CA2133946C - Silanes for the surface coating of dielectric materials - Google Patents
Silanes for the surface coating of dielectric materials Download PDFInfo
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- CA2133946C CA2133946C CA002133946A CA2133946A CA2133946C CA 2133946 C CA2133946 C CA 2133946C CA 002133946 A CA002133946 A CA 002133946A CA 2133946 A CA2133946 A CA 2133946A CA 2133946 C CA2133946 C CA 2133946C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Abstract
The present invention is concerned with novel silanes and their application for the silanization of dielectric materials for anchoring biologically active compounds. The silanes have the general formula I
(R1R2R3)Si-Y-X
wherein R1, R2 and R3 signify alkyl, alkoxy or halogen, but at least one of these groups is alkoxy or halogen, Y signifies an alkylene chain [-CH2-(CH2)n-CH2-], a fluoroalkylene chain [-CH2-(CF2)n-CH2-], (-CH2-(CF2)n-CF2-] with n = 1-20 or an oligooxyalkylene chain -[(CH2)n'-O-(CH2)n"]m- with n', n" =
2-6 and m = 2-6 and X signifies an epoxide, an anhydride of a dicarboxylic acid with 4-5 C atoms, an isothiocyanate, an aryl carboxylic acid chloride or an aryl sulphonic acid chloride, provided that at least one of R1, R2 and R3 is halogen when X signifies an epoxide.
The new silanes according to the invention offer the following advantages:
The reactive groups X of the silanes are hydrolysis-stable but sufficiently reactive for the immobilization of an organic or biological recognition molecule to take place without further activation of the silane layer.
The silanes are suitable for the direct coating of dielectric materials, in particular of dielectric waveguides which are preferably made of ZrO2, HfO2, Ta2O5, SiO2, Al2O3 or TiO2.
The silanes can be applied to the surface of dielectric materials not only from solution, but also from the gas phase.
The hydrolysis stability of the reactive groups gives rise to better stability during storage of silane layers and permits their direct application in an aqueous medium.
(R1R2R3)Si-Y-X
wherein R1, R2 and R3 signify alkyl, alkoxy or halogen, but at least one of these groups is alkoxy or halogen, Y signifies an alkylene chain [-CH2-(CH2)n-CH2-], a fluoroalkylene chain [-CH2-(CF2)n-CH2-], (-CH2-(CF2)n-CF2-] with n = 1-20 or an oligooxyalkylene chain -[(CH2)n'-O-(CH2)n"]m- with n', n" =
2-6 and m = 2-6 and X signifies an epoxide, an anhydride of a dicarboxylic acid with 4-5 C atoms, an isothiocyanate, an aryl carboxylic acid chloride or an aryl sulphonic acid chloride, provided that at least one of R1, R2 and R3 is halogen when X signifies an epoxide.
The new silanes according to the invention offer the following advantages:
The reactive groups X of the silanes are hydrolysis-stable but sufficiently reactive for the immobilization of an organic or biological recognition molecule to take place without further activation of the silane layer.
The silanes are suitable for the direct coating of dielectric materials, in particular of dielectric waveguides which are preferably made of ZrO2, HfO2, Ta2O5, SiO2, Al2O3 or TiO2.
The silanes can be applied to the surface of dielectric materials not only from solution, but also from the gas phase.
The hydrolysis stability of the reactive groups gives rise to better stability during storage of silane layers and permits their direct application in an aqueous medium.
Description
~13~9!~ 6 RAN 4090/24$
The present invention is concerned with novel silanes and their application for the silanization of dielectric materials and s for anchoring biologically active compounds. Dielectric materials equipped with silane layers are used as solid phases in analytic methods (Methods in Enzymology 44 ( 1976), 134). The new silanes are preferably used for coating signal transformers, e.g. an optical waveguide in sensor analysis.
w Optical biosensors consist, for example, of a recognition element and an optical signal transformer (Trends in Biotechnol.
The present invention is concerned with novel silanes and their application for the silanization of dielectric materials and s for anchoring biologically active compounds. Dielectric materials equipped with silane layers are used as solid phases in analytic methods (Methods in Enzymology 44 ( 1976), 134). The new silanes are preferably used for coating signal transformers, e.g. an optical waveguide in sensor analysis.
w Optical biosensors consist, for example, of a recognition element and an optical signal transformer (Trends in Biotechnol.
2 (1984), 59); (Opt. L_ett. 9 (1984) 137); (Sensors and Actuators A, 25 (1990) 185); (Sensors and Actuators B, 6 (1992) 122); (Proc.
~ Biosensors 92, extended abstracts 1992, pp. 339 and 347). The task of the recognition element consists in selectively binding or converting the analyte. This task is accomplished by immobilizing biological recognition molecules (e.g., antibodies, antigens, ligands, ssDNA) on the surface of a signal transformer. In general, ~o for this purpose the surface of the signal transformer (e.g. the surface of a dielectric waveguide) is provided with an organic carrier layer to which the recognition molecules are bound cova-lently. Organic carrier layers with an ordered, compact molecule arrangement, as described in European Patent Application EPA-~ 596421, have proved particularly well-adapted in this context.
These recognition molecules can be used both in their naturally occurring and isolated form, as well as in their chemically or biologically produced form.
ao These types of biosensors can be employed to determine analyte concentrations, e.g. in human and animal diagnostics, in environmental analyses and in food analyses or in the field of biochemical research for quantifying intermolecular interactions of biologically active substances (e.g. antibody-antigen inter-~ actions, receptor-ligand interactions, DNA-protein interactions, etc. ).
Hu/So 23.8.94 2~339~6 For example, the organic carrier layer is constructed by treating the waveguide surface with silanes of general formula I.
(R~R2R3)Si-Y-X
- Si(R~ R2R3) represents a coupling group to the wave-guiding layer. R~~ R2 and R3 signify alkyl, alkoxy or halogen, with at least one being halogen or alkoxy.
- Y is a spacer group and, as such, can be, for example, an alkylene chain, a fluoroalkylene chain or an oligooxyalkylene chain.
