Gel sensors and method of use thereof

• US 6,180,288 B1
• Filed: 03/21/1997
• Issued: 01/30/2001
• Est. Priority Date: 03/21/1997
• Status: Expired due to Term

• Current Assignee: Kimberly-Clark Worldwide Incorporated (Kimberly-Clark Corporation)
• Original Assignee: Kimberly-Clark Worldwide Incorporated (Kimberly-Clark Corporation)
• Inventors: Everhart, Dennis S., Jones, Mark L., Kaylor, Rosann M.
• Primary Examiner(s): ANGEBRANNDT, MARTIN J
• Application Number:
  US08/821,464
• Time in Patent Office: 1,411 Days
• Field of Search: 430/320, 430/321, 430/2, 430/1, 264/1.1, 422/82.05, 422/82.03, 422/82.04, 422/82.06, 436/529, 436/531
• US Class Current: 430/2
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: G01N 33/54373 involving physiochemical end-point determination, e.g. wave-guides, FETS, gratings
• CPC Class Codes: G03F 7/00 Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor using photoresist structures for special production processes, see the relevant places, e.g. B44C, H01L, e.g. H01L21/00, H05K
• CPC Class Codes: G03F 7/0002 Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
• CPC Class Codes: G03F 7/165 Monolayers, e.g. Langmuir-Blodgett
• CPC Class Codes: G03H 2001/0033 in hologrammetry for measuring or analysing

Abstract

The present invention comprises an optically diffracting sensing device whose diffraction pattern changes upon exposure to some stimuli. The diffraction pattern may be two or three dimensional, and in one embodiment the change in diffraction patterns is recognizable to the untrained eye. The device comprises one or more gels coated onto patterned, self-assembling monolayers of alkanethiolates, carboxylic acids, hydroxamic acids, and phosphonic acids printed onto a variety of substrates, including glass, silicon, aluminum oxide, and thermoplastic films metallized with gold, or with an alloy such as nickel/gold. The present invention also comprises the method of making this device, and the use of this device.

Claims

1. A sensing device comprising:

(a) a self-assembling monolayer stamped in a pattern on a substrate using a stamping means;

(b) a responsive gel associated with the self-assembling monolayer, the gel capable of responding to a stimulus, wherein the gel is formed from polymers of acrylamides or copolymers containing acrylamides; and

(c) an additional material on the substrate, the additional material being located on a non-stamped area of the substrate, the additional material being selected such that the responsive gel does not associate with the additional material;

wherein the self-assembling monolayer is stamped in a pattern such that when the gel responds to the stimulus, the gel undergoes a physical change such that the sensing device produces a change in its diffraction of transmitted electromagnetic radiation, thereby indicating the presence of the stimulus, wherein the change in diffraction is visible to an unaided eye,

further wherein the physical change occurs discontinuously at a specific stimulus level with a discontinuous change in gel volume.

2. The device of claim 1, wherein the sensing device can form a hologram when electromagnetic radiation is transmitted through the device.

3. The device of claim 2, wherein the hologram changes to a second hologram upon exposure to the stimulus.

4. The device of claim 1, wherein the substrate is selected from the group consisting of glass, silicon dioxide, aluminum oxide, and metallized polymer films.

5. The device of claim 4, wherein the substrate is a polymer film having a metal or metal oxide thereon, and wherein the self-assembling monolayer is formed from compounds with the following general formula:

6. The device of claim 5, wherein:

X is an asymmetrical or symmetrical disulfide (—

R′

SSR, —

RSSR), sulfide (—

R′

SR, —

RSR), diselinide (—

R′

SeSeR), selenide (—

R′

SeR, —

RSeR), thiol (—

SH), nitrile (—

CN), isonitrile, nitro (—

NO₂), selenol (—

SeH), trivalent phosphorous compounds, isothiocyanate, xanthate, thiocarbamate, phosphine, thioacid, dithioacid, carboxylic acids, hydroxylic acids, or hydroxamic acids;

R and R′

are hydrocarbon chains which may be interrupted by hetero atoms, and which may be perfluorinated; and

Y is a hydroxy, carboxyl, amino, aldehyde, hydrazide, carbonyl, epoxy, or vinyl group.

7. The device of claim 5, wherein R is greater than 7 carbon atoms in length.

8. The device of claim 5, wherein R is a compound of the form (CH₂)_a—

Z—

(CH₂)_b, wherein a≧

0, b≧

7, and Z is any chemical functionality of interest.

9. The device of claim 8, wherein Z is selected from the group consisting of sulfones, lactams, and urea.

10. The device of claim 4, wherein the substrate is a metallized polymer film, the polymer film comprising polyethylene-terephthalate, acrylonitrile-butadiene-styrene, acrylonitrile-methyl acrylate copolymer, cellophane, cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose triacetate, cellulose triacetate, polyethylene, polyethylene-vinyl acetate copolymers, ionomers (ethylene polymers) polyethylene-nylon copolymers, polypropylene, methyl pentene polymers, polyvinyl fluoride, or aromatic polysulfones.

11. The device of claim 10, wherein the metallized polymer film is optically transparent.

12. The device of claim 10, wherein the metallized polymer film is metallized with metals comprising gold, silver, nickel, platinum, aluminum, iron, copper, zirconium, or alloys thereof.

13. The device of claim 1, wherein the gel is derivatized to contain hydroxyl, carboxyl, amino, aldehyde, carbonyl, epoxy, crown, or vinyl groups.

