Photopolymerizable Silicone Materials Forming Semipermeable Membranes for Sensor Applications

• US 20080277276A1
• Filed: 06/21/2005
• Published: 11/13/2008
• Est. Priority Date: 08/11/2004
• Status: Active Grant

• Current Assignee: Dow, Inc.
• Original Assignee: Dow, Inc.
• Inventors: Maghsoodi, Sina, Harkness, Brian Robert, Gardner, Geoffrey Bruce
• Granted Patent: US 8,486,615 B2
• Time in Patent Office: Days
• US Class Current: 204/403.06
• CPC Class Codes: C12Q 1/002 Electrode membranes
• CPC Class Codes: G01N 33/5438 Electrodes
• CPC Class Codes: G03F 7/0757 Macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence
• CPC Class Codes: Y10T 428/24802 Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Abstract

A method for preparing sensing devices (biosensors) includes the steps of: (1) applying a photopatternable silicone composition to a surface in a sensing device to form a film, (2) photopatterning the film by a process comprising exposing the film to radiation through a photomask without the use of a photoresist to produce an exposed film; (3) removing regions of the non-exposed film with a developing solvent to form a patterned film, which forms a permselective layer or an analyte attenuation layer covering preselected areas of the sensing device.

Claims

1. A method comprising:

(1) applying a photopatternable silicone composition to a surface in a sensing device to form a film,

(b 2) photopatterning the film by a process comprising exposing the film to radiation through a photomask without using a photoresist to produce an exposed film;

(3removing regions of the non-exposed film with a developing solvent to form a patterned film;

optionally (4) heating the patterned film.

2. The method of claim 1, where the photopatternable silicone composition comprises:

(A) an organopolysiloxane containing an average of at least two silicon-bonded aliphatically unsaturated organic groups per molecule,

(B) an organosilicon compound containing an average of at least two silicon-bonded hydrogen atoms per molecule in a concentration sufficient to cure the photopatternable silicone composition,

(C) a catalytic amount of a photoactivated hydrosilylation catalyst,

optionally (D) an inhibitor,

optionally (E) a filler,

optionally (F) a treating agent for the filler,

optionally (G) a vehicle,

optionally (H) a spacer,

optionally (I) an adhesion promoter,

optionally (J) a surfactant,

optionally (K) a photosensitizer, and

optionally (L) a colorant; and

the method further comprises heating the exposed film before step (3) for an amount of time such that exposed regions of the exposed film are substantially insoluble in the developing solvent and non-exposed regions of the exposed film are soluble in the developing solvent.

3. The method of claim 1, where the photopatternable silicone composition comprises:

(a) an acrylic functional silicone resin, a vinyl ether functional silicone resin, an epoxy functional silicone resin, or a combination thereof,

(b) a photoinitiator,

optionally (c) an inhibitor,

optionally (d) a filler,

optionally (e) a treating agent for the filler,

optionally (f) a vehicle,

optionally (g) a spacer,

optionally (h) an adhesion promoter,

optionally (i) a surfactant,

optionally (j) a photosensitizer, and

optionally (k) a colorant.

4. The method of claim 1, where the photopatternable silicone composition comprises:

(a) an acrylic functional silicone resin comprising units of formulae [(CH₂═

CR¹³COOR¹⁴)SiO_3/2] and [R¹⁵SiO_3/2], where

each R¹³ is independently a hydrogen atom or methyl group,

each R¹⁴ is independently a hydrocarbylene group having 1 to 8 carbon atoms, and

each R¹⁵ is independently an alkyl, cyclic alkyl, aryl or alkenyl group having 1 to 8 carbon atoms; and

(b) a photoinitiator.

5. The method of claim 2, where the photopatternable silicone composition comprises a solvent, and the solvent is removed during or after step (1).

6. The method of claim 5, where step (1) is performed by spin coating the photopatternable silicone composition on the surface in the sensing device.

7. The method of any of one of the preceding claims, where the surface comprises a wafer on which a first structure comprising a base sensor is mounted.

8. The method of claim 7, further comprising interposing an electrolyte layer between the base sensor and the patterned film.

9. The method of claim 1, further comprising applying a biolayer over at least a portion of the patterned film.

10. The method of claim 9, further comprising applying an analyte attenuation layer over at least a portion of the biolayer.

11. A semipermeable membrane prepared by the method of claims 1.

12. The semipermeable membrane of claim 11, where the semipermeable membrane is a permselective layer or an analyte attenuation layer.