- X is a chemically reactive group by means of which bio-logical recognition molecules can be bound' to the organic carrier layer. Known reactive groups are, for example, carboxylic acid halides (-COHaI), olefins (-CH=CH2), nitrites (-CN), thiocyanates (-SCN), thioacetates (-SCOCH3).
The dielectric waveguides coated with aforementioned silanes are hydrolysis-unstable when the reactive group X is e.g. a carboxylic acid halide. When, for example, the reactive group X is an olefin, then the olefin has to be modified and activated in a follow-up step for the subsequent immobilization of biological recognition molecules. This follow-up treatment leads to hydrolysis-stable organic carrier layers with reactive groups.
Such subsequently formed reactive groups are, for example, epoxides, N-hydroxysuccinimide-activated carboxylic acids, ao thiols and the like. In general, it is very expensive to produce such reactive groups quantitatively at a surface.
Accordingly, the object of invention is to provide silanes which can be bound to dielectric materials, with the silanes as already being provided with hydrolysis-stable, reactive X groups which permit the direct immobilization of an organic or bio-logical recognition molecule on the surface without an additional activation step.
~ Biosensors 92, extended abstracts 1992, pp. 339 and 347). The task of the recognition element consists in selectively binding or converting the analyte. This task is accomplished by immobilizing biological recognition molecules (e.g., antibodies, antigens, ligands, ssDNA) on the surface of a signal transformer. In general, ~o for this purpose the surface of the signal transformer (e.g. the surface of a dielectric waveguide) is provided with an organic carrier layer to which the recognition molecules are bound cova-lently. Organic carrier layers with an ordered, compact molecule arrangement, as described in European Patent Application EPA-~ 596421, have proved particularly well-adapted in this context.
These recognition molecules can be used both in their naturally occurring and isolated form, as well as in their chemically or biologically produced form.
ao These types of biosensors can be employed to determine analyte concentrations, e.g. in human and animal diagnostics, in environmental analyses and in food analyses or in the field of biochemical research for quantifying intermolecular interactions of biologically active substances (e.g. antibody-antigen inter-~ actions, receptor-ligand interactions, DNA-protein interactions, etc. ).
Hu/So 23.8.94 2~339~6 For example, the organic carrier layer is constructed by treating the waveguide surface with silanes of general formula I.
(R~R2R3)Si-Y-X
- Si(R~ R2R3) represents a coupling group to the wave-guiding layer. R~~ R2 and R3 signify alkyl, alkoxy or halogen, with at least one being halogen or alkoxy.
- Y is a spacer group and, as such, can be, for example, an alkylene chain, a fluoroalkylene chain or an oligooxyalkylene chain.
- X is a chemically reactive group by means of which bio-logical recognition molecules can be bound' to the organic carrier layer. Known reactive groups are, for example, carboxylic acid halides (-COHaI), olefins (-CH=CH2), nitrites (-CN), thiocyanates (-SCN), thioacetates (-SCOCH3).
The dielectric waveguides coated with aforementioned silanes are hydrolysis-unstable when the reactive group X is e.g. a carboxylic acid halide. When, for example, the reactive group X is an olefin, then the olefin has to be modified and activated in a follow-up step for the subsequent immobilization of biological recognition molecules. This follow-up treatment leads to hydrolysis-stable organic carrier layers with reactive groups.
Such subsequently formed reactive groups are, for example, epoxides, N-hydroxysuccinimide-activated carboxylic acids, ao thiols and the like. In general, it is very expensive to produce such reactive groups quantitatively at a surface.
Accordingly, the object of invention is to provide silanes which can be bound to dielectric materials, with the silanes as already being provided with hydrolysis-stable, reactive X groups which permit the direct immobilization of an organic or bio-logical recognition molecule on the surface without an additional activation step.
This object is achieved by silanes of general formula I
(R~R.2R3)Si-Y-X I
wherein R~, R2 and R3 signify halogen, Y signifies an alkylene chain [-CH2-(CH2)n-CH2-], a fluoroalkylene chain [-CHz-(CF2)~-CH2-], [-CH2,-(CF2)~-CF2-] with n = 1-20 or an oligooxyalkylene chain -[(CH2)~'-O-(CH2)n"]m- with n', n"= 2-6 and m = 2-6 and X signifies an epoxide or an anhydride of a dicarboxylic acid with 4-5 C atoms.
The Si(R~ RZR3) group represents a coupling group to the wave-guiding layer. In the scope of the present invention the term "halogen" signifies chlorine or bromine. Chlorine is preferred. By ~o using trichlorosilanes as organic carrier layers on dielectric waveguides it is possible to produce very stable, compact and ordered sensor surfaces with good optical properties.
The term "alkyl" signifies in the scope of the present 25 invention straight or branched alkyl chains with 1-6 C atoms such as, for example, methyl, ethyl, n-propyl, isopropyl, butyl, tert.-butyl, pentyl, hexyl and the like.
The term "alkoxy" signifies in the scope of the present 3o invention groups in which the alkyl group has the foregoing significance.
The term "aryl" signifies an unsubstituted or substituted phenyl or naphthyl group or the like. An alkyl group is, for a~ example, a suitable substituent.
The X group is a hydrolysis-stable, reactive group which is used for the anchoring of additional organic molecules or for the anchoring of biomolecules after application of the silane to the surface.
The novel silanes according to the invention have the s following advantages:
The reactive groups X of the silanes are hydrolysis-stable, but sufficiently reactive for the immobilization of an organic or biological recognition molecule to take place without further w activation of the silane layer.
The silanes are suitable for the direct coating of dielectric materials, in particular of dielectric waveguides which are preferably made of Zr02, Hf02, Ta205, Si02, A1203, or Ti02.
The silanes can be applied to the surface of dielectric materials not only from solution, but also from the gas phase.
The hydrolysis stability of the reactive groups gives rise to 2o better stability during storage of silane layers and permits their direct application in an aqueous medium.
Short-chain silanes having, for example, an alkylene chain [-CH2-(CH2)~-CH2-] with n = 1-3 are also suitable for silaniz-~s ations, but long-chain analogues are preferred for the construct-ion of oriented, compact layers as are used, for example, in bio-sensors.
