Chemical sensors based on carbon nanotubes functionalised by conjugated polymers for analysis in aqueous medium

Patent metadata

Field	Value
Publication number	US-11697707-B2
Application number	US-201816604423-A
Country	US
Kind code	B2
Filing date	Apr 10, 2018
Priority date	Apr 10, 2017
Publication date	Jul 11, 2023
Grant date	Jul 11, 2023

Abstract

Disclosed are conjugated polymers bearing chemical probes and the use thereof for the preparation of chemical sensors based on carbon nanotubes allowing the selective detection of analytes in water.

First claim

The invention claimed is:

1. A conjugated polymer comprising monomer units A chosen from the monomer units of formulas:

where X denotes a carbon, silicon or germanium atom,
R 1 and R 2 , identical or different when they are present in the same monomer unit, are monovalent groups containing at least one group T chosen from the groups oxime, iminodiacetic acid or one of the salts thereof, a macrocyclic group including from 9 to 36 atoms of which at least 3 heteroatoms chosen from oxygen, nitrogen and the combinations thereof, or a group of formula T1:

where W denotes a sulphur or oxygen atom, R U1 and R U2 denote independently a hydrogen atom, an optionally substituted alkyl group or an aryl group,
denotes the attachment point of the monomer unit to the polymer chain, the carbon atoms of the monomer units A being optionally substituted, and
the groups R1 and/or R2 are groups of formula -L-T, where L denotes a divalent group.

2. The conjugated polymer of claim 1 , further comprising monomer units B chosen from the monomer units of formulas:

where X denotes a carbon, silicon or germanium atom; Y denotes a sulphur, oxygen or selenium atom; Z denotes a carbon or nitrogen atom, the carbon atoms of the monomer units B being optionally substituted,
denotes the attachment point of the monomer unit to the polymer chain, the groups R′ 1 and R′ 2 , identical or different when they are present in the same monomer unit, represent alkyl or alkoxyl groups comprising from 4 to 20 carbon atoms, linear or branched,
the group R′ 3 represents an alkyl group comprising from 4 to 20 carbon atoms, linear or branched, an aryl group substituted by one or a plurality of alkyl groups comprising from 4 to 20 carbon atoms, linear or branched, or an acyl group of formula —C(O)R′ 5 , where R′ 5 represents an alkyl group comprising from 4 to 20 carbon atoms, linear or branched,
the group R′ 4 represents an aryl group or an alkyl group comprising from 4 to 20 carbon atoms, linear or branched.

3. The conjugated polymer of claim 1 , further comprising monomer units of formula B1a:

where X denotes a carbon, silicon or germanium atom;
denotes the attachment point of the monomer unit to the polymer chain, and
the groups R′ 1 and R′ 2 , identical or different when they are present in the same monomer unit, represent alkyl or alkoxyl groups comprising from 4 to 20 carbon atoms, linear or branched.

4. The conjugated polymer of claim 1 , wherein it comprises monomer units of formula A3a or A3b, where L denotes a divalent group and T comprises at least one oxime function:

5. The conjugated polymer of claim 1 , wherein it comprises monomer units of formulas A1a′ or A1a″, where L denotes a divalent group, T1 is as defined in claim 1 and T2 includes an iminodiacetic acid group or one of the salts thereof connected via the nitrogen atom thereof:

6. The conjugated polymer of claim 1 , wherein it complies with one of the following formulas:

wherein p and q are identical or different integers ranging from 1 to 5 for p and from 0 to 20 for q and n denotes the degree of polymerisation.

7. A carbon nanotubes functionalised by at least one conjugated polymer comprising monomer units A chosen from the monomer units of formulas:

where X denotes a carbon, silicon or germanium atom,
R 1 and R 2 , identical or different when they are present in the same monomer unit, are monovalent groups containing at least one group T chosen from the groups oxime, iminodiacetic acid or one of the salts thereof, a polydentate Lewis base including at least two coordinating nitrogen and/or oxygen atoms, a macrocyclic group including from 9 to 36 atoms of which at least 3 heteroatoms chosen from oxygen, nitrogen and the combinations thereof, or a group of formula T1:

where W denotes a sulphur or oxygen atom, R U1 and R U2 denote independently a hydrogen atom, an optionally substituted alkyl group or an aryl group,
denotes the attachment point of the monomer unit to the polymer chain, the carbon atoms of the monomer units A being optionally substituted, and
the groups R 1 and/or R 2 are groups of formula -L-T, where L denotes a divalent group.

8. The carbon nanotubes of claim 7 , wherein the functionalisation of the carbon nanotubes by said at least one conjugated polymer is of non-covalent nature.

9. The carbon nanotubes of claim 7 , wherein the conjugated polymer complies with one of the following formulas:

10. The carbon nanotubes of claim 7 , wherein the group T is a polydentate Lewis base including at least two coordinating nitrogen atoms chosen from the following groups, optionally substituted: 2,2′-bipyridine (D5), 1,10-phenanthroline (D4), 2,9-dimethyl-1,10-phenanthroline, 1,10-phenanthroline-5,6-dione, imidazo[4,5-f]-1,10-phenanthroline of formula D1, 2,2′-bipyrimidine (D3), 2,2′:6′,2″-terpyridine (D7), dipyrido-[3,2-a:2,3′-c]phenazine (D2), a 2,6-bis(2-benzimidazolyl)pyridine of formula D6, a 2-(2-pyridyl)benzimidazole of formula D8, thiabendazole (D9), R 3 , R 3a in the formulas hereinafter denoting independently from one another a hydrogen atom or an optionally substituted alkyl, optionally substituted alkylene, aryl, or arylene group:

11. A system for the detection and/or assay of one or a plurality of ionic chemical species in a fluid, comprising at least one chemical sensor, said chemical sensor comprising a support and at least two electrodes disposed on said support, the support being at least partially coated with a layer of a composition comprising carbon nanotubes functionalised by at least one conjugated polymer of claim 1 , said composition layer ensuring electrical contact between the electrodes and forming the sensitive element of the sensor.

12. The system of claim 11 , comprising at least two chemical sensors, for the detection and/or assay of at least two ionic chemical species in a fluid.

13. The system of claim 11 , wherein the ionic chemical species is chosen from hypochlorite, chl

Assignees

• Ecole Polytech
• Centre Nat Rech Scient
• Institut Francais Des Sciences Et Technologies Des Transp De Lamenagement Et Des Reseaux Ifsttar

Inventors

• Zucchi Gaël
• Lebental Bérengère
• Loisel Loic
• Ramachandran Sasikumar
• Flores Gutiérrez Alfredo
• Wang Xinyang
• Godumala Mallesham
• Bodelot Laurence

Classifications

• C08G2261/148

  Side-chains having aromatic units · CPC title

• G01N27/127

  comprising nanoparticles · CPC title

• C08G2261/12

  Copolymers · CPC title

• C01B32/174

  Derivatisation; Solubilisation; Dispersion in solvents · CPC title

• C08G2261/143

  Side-chains containing nitrogen · CPC title