Macrocycle embedded organic electronic materials, composites, and compositions for chemical sensing

Patent metadata

Field	Value
Publication number	US-12320774-B2
Application number	US-202117519083-A
Country	US
Kind code	B2
Filing date	Nov 4, 2021
Priority date	Nov 4, 2020
Publication date	Jun 3, 2025
Grant date	Jun 3, 2025

Abstract

A semiconductor sensor device for detecting an analyte including a semiconducting layer, one or more organic molecules in the semiconducting layer, and one or more receptor molecules, comprising a poly-cyanostilbene macrocycle, wherein the one or more receptors is embedded within or onto the semiconducting layer of the semiconductor sensor device. Also disclosed is a method of preparing the semiconductor sensor device including a step of coupling the one or more receptor molecules into or onto the semiconducting layer of the semiconductor sensor device, a dielectric surface, or an electrode surface. Also described is chemical sensing device including the semiconductor sensor device and other elements of a sensing device.

First claim

The invention claimed is:

1. A semiconductor sensor device for detecting an analyte, comprising
a semiconducting layer,
one or more organic molecules in the semiconducting layer comprising a π-conjugated polymer having at least 2 repeating units, and
one or more receptor molecules, comprising a poly-cyanostilbene macrocycle according to Formula I:

wherein R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of an alkenyl group comprising from 2 to 20 carbon atoms, an alkyl group comprising from 2 to 20 carbon atoms, an alkoxy group comprising from 2 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, —(CH 2 ) 1-20 —NH—(CH 2 ) 1-20 —CH 3 , hydrogen, ethynyl, arylethynylene, -halo, —OR 9 , —N(R 10 R 11 ), —CO 2 R 12 , and —C(O)—N(R 13 R 14 ), wherein R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are each independently selected from the group consisting of an alkenyl group comprising from 2 to 20 carbon atoms, an alkyl group comprising from 2 to 20 carbon atoms, an alkoxy group comprising from 2 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon and atoms, —(CH 2 ) 1-20 —NH—(CH 2 ) 1-20 —CH 3 , and hydrogen, wherein the one or more receptor molecules are embedded within or onto the semiconducting layer of the semiconductor sensor device, wherein the semiconductor sensor device is stable in aqueous environments.

2. The semiconductor sensor device of claim 1 , wherein the one or more organic molecules in the semiconducting layer further comprises small molecules having a number average molecular weight of from about 50 g/mol to about 5,000 g/mol, as measured by gel permeation chromatography and/or NMR.

3. The semiconductor sensor device of claim 1 , wherein the π-conjugated polymer comprises repeat units (n)≥15, and having a molecular weight from about 15,000 g/mol to about 500,000 g/mol, as measured by gel permeation chromatography.

4. The semiconductor sensor device of claim 1 , having a loading percentage of the one or more organic molecules to the one or more receptor molecules of from about 1 wt. % to about 50 wt. %.

5. The semiconductor sensor device of claim 1 , wherein the R 1 , R 2 , R 3 , R 4 and R 5 are each a tert-butyl group.

6. The semiconductor sensor device of claim 1 , wherein the one or more organic molecules comprises poly[[2,5-bis(2-decyltetradecyl)-2,3,5,6-tetrahydro-3,6-dioxopyrrolo[3,4-c]pyrrole-1,4-diyl][2,2′-bithiophene]-5,5′-diyl-(1E)-1,2-ethenediyl[2,2′-bithiophene]-5,5′-diyl](PDVT).

7. The semiconductor sensor device of claim 1 , wherein the π-conjugated polymer has a repeat unit according to Formula (II):

wherein E represents an “electron donating group”, R 6 and R 7 are each independently selected from a hydrocarbyl group comprising from 1 to about 50 carbon atoms, R 8 may be a hydrocarbyl group comprising from 1 to about 20 carbon atoms, or a thiophene group, and n may be an integer of greater than 15.

8. The semiconductor sensor device of claim 1 , further comprising a two-terminal chemresistor, comprising a source electrode and a drain electrode with a chemically sensitive semiconductor material comprising a channel.

9. The semiconductor sensor device of claim 1 , further comprising a three-terminal transistor, comprising a source, a drain, and a gate electrode, configured to enhance an electrical conductivity of a chemically sensitive semiconductor material.

10. A method of preparing the semiconductor sensor device of claim 1 , comprising a step of coupling the one or more receptor molecules into or onto the semiconducting layer of the semiconductor sensor device, a dielectric surface, or an electrode surface.

11. The method of claim 10 , wherein the one or more organic molecules and the one or more receptor molecules are deposited via spin-coating, drop-casting, dip-coating, slot-die coating, doctor blading, or bar coating to form one or more of the semiconducting layers.

12. The method of claim 10 , wherein the one or more organic molecules and the one or more receptor molecules are within the semiconducting layer of the semiconductor sensor device.

13. The method of claim 10 , wherein the one or more receptor molecules are chemically incorporated into the one or more organic molecules via chemical reaction throughout the semiconducting layer of the semiconductor sensor device.

14. The method of claim 10 , wherein the one or more receptor molecules are physically entrapped in the semiconducting layer.

15. A chemical sensor system for detecting analyte comprising a semiconductor sensor device including
one or more transistors each having a conductive channel including a semiconducting layer comprising
one or more organic molecules including a π-conjugated polymer having at least 2 repeating units, and
one or more receptor molecules comprising a poly-cyanostilbene macrocycle according to Formula (I):

wherein R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of an alkenyl group comprising from 2 to 20 carbon atoms, an alkyl group comprising from 2 to 20 carbon atoms, an alkoxy group comprising from 2 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, —(CH 2 ) 1-20 —NH—(CH 2 ) 1-20 —CH 3 , hydrogen, ethynyl, arylethynylene, -halo, —OR 9 , —N(R 10 R 11 ), —CO 2 R 12 , and —C(O)—N(R 13 R 14 ), wherein R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are each independently selected from the group consisting of an alkenyl group comprising from 2 to 20 carbon atoms, an alkyl group comprising from 2 to 20 carbon atoms, an alkoxy group comprising from 2 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, —(CH 2 ) 1-20 —NH—(CH 2 ) 1-20 —CH 3 , and hydrogen, wherein the one or more receptor molecules is embedded within or located on a surface of the semiconducting layer of the semiconductor sensor device, a sample configured to hold a target molecule and the target molecule has a selective affinity to bind with the one or more receptor molecules, an assay system configured to bring the semiconductor sensor device in contact with the sample, a digital read-out, and a data processing system.

16. The chemical sensor system of claim 15 , wherein the system comprises two or more of the semiconductor sensor devices.

17. The chemical s

Assignees

• Univ Of Southern Mississippi
• Univ Indiana Trustees

Inventors

• Azoulay Jason
• Tropp Joshua
• Kaphle Vikash
• Benasco Anthony
• Flood Amar

Classifications

• G01N27/4145

  specially adapted for biomolecules, e.g. gate electrode with immobilised receptors · CPC title

• H10K10/40

  Organic transistors · CPC title

• H10K85/111

  comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene · CPC title

• H10K85/60

  Organic compounds having low molecular weight (H10K85/10 - H10K85/50 take precedence) · CPC title

• H10K10/484

  characterised by the channel regions · CPC title