A further object of the present invention is to provide ao dielectric waveguides provided with oriented, compact organic carrier layers.
This object is achieved by a dielectric waveguide to whose surface is bound an organic carrier layer, which is constructed ~ from silanes as described above and which consists of sub-units of the general formula Si-Y-X II
wherein Y signifies an alkylene chain [-CHz-(CH2)n-CH2-], a fluoroalkylene chain [-CHZ-(CF2)~,-CH2-], [-CH2-(CFZ)n-CF2-]
with n = 6-20 or an oligooxyalkylene chain -[(CH2)n~-0-(CH2)n"]m- with n', n'" = 2-6 and m = 2-6 and X is an epoxide, an anhydride of a dic:arboxylic acid with 4-5 C atoms.
m The silane layers can be made up of pure alkylene chains, fluoroalkylene chains or oiigooxyalkylene chains or a combination of alkylene chains and fluoroalkylene chains or a combination of alkylene chains and oligooxyalkylene chains.
Due to the long spacer group Y, self-aligning mono-layers are formed during silanization. These layers are compact, exhibit a high degree of order with respect to reactive groups X and they do not affect the optical properties of the waveguide.
m A further object of the invention is concerned with the application of the novel silanes of formula I according to the invention for coating dielectric materials, in particular dielectric waveguides which are preferably made of Zr02, Hf02, ~~ Ta205 or Ti02. If necessary, another thin layer (d < 20 nm) of a silanizable material (Si02, A1203 etc.) can first be applied to the actual waveguide. This supplementary organic layer is used for coupling additional organic molecules or for coupling biologically active molecules.
m After coating dielectric waveguides ~~~rith the novel silanes according to the invention additional molecules can be coupled to reactive group X, as described in the European Patent Application EPA-596421, so as to form an ordered layer consisting of sub-~ units according to general formula Ila Si-Y-Z IIa with the Si atom being bound directly to the solid phase, e.g. of a dielectric waveguide.
w In this case Z signifies:
- hydroxyl, carboxyl, amine, methyl, alkyl, fluoroalkyl groups;
- derivatives of hydrophilic, short-chain molecules such as oligovinyl alcohols, oligoacrylic acids, oligoethylene glycols;
- derivatives of mono- or oligo-saccharides with 1-7 sugar units;
- derivatives of carboxyglycosides;
~o - derivatives of aminoglycosides such as fradiomycin, kanamycin, streptomycin, xylostasin, butirosin, chitosan;
- derivatives of hydrogel-forming groups of natural or synthetic origin such as dextran, agarose, alginic acid, 2s starch, cellulose and derivatives of such polysaccharides, or hydrophilic synthetic polymers such as polyvinyl alcohols, polyacrylic acids, polyethylene glycols and derivatives of such polymers;
30 - a recognition molecule, e.g. antibodies, antigens, ligands, ssDNA;
- a group having the above definition of Z to which a recognition molecule is bound.
as ~I339~6 The following Examples illustrate methods for the production and application of the novel compounds.
I. Production of trichlorosilanes which carry an epoxide s as the reactive group.
Examl to a 1 Production of 7,8-epoxy-octyl-trichlorosilane w 0.05-0.2 g of H2PtCl6 was stirred in 20 ml of dry tetra-hydrofuran. 5 ml (7 g) of trichlorosilane were added to the yellow solution. 5 g of 1,7-octadiene monoxide. were carefully added dropwise to the orange suspension obtained. Then, the mixture was stirred for 5 hours at room temperature and subsequently for about 15 hours at 50~C. The reaction mass was concentrated in a water jet vacuum and distilled at 180~C. 7.1 g of a colourless oil were obtained. The compound was characterized by elementary analysis. This showed:
Calculated: C = 36.72; H = 5.78; CI = 40.65.
Found: C = 36.12; H = 6.28; CI = 40.19.
Example 2 Production of 9,10-epoxy-decyl-tricholorosilane 0.05-0.2 g of H2PtClg was stirred in 20 ml of dry tetra-3o hydrofuran. 5 ml (7 g) of trichlorosilane were added to the yellow solution. 6 g of 9,10-epoxydecene (decadiene monoxide) were carefully added dropwise to the orange suspension obtained. Then, the mixture was stirred for 5 hours at room temperature and subsequently for about 1 S hours at SO~C. The reaction mass was concentrated in a water jet vacuum and distilled at 200~C. About 8 g of a colourless oil were obtained. The compound was char-acterized by elementary analysis. This showed:
z~~3~~s Calculated: C = 41.46; H = 6.61; CI = 36.71.
Found: C = 41.92; H = 6.86; CI = 36.17.
s Cxami la a 3 Production of 13,14-epoxy-tetradecyl-tricholorosilane 0.05-0.2 g of H2PtCl6 was stirred in 20 ml of dry tetra-w hydrofuran. 5 ml (7 g) of trichlorosilane were added to the yellow solution. 8 g of 13,14-epoxytetradecene were carefully added dropwise to the orange suspension obtained. Then, the mixture was stirred for 5 hours at room temperature and subsequently for about 15 hours at 50~C. The reaction mass was concentrated in a ~s water-jet vacuum and distilled at 230~C. About 10 g of a colour-less oil were obtained. The compound was characterized by elementary analysis. This showed:
Calculated: C = 48.63; H = 7.87; CI = 30.76.
~o Found: C = 48.01; H = 7.45; CI = 31.19.
I1. Production of trichlorosilanes carrying an isothio-cyanate as the reactive group.
8xamal,~ 4 Production of 3-(trichlorosilyl)propyl-isothiocyanate 30 0.1 g of H2PtClg was suspended in 5 ml of trichlorosilane.
ml of allyl-isothiocyanate (allyl mustard oil) were added drop-wise to the suspension. Then, the mixture was stirred for about hours at room temperature. The reaction mass was distilled under a water jet vacuum at 130~C in a bulb tube. 8.6 g of a colourless, oil were obtained. The compound was characterized by elementary analysis. This showed:
z~33~~s Calculated: C = 20.48; H = 2.58; N = S = 13.67; CI = 45.34.
Found: C = 21.01; H = 2.77; N = 6.43; S = 14.26;
CI = 44.92.
