AT503590B1 - PHOTOREACTIVE SURFACE COATINGS - Google Patents

Description

2 AT 503 590 B1

The present invention relates to functional surface layers and surface coatings whose properties can be altered by the action of high-energy radiation, in which context high-energy radiation means ultraviolet (UV) light, visible light, X-radiation, gamma radiation or beta radiation. One goal is to strongly bond the surface layer to the surface to be coated, as well as to selectively couple other molecules (eg, biomolecules, dyes, or metals) in the radiation exposed areas.

From the scientific and technical literature, molecular surface coatings based on compounds (molecules) having the general structure A-B-C are known. Here, A is an anchor group for coupling the compound to a surface, B is a connecting group ("spacer") and C is a further group, where C is a reactive chemical group, but also a non-reactive chemical group (eg alkyl) can be. Optionally, the structural element B ("spacer") also be omitted, so that a general structure A-C may be present.

As anchor groups, for example, the groups trichlorosilyl, trialkoxysilyl, thiol or phosphonic acid have been described. These anchor groups are suitable for the immobilization of molecules on inorganic surfaces. The trichlorosilyl and the trialkoxysilyl substituents allow covalent attachment to oxidic surfaces, for example glass, quartz, titanium oxide. With thiol groups as anchor groups, it is known that attachment to gold surfaces is possible; For example, molecules containing phosphonate groups can be attached to indium-tin oxide surfaces.

For example, compounds having trialkoxysilyl anchor groups are used in the art as adhesion promoters, to modify particles and pigments, and to hydrophobize surfaces. In other fields of application, for example, long-chain alkane thiols are used to modify gold surfaces. Monolayers form on the metal surface under suitable conditions, which are described in the literature as "soap-assembled monolayers" (abbreviation: SAM).

Through such molecular surface coatings, the properties of surfaces can be modified in a wide range and adapted for technical applications. Most of these surface layers have the property that they are unreactive under light, so that the surface properties once generated remain intact even under the influence of light over a longer period of time.

In the scientific literature, there are only a few examples of photoreactive compounds having a general structure A-B-C or A-C, wherein the group C is such that it undergoes a photochemical reaction under UV irradiation.

For example, surface layers containing UV-reactive cinnamic acid units which can dimerize have been described in the articles of Q. Xia, W.-S. Feng, J. Mu, K.-Z. Yang, Langmuir 14 (1998), 3333-3338 and by J. Zhao, H. Akiyama, K. Abe, Z. Liu, F. Nakanishi, Langmuir 16 (2000), 2275. Similarly, molecules with cinnamylidene units are known (A. Yabe, Y. Kawabata, A. Ouchi, M. Tanaka, Langmuir 3 (1987), 405-409). The dimerization creates cyclobutane derivatives, which are not chemically reactive groups.

Photoinduced cleavage reactions leading to cleavage of moieties have been described, for example, for surface coatings containing ortho-nitrobenzyl esters, see K. Critchley, J.P. Jeyadevan, H. Fukushima, M. Ishida, T. Shimoda, R. J. Bushby, S.D. Evans, Langmuir 21 (2005), 4554-4561 and D. Ryan, B.A. Parviz, V. Linder, V. Semetey, S.K. Sia, J. Su, M. Mrksich, G.M. Whitesides, Langmuir 20 (2004), 9080-9088. 3 AT 503 590 B1

Also, the UV-induced cleavage of nitrogen (N2) from immobilized (SAM) molecules is known. This concerns z. See, for example, the cleavage reaction of photolabile organic azides (R-N3), see the articles by E.W. Wollman, D. Kang, D. Frisbie, I.M. Lorkovic, M.S. Wrighton, J. Am. Chem. Soc. 116 (1994), 4395-4404, C.D. Frisbie, E.W. Wollman, M.S. Wrighton, Langmuir 11 (2005), 2563-2571 and S. Monsathporn, F. Effenberger, Langmuir 20 (2004), 10375-10378 on organic azides. Nitrogen (N2) can also be developed under irradiation from immobilized diazoketones (R = N2), see the article by J. Hu, Y. Liu, C. Khemtong, JM El Khoury, TJ McAfoos, IS Taschner, Langmuir 20 (2004) , 4933-4938. Both azides and diazoketones form highly unstable reaction products (nitrenes or carbenes) as a result of UV irradiation.

The reversible photochemical cis-trans equilibrium of azobenzene units has also been studied on surfaces (A. Manna, P.-L.Chen, H. Akiyama, T.-X., Wie, K. Tamada, W. Knoll, Chem. Mater. 15 (2003), 20-28 and H. Akiyama, K. Tamada, J. Nagasawa, K. Abe, T. Tamaki, J. Phys. Chem B 107 (2003), 130-135), as well as the photoinduced transformations in Komats, K. Yamada, T. Murakami, K. Kimura, J. Am. Chem. Soc., 127 (2005), 3026-3030). In these reactions, however, no chemically reactive groups are formed by the UV irradiation.

