Sol-gel based matrix

Patent metadata

Field	Value
Publication number	US-10233328-B2
Application number	US-201415028600-A
Country	US
Kind code	B2
Filing date	Oct 24, 2014
Priority date	Oct 24, 2013
Publication date	Mar 19, 2019
Grant date	Mar 19, 2019

Abstract

The present invention relates to a method for the production of a sol-gel based matrix. The method comprises the steps of: a) providing a first alkoxysilane of the general formula: R 1 —Si(OR 2 ) 3 and a second alkoxysilane of the general formula (I): b) preparing a first sol-gel component by polymerization of the first alkoxysilane in the presence of an acid catalyst, c) preparing a second sol-gel component by polymerization of the second alkoxysilane in the presence of an Lewis acid catalyst, d) Mixing the first sol-gel component and the second sol-gel component for the preparation of a sol-gel based matrix. The above method results in a sol-gel based matrix with high stability and high porosity. The sol-gel based material may be used for the production of a composite or sensor suitable for monitoring analytes. Methods for preparing these composites or sensors are provided as well.

First claim

The invention claimed is:

1. A method for the production of a sol-gel based matrix comprising the steps of:
a) providing a first alkoxysilane of the general formula:
R 1 —Si(OR 2 ) 3

and a second alkoxysilane of the general formula:

wherein
R 1 represents a straight or branched C 1 -C 6 alkyl or C 2 -C 6 alkenyl, a C 3 -C 6 cycloalkyl, a C 1 -C 6 aminoalkyl, a C 1 -C 6 hydroxyalkyl, a C 1 -C 6 cyanoalkyl, a phenyl, a group of the formula —Y—(X—Y) n H, wherein Y independently is selected from straight or branched C 1 -C 6 alkylene, X is a hetero atom or group selected among O, S, NH, and n is an integer of 1-5,
or R 1 represents a C 1 -C 6 alkyl substituted with a group Z,
wherein Z independently is selected form the group comprising hydrogen, cyano, halogen, hydroxy, nitro, amide C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl, C 2 -C 24 -alkenyl, C 2 -C 24 -alkynyl, aryl, C 1 -C 24 -alkoxy, C 1 -C 24 -alkylsulfonyl, amino, aminocarbonyl, aminothiocarbonyl, aminocarbonylamino, aminothiocarbonylamino, aminocarbonyloxy, aminosulfonyl, aminosulfonyloxy, aminosulfonylamino, amidino, carboxyl, carboxyl ester comprising a C 1 -C 6 alkyl alcohol moiety, (carboxyl ester)amino comprising a C 1 -C 6 alkyl alcohol moiety, (carboxyl ester)oxy comprising a C 1 -C 6 alkyl alcohol moiety, sulfonyl, sulfonyloxy, thiol, thiocarbonyl, C 1 -C 24 -alkylthio, 5 or 6 membered heteroaryl, or a C 3 -C 7 cycloalkyl;
R 2 independently represents a straight or branched C 1 -C 6 alkyl; and
R 3 represents a linker chosen from a group of the formula
—R 4 —(X—R 4 ) n —

wherein R 4 independently is selected from straight or branched C 2 -C 6 alkylene, C 2 -C 24 -haloalkylene, X is a hetero atom or group selected among O, S, NH, and n is an integer of 0-12,
b) preparing a first sol-gel component by polymerisation of the first alkoxysilane in the presence of an acid catalyst,
c) preparing a second sol-gel component by polymerisation of the second alkoxysilane in the presence of Lewis acid catalyst,
wherein an additional alkoxysilane is added in at least one of steps b) or c), said additional alkoxysilane being of the formula:
R 5 —Si(OR 2 ) 3

wherein R 2 is as defined above and R 5 represents a group having covalently attached an indicator or reference dye,
d) Mixing the first sol-gel component and the second sol-gel component for the preparation of a sol-gel based matrix.

2. The method according to claim 1 , wherein R 5 is of the general formula
—R 3 —NH—C(═O)—X—R 3 -Q

wherein R 3 is as defined above and independently selected, and Q represents an indicator and/or a reference dye.

3. The method according to claim 2 , wherein Q is an indicator dye derived from 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS), fluorescein, or rhodamine B.

4. The method according to claim 2 , wherein Q is a reference dye derived from triangulenium compounds, acridinium compounds, ruthenium doped sol-gel particles, ruthenium-based compounds with α-diimine ligands, porphorin with Pt or Pd as the central metal atom, Ru(bpy) 2 (dpp)Cl 2 , Ru(bpy) 3 Cl 2 , a lanthanide containing complex, or polymeric metal containing structure.

5. The method according to claim 1 , wherein the Lewis acid catalyst is selected from the group consisting of TiCl 3 , AlCl 3 , and BF 3 , or solvates or etherates thereof.

6. The method according to claim 1 ,
wherein one of a reference dye or an indicator dye is added to the first sol-gel component of step b) and the other one of a reference dye or indicator dye is added to the second sol-gel component of step c).

7. The method according to claim 1 , wherein the first alkoxysilane is selected from the group consisting of ethyltriethoxysilane (ETEOS), methyltriethoxysilane (MTEOS), propyltriethoxysilane (PrTEOS), n-octyltriethoxysilane (n-octyl TEOS), methyltrimethoxysilane (MTMOS), aminopropyltrimethoxysilane (APTMOS), phenyltriethoxysilane (PhTEOS), and phenyl trimethoxysilane (PhTMOS).

8. The method according to claim 1 , wherein the second alkoxysilane is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane (GPTMS).

9. The method according to claim 1 , wherein the additional alkoxysilane is added to the first sol-gel component in step b).

10. The method according to claim 1 , wherein the additional alkoxysilane is added to the second sol-gel component in step c).

11. The method according to claim 9 , wherein the first sol-gel component is allowed to polymerize for at least 15 minutes before the additional alkoxysilane is added.

12. The method according to claim 10 , wherein the second sol-gel component is allowed to polymerize for at least 15 minutes before the additional alkoxysilane is added.

Assignees

• Univ Copenhagen
• Kobenhavns Univ

Inventors

• Sorensen Thomas Just
• Rosenberg Martin
• Laursen Bo W

Classifications

• G01N2021/7756

  Sensor type · CPC title

• C08L83/04

  Polysiloxanes · CPC title

• C08L83/06 Primary

  containing silicon bound to oxygen-containing groups (C08L83/12 takes precedence) · CPC title

• G01N21/78

  producing a change of colour · CPC title

• C09B69/008

  Dyes containing a substituent, which contains a silicium atom · CPC title