III. Production of triethoxysilanes carrying an isothio-cyanate as the reactive group.
Exam Ip a 5 w Production of 3-(triethoxysilyl)propyl-isothiocyanate 0.1 g of H2PtCl6 was suspended in 5 ml of triethoxysilane.
(R~R.2R3)Si-Y-X I
wherein R~, R2 and R3 signify halogen, Y signifies an alkylene chain [-CH2-(CH2)n-CH2-], a fluoroalkylene chain [-CHz-(CF2)~-CH2-], [-CH2,-(CF2)~-CF2-] with n = 1-20 or an oligooxyalkylene chain -[(CH2)~'-O-(CH2)n"]m- with n', n"= 2-6 and m = 2-6 and X signifies an epoxide or an anhydride of a dicarboxylic acid with 4-5 C atoms.
The Si(R~ RZR3) group represents a coupling group to the wave-guiding layer. In the scope of the present invention the term "halogen" signifies chlorine or bromine. Chlorine is preferred. By ~o using trichlorosilanes as organic carrier layers on dielectric waveguides it is possible to produce very stable, compact and ordered sensor surfaces with good optical properties.
The term "alkyl" signifies in the scope of the present 25 invention straight or branched alkyl chains with 1-6 C atoms such as, for example, methyl, ethyl, n-propyl, isopropyl, butyl, tert.-butyl, pentyl, hexyl and the like.
The term "alkoxy" signifies in the scope of the present 3o invention groups in which the alkyl group has the foregoing significance.
The term "aryl" signifies an unsubstituted or substituted phenyl or naphthyl group or the like. An alkyl group is, for a~ example, a suitable substituent.
The X group is a hydrolysis-stable, reactive group which is used for the anchoring of additional organic molecules or for the anchoring of biomolecules after application of the silane to the surface.
The novel silanes according to the invention have the s following advantages:
The reactive groups X of the silanes are hydrolysis-stable, but sufficiently reactive for the immobilization of an organic or biological recognition molecule to take place without further w activation of the silane layer.
The silanes are suitable for the direct coating of dielectric materials, in particular of dielectric waveguides which are preferably made of Zr02, Hf02, Ta205, Si02, A1203, or Ti02.
The silanes can be applied to the surface of dielectric materials not only from solution, but also from the gas phase.
The hydrolysis stability of the reactive groups gives rise to 2o better stability during storage of silane layers and permits their direct application in an aqueous medium.
Short-chain silanes having, for example, an alkylene chain [-CH2-(CH2)~-CH2-] with n = 1-3 are also suitable for silaniz-~s ations, but long-chain analogues are preferred for the construct-ion of oriented, compact layers as are used, for example, in bio-sensors.
A further object of the present invention is to provide ao dielectric waveguides provided with oriented, compact organic carrier layers.
This object is achieved by a dielectric waveguide to whose surface is bound an organic carrier layer, which is constructed ~ from silanes as described above and which consists of sub-units of the general formula Si-Y-X II
wherein Y signifies an alkylene chain [-CHz-(CH2)n-CH2-], a fluoroalkylene chain [-CHZ-(CF2)~,-CH2-], [-CH2-(CFZ)n-CF2-]
with n = 6-20 or an oligooxyalkylene chain -[(CH2)n~-0-(CH2)n"]m- with n', n'" = 2-6 and m = 2-6 and X is an epoxide, an anhydride of a dic:arboxylic acid with 4-5 C atoms.
m The silane layers can be made up of pure alkylene chains, fluoroalkylene chains or oiigooxyalkylene chains or a combination of alkylene chains and fluoroalkylene chains or a combination of alkylene chains and oligooxyalkylene chains.
Due to the long spacer group Y, self-aligning mono-layers are formed during silanization. These layers are compact, exhibit a high degree of order with respect to reactive groups X and they do not affect the optical properties of the waveguide.
m A further object of the invention is concerned with the application of the novel silanes of formula I according to the invention for coating dielectric materials, in particular dielectric waveguides which are preferably made of Zr02, Hf02, ~~ Ta205 or Ti02. If necessary, another thin layer (d < 20 nm) of a silanizable material (Si02, A1203 etc.) can first be applied to the actual waveguide. This supplementary organic layer is used for coupling additional organic molecules or for coupling biologically active molecules.
m After coating dielectric waveguides ~~~rith the novel silanes according to the invention additional molecules can be coupled to reactive group X, as described in the European Patent Application EPA-596421, so as to form an ordered layer consisting of sub-~ units according to general formula Ila Si-Y-Z IIa with the Si atom being bound directly to the solid phase, e.g. of a dielectric waveguide.
w In this case Z signifies:
- hydroxyl, carboxyl, amine, methyl, alkyl, fluoroalkyl groups;
- derivatives of hydrophilic, short-chain molecules such as oligovinyl alcohols, oligoacrylic acids, oligoethylene glycols;
- derivatives of mono- or oligo-saccharides with 1-7 sugar units;
- derivatives of carboxyglycosides;
~o - derivatives of aminoglycosides such as fradiomycin, kanamycin, streptomycin, xylostasin, butirosin, chitosan;
- derivatives of hydrogel-forming groups of natural or synthetic origin such as dextran, agarose, alginic acid, 2s starch, cellulose and derivatives of such polysaccharides, or hydrophilic synthetic polymers such as polyvinyl alcohols, polyacrylic acids, polyethylene glycols and derivatives of such polymers;
30 - a recognition molecule, e.g. antibodies, antigens, ligands, ssDNA;
- a group having the above definition of Z to which a recognition molecule is bound.
as ~I339~6 The following Examples illustrate methods for the production and application of the novel compounds.
I. Production of trichlorosilanes which carry an epoxide s as the reactive group.
Examl to a 1 Production of 7,8-epoxy-octyl-trichlorosilane w 0.05-0.2 g of H2PtCl6 was stirred in 20 ml of dry tetra-hydrofuran. 5 ml (7 g) of trichlorosilane were added to the yellow solution. 5 g of 1,7-octadiene monoxide. were carefully added dropwise to the orange suspension obtained. Then, the mixture was stirred for 5 hours at room temperature and subsequently for about 15 hours at 50~C. The reaction mass was concentrated in a water jet vacuum and distilled at 180~C. 7.1 g of a colourless oil were obtained. The compound was characterized by elementary analysis. This showed:
Calculated: C = 36.72; H = 5.78; CI = 40.65.
