Biofunctional thiophene monomers and polymers thereof for electronic biomedical devices

Patent metadata

Field	Value
Publication number	US-12252582-B2
Application number	US-202017637108-A
Country	US
Kind code	B2
Filing date	Aug 28, 2020
Priority date	Aug 29, 2019
Publication date	Mar 18, 2025
Grant date	Mar 18, 2025

Abstract

The functionalized 3,4-alkylenedioxythiophene (ADOT+) monomers can be represented by a chemical formula (CR 1 R 2 )(CR 3 R 4 )(CR 4 R 5 ) x O 2 C 4 H 2 S, wherein x=0 or 1; wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is independently selected from hydrogen, a hydrocarbyl moiety, and a heteroatom-containing functional group; and wherein at least one of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 comprises the heteroatom-containing functional group selected from an aldehyde, a maleimide, and their derivatives thereof. Also, disclosed herein are aldehyde derivatives represented by (ADOT-CH 2 —NH) p Y and a maleimide derivative represented by (ADOT-(CH 2 ) q —N) p Z where p=1-2 and each of Y and Z is a hydrocarbyl moiety or a biofunctional hydrocarbyl moiety. In an embodiment of the ADOT+ monomers, one of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is replaced by a direct bond to an amide group, an azide group, or an ester group of a biofunctional hydrocarbyl moiety. Also, disclosed herein are polymers and copolymers made therefrom.

First claim

What is claimed is:

1. A biofunctionalized 3,4-alkylenedioxythiophene monomer represented by a chemical formula (C 1 R 1 R 2 )(C 2 R 3 R 4 )(C 3 R 5 R 6 ) x O 2 C 4 H 2 S (A′DOT+, where A′ represents C 1 R 1 R 2 )(C 2 R 3 R 4 )(C 3 R 5 R 6 ) x ),
wherein x=0 or 1, when x=0, the functionalized 3,4-alkylenedioxythiophene monomer is 3,4-ethylenedioxythiophene (E′DOT+; where E′ represents C 1 R 1 R 2 )(C 2 R 3 R 4 )) and when x=1, the functionalized 3,4-alkylenedioxythiophene monomer is functionalized 3,4-propylenedioxythiophene (Pro′DOT+; where Pro′ represents C 1 R 1 R 2 )(C 2 R 3 R 4 )(C 3 R 5 R 6 )),
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is independently selected from hydrogen, a hydrocarbyl group, and a heteroatom-containing functional group,
wherein one of C 1 , C 2 , or C 3 is bonded to an amide group, an ester group or a

 group of a biofunctional hydrocarbyl moiety directly or through the hydrocarbyl group, and
wherein the biofunctional hydrocarbyl moiety is selected from adamantane, L-cysteine hydrochloride, L-tyrosine, dopamine, tyramine, norepinephrine, 3-methoxytyramine, polyethylene glycol, and polyethylene glycol amine.

2. The biofunctionalized 3,4-alkylenedioxythiophene monomer according to claim 1 having one of the following structures:

3. A method of making a functionalized polymer, the method comprising polymerizing at least one monomer in accordance with claim 1 .

4. The method in accordance with claim 3 , wherein the step of polymerizing comprises electropolymerizing.

5. An electronic biomedical device comprising the polymer of claim 3 .

6. A functionalized polymer prepared by polymerization of at least one monomer in accordance with claim 1 , wherein the functionalized polymer is represented by a chemical formula: [(CR 1 R 2 )(CR 3 R 4 )(CR 5 R 6 ) x O 2 C 4 S] m , where m is a degree of polymerization and is in a range of 2 to 100.

7. A functionalized polymer prepared by copolymerization of at least one monomer in accordance with claim 1 and at least one additional monomer.

8. A biofunctionalized 3,4-alkylenedioxythiophene monomer represented by a chemical formula (C 1 R 1 R 2 )(C 2 R 3 R 4 )(C 3 R 5 R 6 ) x O 2 C 4 H 2 S (A′DOT+, where A′ represents (CR 1 R 2 )(CR 3 R 4 )(CR 5 R 6 ) x ),
wherein x=1, and the biofunctionalized 3,4-alkylenedioxythiophene monomer is functionalized 3,4-propylenedioxythiophene (Pro′DOT+; where Pro′ represents (C 1 R 1 R 2 )(C 2 R 3 R 4 )(C 3 R 5 R 6 )),
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is independently selected from hydrogen, a hydrocarbyl group, and a heteroatom-containing functional group, and
wherein one of C 1 , C 2 , or C 3 is bonded to an amide group, an azide group, or an ester group of a biofunctional hydrocarbyl moiety directly or through the hydrocarbyl group.

9. The biofunctionalized 3,4-alkylenedioxythiophene monomer according to claim 8 , wherein the biofunctional hydrocarbyl moiety is selected from adamantane, cholesterol, L-cysteine hydrochloride, L-tyrosine, dopamine, tyramine, norepinephrine, 3-methoxytyramine, polyethylene glycol, polyethylene glycol amine, and phospholipids.

10. The biofunctionalized 3,4-alkylenedioxythiophene monomer according to claim 8 having one of the following structures:

wherein A′DOT represents 3,4-propylenedioxythiophene (Pro′DOT).

11. A biofunctionalized 3,4-alkylenedioxythiophene monomer represented by a chemical formula (C 1 R 1 R 2 )(C 2 R 3 R 4 )(C 3 R 5 R 6 ) x O 2 C 4 H 2 S (A′DOT+, where A′ represents C 1 R 1 R 2 )(C 2 R 3 R 4 )(C 3 R 5 R 6 ) x ),
wherein x=0 or 1, when x=0, the functionalized 3,4-alkylenedioxythiophene monomer is 3,4-ethylenedioxythiophene (E′DOT+; where E′ represents C 1 R 1 R 2 )(C 2 R 3 R 4 )) and when x=1, the functionalized 3,4-alkylenedioxythiophene monomer is functionalized 3,4-propylenedioxythiophene (Pro′DOT+; where Pro′ represents C 1 R 1 R 2 )(C 2 R 3 R 4 )(C 3 R 5 R 6 )),
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is independently selected from hydrogen, a hydrocarbyl group, and a heteroatom-containing functional group,
wherein one of C 1 , C 2 , or C 3 is bonded to an amide group or an ester group of a biofunctional hydrocarbyl moiety directly or through the hydrocarbyl group, and
wherein the biofunctional hydrocarbyl moiety is selected from adamantane, L-cysteine hydrochloride, L-tyrosine, dopamine, tyramine, norepinephrine, 3-methoxytyramine, polyethylene glycol, and polyethylene glycol amine.

Assignees

• Martin David C
• Nagane Samadhan Suresh
• Sitarik Peter
• Univ Delaware

Inventors

• Martin David C
• Nagane Samadhan Suresh
• Sitarik Peter

Classifications

• H01B1/124

  Intrinsically conductive polymers · CPC title

• C08G2261/94

  Applications in sensors, e.g. biosensors · CPC title

• C08G2261/44

  Electrochemical polymerisation, i.e. oxidative or reductive coupling · CPC title

• C08G2261/334

  containing heteroatoms · CPC title

• C08G2261/148

  Side-chains having aromatic units · CPC title