13. A device comprising:

(i) a substrate,

(ii) a base sensor mounted to the substrate,

optionally (iii) an electrolyte layer covering the base sensor and at least a portion of the silicon substrate,

(iv) a permselective layer covering at least a portion of the base sensor,

optionally (v) a biolayer covering at least a portion of the permselective layer,

optionally (vi) an analyte attenuation layer covering at least a portion of the biolayer,

optionally (vii) a coupling means covering at least a portion of the permselective layer, where the coupling means attach (viii) a ligand receptor or an immunreactive species as an outermost layer of the device;

where the permselective layer is a cured product of a photopatternable silicone composition selected from the group consisting of a photopatternable silicone resin composition and a photopatternable hydrosilylation curable silicone composition.

16. A device according to claim 13, where the device is selected from the group consisting of:

an adenosine-5-triphosphate sensing device, a cardiac troponin 1 sensing device, a chloride ion sensing device, a creatinine sensing device, a creatine sensing device, a dioxygen sensing device, a glucose and cholesterol sensing device, a glucose sensing device, a hematocrit sensing device, a hydrogen peroxide sensing device, an ionized calcium sensing device, a lactate sensing device, a ligand/ligand receptor-based sensing device, a PCO₂ sensing device, a pH sensing device, a PO₂ sensing device, a potassium ion sensing device, a sodium ion sensing device, a urea nitrogen sensing device, a urea sensing device, and a uric acid sensing device.

17. The device of claim 13, where

I) the photopatternable hydrosilylation curable silicone composition comprises

(A) an organopolysiloxane containing an average of at least two silicon-bonded aliphatically unsaturated organic groups per molecule,

(B) an organosilicon compound containing an average of at least two silicon-bonded hydrogen atoms per molecule in a concentration sufficient to cure the photopatternable silicone composition,

(C) a catalytic amount of a photoactivated hydrosilylation catalyst,

optionally (D) an inhibitor,

optionally (E) a filler,

optionally (F) a treating agent for the filler,

optionally (G) a vehicle,

optionally (H) a spacer,

optionally (I) an adhesion promoter,

optionally (J) a surfactant,

optionally (K) a photosensitizer, and

optionally (L) a colorant;

and

II) the photopatternable silicone resin composition comprises

(a) an acrylic functional silicone resin, a vinyl ether functional silicone resin, an epoxy functional silicone resin, or a combination thereof,

(b) a photoinitiator,

optionally (c) an inhibitor,

optionally (d) a filler,

optionally (e) a treating agent for the filler,

optionally (f) a vehicle,

optionally (g) a spacer,

optionally (h) an adhesion promoter,

optionally (i) a surfactant,

optionally (j) a photosensitizer, and

optionally (k) a colorant.

14. A device comprising:

(i) a substrate,

(ii) a base sensor mounted to the substrate,

optionally (iii) an electrolyte layer covering the base sensor and at least a portion of the silicon substrate,

(iv) a permselective layer covering at least a portion of the base sensor,

(v) a biolayer covering at least a portion of the permselective layer, and

(vi) an analyte attenuation layer covering at least a portion of the biolayer;

where the analyte attenuation layer is a cured product of a photopatternable silicone composition selected from the group consisting of a photopatternable silicone resin composition and a photopatternable hydrosilylation curable silicone composition.

15. The device of claim 14, where

I) the photopatternable hydrosilylation curable silicone composition comprises

(A) an organopolysiloxane containing an average of at least two silicon-bonded aliphatically unsaturated organic groups per molecule,

(B) an organosilicon compound containing an average of at least two silicon-bonded hydrogen atoms per molecule in a concentration sufficient to cure the photopatternable silicone composition,

(C) a catalytic amount of a photoactivated hydrosilylation catalyst,

optionally (D) an inhibitor,

optionally (E) a filler,

optionally (F) a treating agent for the filler,

optionally (G) a vehicle,

optionally (H) a spacer,

optionally (I) an adhesion promoter,

optionally (J) a surfactant,

optionally (K) a photosensitizer, and

optionally (L) a colorant;

and

II) the photopatternable silicone resin composition comprises

(a) an acrylic functional silicone resin, a vinyl ether functional silicone resin, an epoxy functional silicone resin, or a combination thereof,

(b) a photoinitiator,

optionally (c) an inhibitor,

optionally (d) a filler,

optionally (e) a treating agent for the filler,

optionally (f) a vehicle,

optionally (g) a spacer,

optionally (h) an adhesion promoter,

optionally (i) a surfactant,

optionally (j) a photosensitizer, and

optionally (k) a colorant.