Found: C = 36.12; H = 6.28; CI = 40.19.
Example 2 Production of 9,10-epoxy-decyl-tricholorosilane 0.05-0.2 g of H2PtClg was stirred in 20 ml of dry tetra-3o hydrofuran. 5 ml (7 g) of trichlorosilane were added to the yellow solution. 6 g of 9,10-epoxydecene (decadiene monoxide) were carefully added dropwise to the orange suspension obtained. Then, the mixture was stirred for 5 hours at room temperature and subsequently for about 1 S hours at SO~C. The reaction mass was concentrated in a water jet vacuum and distilled at 200~C. About 8 g of a colourless oil were obtained. The compound was char-acterized by elementary analysis. This showed:
z~~3~~s Calculated: C = 41.46; H = 6.61; CI = 36.71.
Found: C = 41.92; H = 6.86; CI = 36.17.
s Cxami la a 3 Production of 13,14-epoxy-tetradecyl-tricholorosilane 0.05-0.2 g of H2PtCl6 was stirred in 20 ml of dry tetra-w hydrofuran. 5 ml (7 g) of trichlorosilane were added to the yellow solution. 8 g of 13,14-epoxytetradecene were carefully added dropwise to the orange suspension obtained. Then, the mixture was stirred for 5 hours at room temperature and subsequently for about 15 hours at 50~C. The reaction mass was concentrated in a ~s water-jet vacuum and distilled at 230~C. About 10 g of a colour-less oil were obtained. The compound was characterized by elementary analysis. This showed:
Calculated: C = 48.63; H = 7.87; CI = 30.76.
~o Found: C = 48.01; H = 7.45; CI = 31.19.
I1. Production of trichlorosilanes carrying an isothio-cyanate as the reactive group.
8xamal,~ 4 Production of 3-(trichlorosilyl)propyl-isothiocyanate 30 0.1 g of H2PtClg was suspended in 5 ml of trichlorosilane.
ml of allyl-isothiocyanate (allyl mustard oil) were added drop-wise to the suspension. Then, the mixture was stirred for about hours at room temperature. The reaction mass was distilled under a water jet vacuum at 130~C in a bulb tube. 8.6 g of a colourless, oil were obtained. The compound was characterized by elementary analysis. This showed:
z~33~~s Calculated: C = 20.48; H = 2.58; N = S = 13.67; CI = 45.34.
Found: C = 21.01; H = 2.77; N = 6.43; S = 14.26;
CI = 44.92.
III. Production of triethoxysilanes carrying an isothio-cyanate as the reactive group.
Exam Ip a 5 w Production of 3-(triethoxysilyl)propyl-isothiocyanate 0.1 g of H2PtCl6 was suspended in 5 ml of triethoxysilane.
5 ml of allyl-isothiocyanate (allyl mustard oil) were added drop-~5 wise to the suspension. Then, the mixture was stirred for about hours at room temperature. The reaction mass was distilled in a water jet-vacuum at 140~C in a bulb tube. 8.2 g of a colourless oil were obtained. The compound was characterized by elementary analysis. This showed:
~o Calculated: C = 45.60; H = 8.04; N = 5.32; S = 12.17.
Found: C = 45.91; H = 7.71; N = 5.69; S = 12.64.
~5 IV. Production of trichlorosilanes carrying an acid anhydride as the reactive group.
ao Production of .2-(11-trichlorosilyl-undecenyl)-succinic anhydride 0.01 g of H2PtClg was stirred in 10 ml of dry tetrahydro-furan. 0.3 ml (0.35 g) of trichlorosilane was added to the yellow solution. 0.3 g of 2-(10-undecenyl)-succinic anhydride was carefully added dropwise to the orange suspension obtained. Then, . the mixture was stirred for 5 hours at room temperature and sub-sequently for about 1 S hours at 50~C. The reactio~~ mass was 21~3~t~6 concentrated in a water-jet vacuum and distilled at 230~C. About 0.4 g of a colourless oil was obtained. The compound was char-acterized by elementary analysis. This showed:
s Calculated: C = 46.46; H = 6.50; CI = 27.43.
Found: C = 47.01; H = 6.92; CI = 26.83.
V. Production of the starting materials.
w Exam Ip a 7 Production of 2-(10-undecenyl)-succinic anhydride (Grignard reaction) 0.1 mol of 10-undecenyl-magnesium halide was added drop-wise at -78~C to a suspension of 30 g of malefic anhydride and 10 g of copper I iodide in 100 ml of dry tetrahydrofuran. The reaction mass was heated to room temperature and subsequently 2o stirred for about 15 hours. The reaction mass was concentrated and the residue was taken up in 100 ml of diethyl ether con-taining 2% water and stirred for a further 5 hours. The resulting suspension was filtered and the residue was washed with dry ether. The filtrate was concentrated and distilled in a water jet 2s vacuum at 230~C in a bulb tube. 9.2 g of 2-(10-undecenyl)succinic anhydride were obtained. The compound was characterized by elementary analysis. This showed:
Calculated: C = 71.39; H = 9.59.
so Found: C = 71.12; H = 9.64.
Examiole 8 Production of 2-(10-undecenyl)-succinic anhydride from 2-(10-undecenyl)-succinic acid 2.7 g ofi 2-(10-undecenyl)-succinic acid were stirred with ml of acetic anhydride at 100~C and subsequently concentrated and distilled in a water-jet vacuum at 230~C. 2.5 g of 2-(10-undecenyl)-succinic anhydride were obtained.
Exam~l~ 9 Production of 2-(10-undecenyl)-succinic acid firom methyl 2-(10-undecenyl)-succinate or ethyl 2-(10-undecenyl)-succinate w 2.8 g of methyl 2-(10-undecenyl)-succinate or 3.0 g of ethyl 2-(10-undecenyl)-succinate were stirred with cone. sulphuric acid for 1 hour at room temperature. 2.4 g of 2-(10-undecenyl)-succinic anhydride were obtained after extraction with methylene ~5 chloride.