14. The device of claim 1, wherein the gel contains chromophores, metal salts, ions, antibodies, T or B cell receptors, fragments, or epitopes thereof, proteins, peptides, neurotransmitters, hormones, growth factors, cytokines, monokines, lymphokines, nutrients, enzymes, receptors, macromolecular structures, organelles, cells, or microorganisms.

15. The device of claim 1, wherein the gel contains compounds selected from the group consisting essentially of metallo-phthalocyanines, surfactants, NaBr, KBr, NaCl, KCl, NaI, and KI, methanol and glycerol, tetra-alkylammonium bromides, crown ethers, benzo[18]crown-6, and azobenzene chromophores.

16. The device of claim 1, wherein there are two or more self-assembling monolayers with different physical or chemical properties.

17. The device of claim 1, wherein a first self-assembling monolayer is hydrophobic, and a second self-assembling monolayer is hydrophilic.

18. The device of claim 1, wherein the stimulus comprises temperature, solvent composition, mechanical strain, electric field, pH, salt concentration, solvent quality, light intensity, light wavelength, pressure, ionic strength, ion identity, or specific chemical triggers.

19. A method of making a sensing device comprising stamping a pattern of self-assembling monolayers onto a substrate using a stamping means, applying an additional material to non-stamped areas of the substrate, and coating the pattern of self-assembling monolayers with one or more gels, wherein the gel is associated with the self-assembling monolayers and not associated with the additional material, the gel is formed from polymers of acrylamides or copolymers containing acrylamides, the gels being capable of responding to a stimulus, wherein the self-assembling monolayer is stamped in a pattern such that when the gel responds to the stimulus, the gel undergoes a physical change such that the sensing device produces a change in its diffraction of transmitted electromagnetic radiation, thereby indicating the presence of the stimulus, wherein the change in diffraction is visible to an unaided eye, further wherein the physical change occurs discontinuously at a specific stimulus level with a discontinuous change in gel volume.

20. The method of claim 19, wherein the device can form a hologram when electromagnetic radiation is transmitted through the method.

21. The method of claim 20, wherein, wherein the hologram changes to a second hologram upon exposure to the stimulus.

22. The method of claim 19, wherein the substrate is selected from the group consisting of glass, silicon dioxide, aluminum oxide, and metallized polymer films.

23. The method of claim 22, wherein the substrate is a metallized polymer film, the polymer film comprising polyethylene-terephthalate, acrylonitrile-butadiene-styrene, acrylonitrile-methyl acrylate copolymer, cellophane, cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose triacetate, cellulose triacetate, polyethylene, polyethylene-vinyl acetate copolymers, ionomers (ethylene polymers) polyethylene-nylon copolymers, polypropylene, methyl pentene polymers, polyvinyl fluoride, or aromatic polysulfones.

24. The method of claim 23, wherein the metallized polymer film is optically transparent.

25. The method of claim 23, wherein the metallized polymer film is metallized with metals comprising gold, silver, nickel, platinum, aluminum, iron, copper, zirconium, or alloys thereof.

26. The method of claim 19, wherein the gel is derivatized to contain hydroxyl, carboxyl, amino, aldehyde, carbonyl, epoxy, crown, or vinyl groups.

27. The method of claim 26, wherein the gel contains chromophores, metal salts, ions, antibodies, T or B cell receptors, fragments, or epitopes thereof, proteins, peptides, neurotransmitters, hormones, growth factors, cytokines, monokines, lymphokines, nutrients, enzymes, receptors, macromolecular structures, organelles, cells, or microorganisms.

28. The method of claim 19, wherein the gel contains compounds selected from the group consisting essentially of metallo-phthalocyanines, surfactants, NaBr, KBr, NaCl, KCl, NaI, and KI, methanol and glycerol, tetra-alkylammonium bromides, crown ethers, benzo[18]crown-6, azobenzene chromophores.

29. The method of claim 19, wherein there are two or more self-assembling monolayers with different physical or chemical properties.

30. The method of claim 19, wherein a first self-assembling monolayer is hydrophobic, and a second self-assembling monolayer is hydrophilic.

31. The method of claim 19, wherein the substrate is a polymer film having a metal or metal oxide thereon, and wherein the self-assembling monolayer is formed from compounds with the following general formula:

32. The method of claim 31, wherein:

X is an asymmetrical or symmetrical disulfide (—

R′

SSR, —

RSSR), sulfide (—

R′

SR, —

RSR), diselinide (—

R′

SeSeR), selenide (—

R′

SeR, —

RSeR), thiol (—

SH), nitrile (—

CN), isonitrile, nitro (—

NO₂), selenol (—

SeH), trivalent phosphorous compounds, isothiocyanate, xanthate, thiocarbamate, phosphine, thioacid, dithioacid, carboxylic acids, hydroxylic acids, or hydroxamic acids;

R and R′

are hydrocarbon chains which may be interrupted by hetero atoms, and which may be perfluorinated; and

Y is a hydroxy, carboxyl, amino, aldehyde, hydrazide, carbonyl, epoxy, or vinyl group.

33. The method of claim 31, wherein R is greater than 7 carbon atoms in length.

34. The method of claim 31, wherein R is a compound of the form (CH₂)_a—

Z—

(CH₂)_b, wherein a≧

0, b≧

7, and Z is any chemical functionality of interest.

35. The method of claim 34, wherein Z is selected from the group consisting of sulfones, lactams, and urea.

36. The method of claim 19, wherein the stimulus comprises temperature, solvent composition, mechanical strain, electric field, pH, salt concentration, solvent quality, light intensity, light wavelength, pressure, ionic strength, ion identity, or specific chemical triggers.