Granted Patent B2

US 12,369,815 · App. 17/689,760 · Granted Jul 29, 2025

Inventors: Blair K. Troudt (St. Paul, MN); Philippe Pierre Joseph Buhlmann (Minneapolis, MN); Steven Koester (Edina, MN); Xue Zhen (Plymouth Meeting, PA)

Assignee: REGENTS OF THE UNIVERSITY OF MINNESOTA

A61B5/082A61B5/05B05D1/007C01B32/194G01N27/22A61B2562/125C01B2204/22G01N2027/222

Abstract

Claims (51)

1. A medical device comprising:

a graphene varactor comprising:

a graphene layer;

a self-assembled monolayer disposed on an outer surface of the graphene layer through electrostatic interactions between a partial positive charge on hydrogen atoms of one or more hydrocarbons of the self-assembled monolayer and π-electron system of graphene; and

wherein the self-assembled monolayer comprises one or more compounds comprising one or more hydrazine groups or hydroxylamine groups, substituted hydrazine or hydroxylamine groups, or derivatives thereof.

2. The medical device of claim 1 , wherein the self-assembled monolayer provides a Langmuir theta value of at least 0.9.

3. The medical device of claim 1 , wherein the self-assembled monolayer provides coverage over the graphene from 50% to 150% by surface area.

4. The medical device of claim 1 , wherein the self-assembled monolayer further includes an acidic compound effective to catalyze a reaction between the hydrazine groups or hydroxylamine groups and an aldehyde or ketone.

5. The medical device of claim 1 , the self-assembled monolayer comprising compounds of a formula:

wherein Z comprises NH or O;

wherein R 1 comprises (CH 2 ) m CH 3 , wherein 50>m>5;

wherein X comprises CH 2 , O, NH, N(CH 2 ) n CH 3 , —C(═O)O—, —OC(═O)—, —C(═O)NH—, —NHC(═O)—, —C(═O)N((CH 2 ) n CH 3 )—, —N((CH 2 ) n CH 3 )C(═O)—, —S, —S(═O)—, —S(═O) 2 —, —S(═O) 2 O—, —OS(═O) 2 —, —S(═O) 2 NH—, —NHS(═O) 2 —, —S(═O) 2 N((CH 2 ) n CH 3 )—, —N((CH 2 ) n CH 3 )S(═O) 2 —, and wherein n is 0, or 1 to 20;

wherein Y comprises (C 6 H 4 ) p or (CH 2 ) p , wherein p is 0, 1, or 2;

wherein W comprises H, (CH 2 ) q OH, (CH 2 ) q COOH, (CH 2 ) q SO 2 OH, or (CH 2 ) q PO 2 OH, wherein q is 0, 1, or 2;

wherein V comprises H, NO, NO 2 , Cl, Br, I, F, CF 3 , —CN, —NC, C 6 H 5 (phenyl), OR, —C(═O)R, SR, COOR, OCOOR, —S(═O)R, —S(═O) 2 R, —S(═O) 2 OR, —OS(═O) 2 R, —S(═O) 2 NHR, —NHS(═O) 2 R, —S(═O) 2 NRR 2 , —NR 2 S(═O) 2 R, wherein R and R 2 comprise (CH 2 ) k CH 3 and k is 0, 1, or 2;

wherein R 1 X and V can be present in any ring position relative to a YZNH 2 group and W is present in an alpha position relative to the YZNH 2 to provide proximity between W and YZNH 2 ; and

any tautomers thereof.

6. The medical device of claim 5 , wherein W is present in the alpha position effective to permit interaction of an acidic hydrogen atom on W with an aldehyde molecule so as to catalyze a reaction of the aldehyde with the hydrazine group or hydroxylamine group.

7. The medical device of claim 5 , wherein the formula comprises more than one R 1 X moiety effective to induce self-assembly of the compound.

8. The medical device of claim 5 , wherein the formula comprises more than one V moiety effective to provide electron density to the compound.

9. The medical device of claim 1 , the self-assembled monolayer comprising compounds of the formula:

wherein R 1 comprises (CH 2 ) m CH 3 , wherein 50>m>5;

wherein X comprises CH 2 , O, NH, N(CH 2 ) n CH 3 , —C(═O)O—, —OC(═O)—, —C(═O)NH—, —NHC(═O)—, —C(═O)N((CH 2 ) n CH 3 )—, —N((CH 2 ) n CH 3 )C(═O)—, —S, —S(═O)—, —S(═O) 2 —, —S(═O) 2 O—, —OS(═O) 2 —, —S(═O) 2 NH—, —NHS(═O) 2 —, —S(═O) 2 N((CH 2 ) n CH 3 )—, —N((CH 2 ) n CH 3 )S(═O) 2 — and wherein n is 0, or 1 to 20;