Exam Ip a 10 Production of methyl 2-(10-undecenyl)-succinate 1.76 g of methyl succinate were converted in dry tetra-hydrofuran using 6 mmol of Li diisopropylamide (LDA) into the enolate and then reacted with 10-undecenyl iodide. The reaction mass was treated with 1 ml of methanol and subsequently with 25 10 ml of water and extracted 3 times with 20 ml of diethyl ether. The organic phases were dried, concentrated and distilled under a water jet vacuum at 200~C in a bulb tube. 534 mg of colourless oil were obtained. The compound was characterized by elementary analysis. This showed:
so Calculated: C = 68.42; H = 10.13.
Found: C = 68.61; H = 9.92.
a5 Exam Ip a 1 1 Production of 10-undecenyl iodide ~~p~~~~s 0.27 mol of 10-undecenyl tosylate was reacted with 250 g of sodium iodide and 4.4 g of tetrabutylammonium oxide as the phase transfer catalyst for about 15 hours under reflux. The reaction mass was extracted 3 times with 400 ml of hexane. The s organic phases were combined, decolorized with sodium bisulphite and dried with sodium sulphate. Concentration and vacuum distillation followed. B.p. (0.3 mbar) 100~C. 72.3 g of a colourless oil were obtained. The compound was characterized by elementary analysis. This showed:
w Calculated: C = 47.15; H = 7.55; I = 45.29.
Found: C = 47.42; H = 7.72; I = 45.01.
VI. Application of densely packed, organic mono-layers to Ti02 surfaces, e.g. from the gas phase to the wave-guiding layer of an optical signal transformer.
Exam I_p a 12 Formation of an organic mono-layer on Ti02 surfaces by treatment with CI3Si-(CH2)~ 2-CH-CJ-12 in a CVD process (chemical vapour deposition). 0 2s A reaction vessel, which can be operated under a pressure of 10-5 mbar and in which the probe to be coated can be heated to temperatures between 30-100~C, was provided for the deposition of silanes of formula I from the gas phase. This reaction vessel was connected to an evacuatable and heatable supply vessel in ao which the compound used for coating can be placed (alternatively, the apparatus can also be epuipped with several of such supply vessels).
For the coating, the optical signal transformer was placed as in the reaction vessel. After introducing the silane Cl3Si-(CH2)~2- \-CH2 into the supply vessel, the supply vessel and the za~~~~6 reaction chamber were brought to a working pressure of 10-5 mbar. The probe to be coated was heated to 100oC. After warming the silane placed in the supply vessel to 50~C the surface was treated for 1 hour with reagent from the gas phase. Subsequently s the flow of reagent was stopped and the probe was subjected to post-treatment in a vacuum at 150~C for 15 min.
The detection of organic mono-layers on surfaces is effected by XPS (X-ray photoelectron spectroscopy) and contact ~o angle measurements).
All silanes of general formula I can be applied to a surface from the gas phase by an analogous procedure.
VII. Application of densely packed, organic mono-layers to Ti02 surfaces, e.g. to the wave-guiding layer of an optical signal transformer using a (CI3Si-(CH2)~ 2-CH-CH2) solution.
y ~o A 0.5% (v/v) solution of (CI3Si-(CH2)~2-CH-CH2) in CCI4 was placed in a reaction vessel under an inert gas atmosphere.
The surface to be coated was brought into contact with this solution for 25 min. under an inert gas. After this treatment the 2s surface was cleaned with CCI4, ethanol and water.
All silanes of general formula I can be applied to a surface from the liquid phase by an analogous procedure.
~o Calculated: C = 45.60; H = 8.04; N = 5.32; S = 12.17.
Found: C = 45.91; H = 7.71; N = 5.69; S = 12.64.
~5 IV. Production of trichlorosilanes carrying an acid anhydride as the reactive group.
ao Production of .2-(11-trichlorosilyl-undecenyl)-succinic anhydride 0.01 g of H2PtClg was stirred in 10 ml of dry tetrahydro-furan. 0.3 ml (0.35 g) of trichlorosilane was added to the yellow solution. 0.3 g of 2-(10-undecenyl)-succinic anhydride was carefully added dropwise to the orange suspension obtained. Then, . the mixture was stirred for 5 hours at room temperature and sub-sequently for about 1 S hours at 50~C. The reactio~~ mass was 21~3~t~6 concentrated in a water-jet vacuum and distilled at 230~C. About 0.4 g of a colourless oil was obtained. The compound was char-acterized by elementary analysis. This showed:
s Calculated: C = 46.46; H = 6.50; CI = 27.43.
Found: C = 47.01; H = 6.92; CI = 26.83.
V. Production of the starting materials.
w Exam Ip a 7 Production of 2-(10-undecenyl)-succinic anhydride (Grignard reaction) 0.1 mol of 10-undecenyl-magnesium halide was added drop-wise at -78~C to a suspension of 30 g of malefic anhydride and 10 g of copper I iodide in 100 ml of dry tetrahydrofuran. The reaction mass was heated to room temperature and subsequently 2o stirred for about 15 hours. The reaction mass was concentrated and the residue was taken up in 100 ml of diethyl ether con-taining 2% water and stirred for a further 5 hours. The resulting suspension was filtered and the residue was washed with dry ether. The filtrate was concentrated and distilled in a water jet 2s vacuum at 230~C in a bulb tube. 9.2 g of 2-(10-undecenyl)succinic anhydride were obtained. The compound was characterized by elementary analysis. This showed:
Calculated: C = 71.39; H = 9.59.
so Found: C = 71.12; H = 9.64.
Examiole 8 Production of 2-(10-undecenyl)-succinic anhydride from 2-(10-undecenyl)-succinic acid 2.7 g ofi 2-(10-undecenyl)-succinic acid were stirred with ml of acetic anhydride at 100~C and subsequently concentrated and distilled in a water-jet vacuum at 230~C. 2.5 g of 2-(10-undecenyl)-succinic anhydride were obtained.