Furthermore, published patent application US 2004/0146715 A1 describes surface-active monolayers. These consist of films containing hydrophilic and hydrophobic blocks as well as covalently bonded photoinitiators in the form of aryl ketones. Photoreactive, polymerizable diacetylene structures with terminal thiol group are described in JP 2001247540. In these reactions, however, stable and simultaneously reactive groups are not formed as a result of irradiation.

Surface coatings can also be made from photoreactive compounds whose photolysis first gives the anchor group to the surface. By means of photolysis, very unstable reactive groups that can be reacted in situ are formed, with which these compounds are immobilized on surfaces. Biocompatible coatings based on molecules endowed with azido groups or aryl ketones as photoinitiators are described in EP 0 407 390 B1. Similarly, US 5,217,492 A describes immobilizing biomolecules on surfaces wherein the biomolecules are equipped with latent photoreactive groups, e.g. As azides, oxazidines, diazoketones, aromatic ketones, diazonium groups or benzoylbenzoic acid. The goal of these compounds, however, is a coupling by photochemical reaction, but not the achievement of a photochemically reactive surface coating.

A major disadvantage of such compounds described in the literature (and surface coatings produced therefrom) is that the irradiation ("activation") creates no functional groups which are stable for a long time and, in addition, a subsequent reaction with other molecules, ions or metals enable. In many cases, it proves to be particularly disadvantageous that an irradiated and thus activated surface can not be stored, so that coupling of further molecules to these surfaces must take place in situ. Therefore, in these methods, molecules that are themselves radiation sensitive can be coupled to the activated surface only under severe conditions.

Those of the photochemical reactions described above, which lead to the cleavage of molecular fragments or gaseous molecules, additionally have the disadvantage that the cleavage products can interfere with the subsequent reactions and that there may be a decrease in the layer thickness of the surface coating.

The present invention sets itself the goal of eliminating the disadvantages mentioned. 4 AT 503 590 B1

This object is achieved by a compound according to claim 1. Advantageous variants of a compound according to the invention are the subject matter of claims 2 to 5.

The object according to the invention is achieved by the use of compounds of the type A-B-C or A-C in which, under high-energy irradiation in the substructure C, isomerization reactions take place such that the group C is converted into a reactive group D. The radiation-reactive group C is such that upon irradiation, a virtually irreversible isomerization (i.e., rearrangement) to a stable group D occurs which has a different chemical reactivity than the group C. Another feature of the invention is that under irradiation no molecular fragments are eliminated from the group C, so that there is no development of gaseous or liquid fission products or that such cleavage products arise only as minor by-products. At the same time, the anchor group A guarantees excellent adhesion of the compounds to the surface to be coated.

Due to this particular chemical composition of the compounds A-B-C or A-C, it is possible to change the properties of the surface coating under high-energy radiation in a precisely defined manner and to adapt it to the requirements. After using lithographic techniques and a structured (ie patterned) UV exposure can be performed, the modification of the surface properties can also be carried out spatially resolved and structured ("patterning").

A further feature of the present invention is that the action of high energy radiation, such as UV radiation, visible light, beta radiation, X-ray or gamma radiation, as a result of the isomerization reaction, provides stable functional groups, which in turn provide a binding capacity for others Have molecules, ions or metals. So a z. B. structured by UV light surface coating in the exposed areas are selectively modified by a subsequent chemical reaction. A surface coating with compounds of the general structure A-B-C is thus converted by energetic radiation by isomerization into a coating with stable compounds A-B-D, where D is the group generated by irradiation. By a subsequent reaction, this surface layer A-B-D is converted into a coating of the type A-B-D-E, where E stands for a coupled further molecule, an ion or a metal. This also applies mutatis mutandis to compounds having the general structure A-C.

According to the invention compounds of the general structure ABC or AC are claimed, wherein the substructure A is an anchor group and may be, for example: -SiX (3-n) Yn with n = 0, 1 or 2, wherein the substituent X is a halogen (chlorine, Bromine, iodine) or a hydroxy or an alkoxy group (-OR), where R can be a straight-chain or branched C 1 -C 5 -alkyl radical, preferably C 1 -C 5 -alkyl radical, or else a phenyl radical. Examples of straight-chain or branched CrCis-alkyls of the group R are methyl, ethyl, propyl, butyl or pentyl. In this case, in the substructure -SiX (3.n) Yn, similar as well as different alkoxy groups (-OR) can be present.

