
  • the scan rate is decreased, the onset of oxidation occurs at less positive potentials, and the current maximum increases.
  • an intermediate scan rate (30 mV s ⁇ 1 ; Figure 3)
  • a nucleation loop is seen as the avidin-bound polymer is electro-oxidised.
  • Electrochemical impedance spectra confirmed this picture.
  • the oxidised form of the polymer showed a 45 ° line at high frequencies, due to Warburg impedance caused by ionic diffusion, and a near-vertical line at lower frequency, where the film behaves as a capacitor. This behaviour can be fitted within the classical dual rail transmission line circuit proposed for the analysis of conducting polymer impedance spectra (Albery et al, 1989; Ren and Pickup, 1993; Ren and Pickup, 2001).
  • Biotin was grafted to copolymer 3 using dicyclohexylcarbodiimide (DCC)-mediated, 4- (dimethylamino)pyridine (DMAP)-catalysed coupling in CHCI 3 .
  • bovine serum albumin 10 "8 mol. in 0.1 cm 3 buffer
  • BSA bovine serum albumin
  • polymer 4 (Scheme 1) can be used to fabricate both electrochemical and solid-state avidin detectors.
  • Figure 6 shows cyclic voltammograms of a drop-cast film of polymer 4 on a Pt disc electrode in 0.1 M Et 4 NBF 4 /CH 3 CN, before and after exposure to 10 ⁇ 9 moles of avidin in 1 mL of aqueous buffer. The large decrease and positive shift in the oxidation wave after exposure to avidin is consistent with the blocking of ion ingress/egress on polymer switching by the protein.
  • Example 3 A solid-state sensor device using biotinylated polyalkylthiophene
  • a simple solid-state device was fabricated by spin-coating ca. 100 nm of polymer 4 (Scheme 1) onto two gold finger electrodes (0.1 x 1 cm; 0.1 cm apart) deposited onto a hexamethyldisilazene-treated glass substrate (Figure 8).
  • Figure 7 shows the effect of avidin exposure on the IV characteristics (shown as log /; the polymers obeyed Ohm's law). While exposure of the polymer to BSA (10 ⁇ 8 moles in 1 cm 3 buffer) causes a very small change in conductivity, exposure of this device to excess avidin (10 " ⁇ moles in 1 cm 3 buffer) causes a lowering of conductivity by nearly four orders of magnitude.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne des procédés de production de polymères de polythiophène définis, destinés à être utilisés comme détecteurs électrochimiques. La copolymérisation de monomères porteurs de récepteurs en des proportions variées de monomères non dérivatisés fournit des polymères ayant une densité déterminée de chaînes latérales de récepteurs et améliore la consistance et la sensibilité lorsqu'ils sont utilisés comme détecteurs. L'invention concerne en outre des procédés améliorés de polymérisation de polythiophène régio-régulier fournissant une série régio-régulière de récepteurs dans un polymère conducteur, convenant pour l'utilisation comme biodétecteur. Enfin, l'invention concerne des fractions de monomères et de récepteurs spécifiques.
PCT/GB2004/003616 2003-08-23 2004-08-23 Detecteurs a base de polythiophene Ceased WO2005019210A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0319900A GB0319900D0 (en) 2003-08-23 2003-08-23 Polythiophene-based sensors
GB0319900.7 2003-08-23

Publications (1)

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WO2005019210A1 true WO2005019210A1 (fr) 2005-03-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101002415B1 (ko) 2008-01-09 2010-12-21 재단법인대구경북과학기술원 바이오 물질 감지 활성 표면용 고분자 링커

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0314009A2 (fr) * 1987-10-29 1989-05-03 Miles Inc. Polymères conductifs fonctionnels et leur application dans des appareils de diagnostic
US5596107A (en) * 1993-06-04 1997-01-21 Industrial Technology Research Institute Hydroxymethypolythiophene derivatives
WO2003024954A1 (fr) * 2001-09-12 2003-03-27 Pusan National University Industry-University Cooperation Foundation Nouveau compose d'acide terthiophene-3-carboxylique et methode de production du compose, polymere de terthiophene conducteur fonctionnalise contenant le compose en tant que monomere, procede de detection d'hybridation de l'adn au moyen du polymere, et methode de production d'une sonde d'adn
US20030195330A1 (en) * 2000-05-23 2003-10-16 Lambertus Groenendaal Functionalized $g(p)-conjugated polymers, based on 3,4-alkylenedioxythiophene

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0314009A2 (fr) * 1987-10-29 1989-05-03 Miles Inc. Polymères conductifs fonctionnels et leur application dans des appareils de diagnostic
US5596107A (en) * 1993-06-04 1997-01-21 Industrial Technology Research Institute Hydroxymethypolythiophene derivatives
US20030195330A1 (en) * 2000-05-23 2003-10-16 Lambertus Groenendaal Functionalized $g(p)-conjugated polymers, based on 3,4-alkylenedioxythiophene
WO2003024954A1 (fr) * 2001-09-12 2003-03-27 Pusan National University Industry-University Cooperation Foundation Nouveau compose d'acide terthiophene-3-carboxylique et methode de production du compose, polymere de terthiophene conducteur fonctionnalise contenant le compose en tant que monomere, procede de detection d'hybridation de l'adn au moyen du polymere, et methode de production d'une sonde d'adn

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BAEUERLE P ET AL: "POST-POLYMERIZATION FUNCTIONALIZATION OF CONDUCTING POLYMERS: NOVELPOLY(ALKYLTHIOPHENE)S SUBSTITUTED WITH EASILY REPLACEABLE ACTIVATED ESTER GROUPS", ADVANCED MATERIALS, VCH VERLAGSGESELLSCHAFT, WEINHEIM, DE, vol. 8, no. 3, 1 March 1996 (1996-03-01), pages 214 - 218, XP000558247, ISSN: 0935-9648 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101002415B1 (ko) 2008-01-09 2010-12-21 재단법인대구경북과학기술원 바이오 물질 감지 활성 표면용 고분자 링커

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