Exam~l~ 9 Production of 2-(10-undecenyl)-succinic acid firom methyl 2-(10-undecenyl)-succinate or ethyl 2-(10-undecenyl)-succinate w 2.8 g of methyl 2-(10-undecenyl)-succinate or 3.0 g of ethyl 2-(10-undecenyl)-succinate were stirred with cone. sulphuric acid for 1 hour at room temperature. 2.4 g of 2-(10-undecenyl)-succinic anhydride were obtained after extraction with methylene ~5 chloride.
Exam Ip a 10 Production of methyl 2-(10-undecenyl)-succinate 1.76 g of methyl succinate were converted in dry tetra-hydrofuran using 6 mmol of Li diisopropylamide (LDA) into the enolate and then reacted with 10-undecenyl iodide. The reaction mass was treated with 1 ml of methanol and subsequently with 25 10 ml of water and extracted 3 times with 20 ml of diethyl ether. The organic phases were dried, concentrated and distilled under a water jet vacuum at 200~C in a bulb tube. 534 mg of colourless oil were obtained. The compound was characterized by elementary analysis. This showed:
so Calculated: C = 68.42; H = 10.13.
Found: C = 68.61; H = 9.92.
a5 Exam Ip a 1 1 Production of 10-undecenyl iodide ~~p~~~~s 0.27 mol of 10-undecenyl tosylate was reacted with 250 g of sodium iodide and 4.4 g of tetrabutylammonium oxide as the phase transfer catalyst for about 15 hours under reflux. The reaction mass was extracted 3 times with 400 ml of hexane. The s organic phases were combined, decolorized with sodium bisulphite and dried with sodium sulphate. Concentration and vacuum distillation followed. B.p. (0.3 mbar) 100~C. 72.3 g of a colourless oil were obtained. The compound was characterized by elementary analysis. This showed:
w Calculated: C = 47.15; H = 7.55; I = 45.29.
Found: C = 47.42; H = 7.72; I = 45.01.
VI. Application of densely packed, organic mono-layers to Ti02 surfaces, e.g. from the gas phase to the wave-guiding layer of an optical signal transformer.
Exam I_p a 12 Formation of an organic mono-layer on Ti02 surfaces by treatment with CI3Si-(CH2)~ 2-CH-CJ-12 in a CVD process (chemical vapour deposition). 0 2s A reaction vessel, which can be operated under a pressure of 10-5 mbar and in which the probe to be coated can be heated to temperatures between 30-100~C, was provided for the deposition of silanes of formula I from the gas phase. This reaction vessel was connected to an evacuatable and heatable supply vessel in ao which the compound used for coating can be placed (alternatively, the apparatus can also be epuipped with several of such supply vessels).
For the coating, the optical signal transformer was placed as in the reaction vessel. After introducing the silane Cl3Si-(CH2)~2- \-CH2 into the supply vessel, the supply vessel and the za~~~~6 reaction chamber were brought to a working pressure of 10-5 mbar. The probe to be coated was heated to 100oC. After warming the silane placed in the supply vessel to 50~C the surface was treated for 1 hour with reagent from the gas phase. Subsequently s the flow of reagent was stopped and the probe was subjected to post-treatment in a vacuum at 150~C for 15 min.
The detection of organic mono-layers on surfaces is effected by XPS (X-ray photoelectron spectroscopy) and contact ~o angle measurements).
All silanes of general formula I can be applied to a surface from the gas phase by an analogous procedure.
VII. Application of densely packed, organic mono-layers to Ti02 surfaces, e.g. to the wave-guiding layer of an optical signal transformer using a (CI3Si-(CH2)~ 2-CH-CH2) solution.
y ~o A 0.5% (v/v) solution of (CI3Si-(CH2)~2-CH-CH2) in CCI4 was placed in a reaction vessel under an inert gas atmosphere.
The surface to be coated was brought into contact with this solution for 25 min. under an inert gas. After this treatment the 2s surface was cleaned with CCI4, ethanol and water.
All silanes of general formula I can be applied to a surface from the liquid phase by an analogous procedure.
Claims (9)
1. Silanes of the general formula I
(R1R2R3) Si-Y-X
wherein R1, R2 and R3 signify halogen, Y signifies an alkylene chain [-CH2-(CH2)n-CH2-], a fluoroalkylene chain [-CH2-(CF2)n CH2-], [-CH2,-(CF2)n-CF2-] with n = 1-20 or an oligooxyalkylene chain -[(CH2)n'-O-(CH2)n"]m- with n', n"= 2-6 and m = 2-6 and X signifies an epoxide or an anhydride of a dicarboxylic acid with 4-5 C atoms.
(R1R2R3) Si-Y-X
wherein R1, R2 and R3 signify halogen, Y signifies an alkylene chain [-CH2-(CH2)n-CH2-], a fluoroalkylene chain [-CH2-(CF2)n CH2-], [-CH2,-(CF2)n-CF2-] with n = 1-20 or an oligooxyalkylene chain -[(CH2)n'-O-(CH2)n"]m- with n', n"= 2-6 and m = 2-6 and X signifies an epoxide or an anhydride of a dicarboxylic acid with 4-5 C atoms.
2. Silanes according to claim 1, wherein Y signifies an alkylene chain [-CH2-(CH2)n-CH2-] with n = 6-20.
3. An optical signal converter comprising a dielectric wave conductor on the surface of which an organic carrier layer is bound, characterized in that the organic carrier layer is composed of silanes as claimed in claim 1 and comprises subunits of the general formula II
in which Y denotes an alkylene chain [-CH2-(CH2)n-CH2-], a fluoroalkylene chain [-CH2-(CF2)n-CH2-], [-CH2-(CF2)n-CF2-]where n= 6-20 or an oligooxyalkylene chain [(CH2)n'-O-(CH2)n"]m where n', n" = 2-6 and m = 2-6 and wherein the group X
denotes an epoxide or an anhydride of a dicarboxylic acid having 4-5 C atoms.
in which Y denotes an alkylene chain [-CH2-(CH2)n-CH2-], a fluoroalkylene chain [-CH2-(CF2)n-CH2-], [-CH2-(CF2)n-CF2-]where n= 6-20 or an oligooxyalkylene chain [(CH2)n'-O-(CH2)n"]m where n', n" = 2-6 and m = 2-6 and wherein the group X
denotes an epoxide or an anhydride of a dicarboxylic acid having 4-5 C atoms.