The substituent Y can be a straight-chain or branched C 1 -C 15 -alkyl, preferably C 1 -C 5 -alkyl, or an aryl group, for example phenyl, or an aralkyl group, for example benzyl.

In a preferred embodiment, the substructures A are the groups 5 AT 503 590 B1

Trichlorosilyl -SiCl 3,

Tribromosilyl -SiBr3,

Trialkoxysilyl -Si (OR) 3 with R = methyl, ethyl or propyl,

Dimethylchlorosilyl-SiCl (CH 3) 2,

Methyldichlorosilyl -SiCI2CH3 before. The organosilicon anchor groups are preferably used for immobilization on oxidic surfaces.

Furthermore, the substructure A can be

Mercapto -SH,

Selenol -SeH,

Silane -SiH.

Thiol and selenol groups are preferably used for immobilization on gold and silver surfaces.

In the compounds according to the invention, the substructure B has the function of a spacer which connects the substructures A and C to one another. The partial structure B can be: a straight-chain or branched CrC20-alkylene, preferably C 2 -C 10 -alkylene which is optionally mono- or polysubstituted by one or more cycloalkyl, aryl, aralkyl, heteroaryl or halogen groups, where the halogen group is fluorine , Chlorine, bromine and iodine are to be understood.

Examples of straight-chain or branched C 1 -C 20 -alkenes of substructure B are methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, isopropylene, isobutylene, neopentylene or neohexylene.

For the substituents of the alkylene groups, cycloalkyl is, for example, cyclopentyl, cyclohexyl or cycloheptyl, aryl being, for example, phenyl, aralkyl being, for example, benzyl or toluyl, heteroaryl being, for example, furyl, pyrrolyl, thiophenyl or pyridinyl.

Furthermore, the substructure B can be

Cycloalkylene, arylene, heteroarylene or arylenealkylene, where cycloalkylene is, for example, cyclohexylene and cyclopentylene, arylene being, for example, phenylene or biphenylene or naphthylene, arylenealkylene being, for example, phenylene-methylene, methylene-phenylene, phenylene-ethylene, ethylene-phenylene or ethylene- phenylene-methylene and under heteroaryls, for example, furylene, pyrrolylene, thiophenylene is to understand and the cycloalkylene, arylene, arylenealkylene and heteroarylene groups may also be substituted, for example with fluorine or chlorine.

Furthermore, the substructure B can be:

Oligo- and polyoxymethylene - (O-CH2) n- with n between 1 and 30,

Oligo- and polyethyleneglycol - (O-CH2-CH2) n- with n between 1 and 30,

Oligo- and polypropyleneglycol - (O-CH 2 -CH 2 -CH 2) n- with n between 1 and 30,

Oligo- and polybutylene glycol - (O-CH 2 -CH 2 -CH 2 -CH 2) n - with n between 1 and 30,

Oligo- and polysiloxane - (SiR ^ -O) ,, -, wherein in the siloxane unit, the substituents Ri and R2 straight-chain or branched Ci-Cs-alkylene radicals, for example methylene, ethylene, propylene, butylene, pentylene or cyclo 6 AT 503 590 B1 hexylene or phenylene.

Substructure C is a radiation-sensitive group which undergoes an isomerization reaction under energy-rich radiation to form a stable and simultaneously reactive group D.

According to the invention, substructure C may be:

Esters of thiocyanic acid -R3-SCN,

Esters of selenocyanic acid -R3-SeCN,

Esters of cyanic acid -R3-OCN, where the substituent may be R3: a linear or branched alkyl group, a substituted alkyl group, for example perfluoroalkyl, an aryl group, such as phenylene, naphthylene, phenanthrenylene, anthracenylene, an aralkyl group, such as e.g. Phenylmethylene, naphthylmethylene,

Phenanthrenylmethylen, anthracenylmethylene, wherein in the substituent R3 to increase the light absorption and carbonyl groups may be included, such as. Phenacyl (phenylcarbonylmethyl) or naphthacyl (naphthylcarbonylmethyl).

Depending on the nature of the substituent R3, a radical rearrangement of the substituents SCN, SeCN and OCN occurs in the substructures C under irradiation, resulting in the isomeric isothiocyanates (-R3-NCS), isoselenocyanates (-R3-NCSe) and isocyanates (- R3-NCO) leads. These groups, which are obtained by photo- or radiation isomerization, are storage stable and have a high reactivity towards aliphatic and aromatic amines (eg with the structure R4-NH2). Under addition reaction, the corresponding thiourea, selenourea or urea derivatives with the general structures R3-NH (C = S) NH-R4, R3-NH (C = Se) NH-R4, R3-NH (C = 0) NH -R4 formed.