wherein W comprises H, (CH 2 ) q OH, (CH 2 ) q COOH, (CH 2 ) q SO 2 OH, or (CH 2 ) q PO 2 OH, wherein q is 0, 1, or 2;

wherein V comprises H, NO, NO 2 , Cl, Br, I, F, CF 3 , —CN, —NC, C 6 H 5 (phenyl), OR, —C(═O)R, SR, COOR, OCOOR, —S(═O)R, —S(═O) 2 R, —S(═O) 2 OR, —OS(═O) 2 R, —S(═O) 2 NHR, —NHS(═O) 2 R, —S(═O) 2 NRR 2 , —NR 2 S(═O) 2 R, wherein R and R 2 comprise (CH 2 ) k CH 3 and k is 0, 1, or 2;

wherein R 1 X and V can be present in any ring position relative to an NNH 2 group and W is present in an alpha position relative to the NNH 2 group; and

any tautomers thereof.

10. The medical device of claim 9 , wherein W is present in the alpha position effective to permit interaction of an acidic hydrogen atom on W with an aldehyde molecule so as to catalyze a reaction of the aldehyde with the hydrazine group or hydroxylamine group.

11. The medical device of claim 1 , the self-assembled monolayer comprising compounds of the formula:

wherein Z comprises NH or O;

where Y comprises (CH 2 ) p , wherein p is from 0 to 20;

wherein Ar comprises an aromatic substituent with 16 or more aromatic carbons; and

any tautomers thereof.

12. The medical device of claim 11 , wherein the aromatic substituent comprises naphthacene, benzanthracene, chrysene, pentacene, dibenzanthracene, triphenylene, pyrene, benzopyrene, picene, perylene, benzoperylene, pentaphene, pentacene, anthanthrene, coronene, ovalene, or derivatives thereof.

13. The medical device of claim 11 , wherein the aromatic substituent further comprises one or more substitutions including (CH 2 ) q OH, (CH 2 ) q COOH, (CH 2 ) q SO 2 OH, or (CH 2 ) q PO 2 OH, in a position alpha to a YZNH 2 group effective to permit interaction of an acidic hydrogen atom on the substitution with an aldehyde molecule so as to catalyze a reaction of the aldehyde with the hydrazine or hydroxylamine group.

14. The medical device of claim 1 , the self-assembled monolayer comprising compounds of the formula:

wherein Ar comprises an aromatic substituent with 16 or more aromatic carbons; and

any tautomers thereof.

15. The medical device of claim 14 , wherein the aromatic substituent comprises naphthacene, benzanthracene, chrysene, pentacene, dibenzanthracene, triphenylene, pyrene, benzopyrene, picene, perylene, benzoperylene, pentaphene, pentacene, anthanthrene, coronene, ovalene, or derivatives thereof.

16. The medical device of claim 14 , wherein the aromatic substituent further comprises one or more substitutions including (CH 2 ) q OH, (CH 2 ) q COOH, (CH 2 ) q SO 2 OH, or (CH 2 ) q PO 2 OH, in a position alpha to a NNH 2 group effective to permit interaction of an acidic hydrogen atom on the substitution with an aldehyde molecule.

17. A method of modifying a surface of graphene to create a graphene varactor, the method comprising:

forming a self-assembled monolayer disposed on an outer surface of the graphene layer through electrostatic interactions between a partial positive charge on hydrogen atoms of more hydrocarbons of the self-assembled monolayer and a π-electron system of graphene;

the self-assembled monolayer comprising one or more compounds comprising hydrazine or hydroxylamine groups, substituted hydrazine or hydroxylamine groups, or derivatives thereof.

18. The method of claim 17 , further comprising quantifying an extent of surface coverage of the self-assembled monolayer using contact angle goniometry, Raman spectroscopy, or x-ray photoelectron spectroscopy.

19. A method for detecting an analyte comprising:

collecting a gaseous sample from a patient;

contacting the gaseous sample with one or more graphene varactors, each of the one or more graphene varactors comprising

a graphene layer;

a self-assembled monolayer disposed on an outer surface of the graphene layer through electrostatic interactions between a partial positive charge on hydrogen atoms of more hydrocarbons of the self-assembled monolayer and a π-electron system of graphene; and

wherein the self-assembled monolayer comprises at least one selected from the group consisting of compounds comprising hydrazine or hydroxylamine groups, substituted hydrazine or hydroxylamine groups, or derivatives thereof.

20. The method of claim 19 , further comprising measuring a differential response in an electrical property of the one or more graphene varactors due to binding of one or more analytes present in the gaseous sample.

Assignments (3)

Continuity (2)

References Cited (256)