4. The optical signal converter according to claim 3, wherein the surface of the signal converter is coated with a combination of alkylene chains and fluoroalkylene chains or a combination of alkylene chains and oligooxyalkylene chains.
5. The optical signal converter according to claim 3, wherein the dielectric wave conductor is made of ZrO2, HfO2, Ta2O5 or TiO2.
6. The optical signal converter according to claim 5, wherein another thin layer (d < 20 nm) of a silanizable material is coated on the dielectric wave conductor.
7. Use of the silanes according to claim 1 for coating dielectric materials.
8. Use of organic carrier layers on dielectric materials according to any one of claims 3 to 6 for the immobilization of organic molecules or biological recognition molecules.
9. The optical signals converter of claim 6, wherein the silanizable material is SiO2 or Al2O3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3400/93 | 1993-11-12 | ||
| CH340093 | 1993-11-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2133946A1 CA2133946A1 (en) | 1995-05-13 |
| CA2133946C true CA2133946C (en) | 2006-04-18 |
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ID=4255163
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002133946A Expired - Fee Related CA2133946C (en) | 1993-11-12 | 1994-10-20 | Silanes for the surface coating of dielectric materials |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0653429B1 (en) |
| JP (1) | JP3730273B2 (en) |
| AT (1) | ATE202110T1 (en) |
| CA (1) | CA2133946C (en) |
| DE (1) | DE59409784D1 (en) |
| DK (1) | DK0653429T3 (en) |
| ES (1) | ES2157943T3 (en) |
| GR (1) | GR3036524T3 (en) |
| PT (1) | PT653429E (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8404621B2 (en) | 2008-03-24 | 2013-03-26 | Fujifilm Corporation | Method for immobilization, physiologically active substance-immobilized carrier, carrier for immobilization, carrier, and process for producing carrier |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10158149A1 (en) * | 2001-11-28 | 2003-06-18 | Bayer Ag | Polymers containing silane groups |
| JP5344835B2 (en) * | 2008-03-24 | 2013-11-20 | 富士フイルム株式会社 | Immobilization method, physiologically active substance immobilization carrier and immobilization carrier |
| JP5388462B2 (en) * | 2008-03-24 | 2014-01-15 | 富士フイルム株式会社 | Carrier and production method thereof |
| US9437371B2 (en) * | 2013-06-04 | 2016-09-06 | Silatronix, Inc. | Nitrile-substituted silanes and electrolyte compositions and electrochemical devices containing them |
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| US3790613A (en) * | 1969-01-31 | 1974-02-05 | Gen Electric | Organosilicon compound with isothiocyanate substituent bonded through divalent bridge |
| DE2028702A1 (en) * | 1969-06-13 | 1970-12-17 | Cabot Corp., Boston, Mass. (V.St.A.)j | Process for the production of surface-modified metal or non-metal oxides |
| JPS5566756A (en) * | 1978-11-14 | 1980-05-20 | Toyo Soda Mfg Co Ltd | Carrier for ion exchange liquid chromatography and its manufacturing method |
| CA1317206C (en) * | 1986-09-22 | 1993-05-04 | Takeyuki Kawaguchi | Method for detecting a component of a biological system and detection device and kit therefor |
| JP2637793B2 (en) * | 1988-10-03 | 1997-08-06 | 株式会社日本触媒 | Composition for coating |
| JPH0333029A (en) * | 1989-06-29 | 1991-02-13 | Tokuyama Soda Co Ltd | Improved porous glass body |
| JPH062808B2 (en) * | 1989-10-20 | 1994-01-12 | 信越化学工業株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
| JP2577486B2 (en) * | 1990-03-30 | 1997-01-29 | ホーヤ株式会社 | Plastic lens |
| JPH04145119A (en) * | 1990-10-05 | 1992-05-19 | Toshiba Silicone Co Ltd | Epoxy resin composition |
| JPH04182491A (en) * | 1990-11-15 | 1992-06-30 | Shin Etsu Chem Co Ltd | Organosilicon compound and production thereof |
-
1994
- 1994-10-20 CA CA002133946A patent/CA2133946C/en not_active Expired - Fee Related
- 1994-11-02 DK DK94117244T patent/DK0653429T3/en active
- 1994-11-02 AT AT94117244T patent/ATE202110T1/en not_active IP Right Cessation
- 1994-11-02 DE DE59409784T patent/DE59409784D1/en not_active Expired - Lifetime
- 1994-11-02 EP EP94117244A patent/EP0653429B1/en not_active Expired - Lifetime
- 1994-11-02 PT PT94117244T patent/PT653429E/en unknown
- 1994-11-02 ES ES94117244T patent/ES2157943T3/en not_active Expired - Lifetime
- 1994-11-11 JP JP27796694A patent/JP3730273B2/en not_active Expired - Fee Related
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8404621B2 (en) | 2008-03-24 | 2013-03-26 | Fujifilm Corporation | Method for immobilization, physiologically active substance-immobilized carrier, carrier for immobilization, carrier, and process for producing carrier |
| US8557748B2 (en) | 2008-03-24 | 2013-10-15 | Fujifilm Corporation | Method for immobilization, physiologically active substance-immobilized carrier, carrier for immobilization, carrier, and process for producing carrier |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0653429B1 (en) | 2001-06-13 |
| PT653429E (en) | 2001-10-31 |
| EP0653429A1 (en) | 1995-05-17 |
| JP3730273B2 (en) | 2005-12-21 |
| DK0653429T3 (en) | 2001-09-17 |
| GR3036524T3 (en) | 2001-12-31 |
| DE59409784D1 (en) | 2001-07-19 |
| CA2133946A1 (en) | 1995-05-13 |
| ES2157943T3 (en) | 2001-09-01 |
| ATE202110T1 (en) | 2001-06-15 |
| JPH07188259A (en) | 1995-07-25 |
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