Similarly, thiols (general structure R4-SH) and alcohols (general structure R4-OH) can add to the photochemically-formed groups -R3-NCS, -R3-NCSe, and isothiocyanate-R3-NCO, yielding the corresponding thiocarbamate and carbamate Structures arise, such. B. the dithiocarbamate -R3-NH (C = S) S-R4 by reaction of -R3-NCS with the thiol R4-SH.

The photoisomerization of organic thiocyanates, selenocyanates and cyanates has been described in the literature, as well as the coupling of amines and thiols to the photoreaction products (W. Kern, AT 400842 (1996), W. Kern, C. Preininger, Austrian Patent Application A 498 / 2002, G. Langer, T. Kavc, W. Kern, G. Kranzelbinder, E. Toussaere, Macromol Chem Phys 202, 2001, 3459-3467). This coupling reaction can be used for the immobilization of small molecules, dyes and biomolecules.

The invention further claims surface coatings of metals, metal oxides, oxide surfaces, inorganic surfaces and plastic surfaces using the radiation-reactive compounds having the general structure A-B-C or A-C, as described in the preceding section.

In a preferred embodiment of the invention, surfaces are coated by one or more immersions in solutions of compound A-B-C in a suitable solvent. In a further embodiment, the surfaces are coated by dropping solutions of compound A-B-C or by spin-coating or spraying with solutions of compound A-B-C. In a further preferred embodiment, the surface is coated by vapor deposition with a compound A-B-C, wherein this type of coating can also be carried out under reduced pressure. Analogously, these methods also apply to the coating of surfaces with compounds of general structure A-C.

To achieve the isomerization reaction in the surface coatings containing compounds A-B-C or A-C, which leads to the structures A-B-D or A-D, high-energy radiation is used. The process of irradiation is also referred to below by the term io "activation". Preferably, but not exclusively, light is used in the wavelength range 150 nm to 800 nm. Very particular preference is given to using ultraviolet light in the wavelength range from 200 nm to 400 nm.

A structured, ie spatially resolved, irradiation is preferably carried out with ultraviolet light 15 using lithographic masks (contact or projection lithography).

Similarly, as high-energy radiation and X-ray or electron radiation can be used, with these types of radiation, a spatially resolved Be-20 radiation is possible.

A coupling of further molecules, biomolecules, ionic compounds, dyes or metals to the described surface coatings is preferably carried out by immersing the activated surface coating in solutions or dispersions of further molecules, biomolecules, ionic compounds, dyes or metals. In a further embodiment, the subsequent coupling of molecules, biomolecules, ionic compounds, dyes and metals can be carried out by vapor deposition, optionally under reduced pressure. In a further embodiment, the irradiation of the surface coating is carried out in the presence of the substance to be coupled or in the presence of 30 solutions of the substance to be coupled.

The reactivity differences in the surface coating achieved by a radiation-chemical reaction can, in certain cases, also be utilized in such a way that a coupling reaction preferably takes place on the non-irradiated areas of the surface coating 35.

Ausführunasbeispiele

Example 1: 40

Preparation of [4- (thiocyanatomethyl) phenyl] trimethoxysilane 45

+ 1.1 NH4SCN

7.62 g (100 mmol) of ammonium thiocyanate are dissolved in 50 ml of methanol. To this solution 50 is added 20 mL (91 mmol) of [4- (chloromethyl) phenyl] trimethoxysilane. The clear, colorless batch is heated to reflux for 2 days with exclusion of light. Thereafter, the resulting white precipitate of sodium chloride under protective gas atmosphere (argon) is separated by means of a reverse frit and the remaining solution in vacuo (1 mbar) evaporated. The remaining yellow oil is taken up in 30 ml of heptane and this solution is filtered. The n-heptane is evaporated in an oil pump vacuum. The product is obtained as yellow liquid. 1 H NMR spectrum (δ, 500 MHz, 20 ° C, CDCl 3): 7.68 (doublet, 2H, aromatic protons), 7.39 (doublet, 2H, aromatic protons), 4.16 (singlet, 2H, -CH2-), 3.63 (singlet, 9H, -OCH3); 13C {1H} NMR (δ, 125 MHz, 20 ° C, CDCl3): 136.8 (1C, phenyl-C1), 135.7 (2C, phenyl-C3 '5), 130.7 (1C, phenyl -C4), 128.6 (2C, phenyl-C2 x 6), 111.9 (1C, -SCN), 51.0 (3C, -OCH3), 38.3 (1C, -CH2-). IR data (film on silicon wafer in transmission, cm'1): 3074-3021, 2976-2892, 2155 (m, SCN), 1603, 1476, 1443, 1392, 1294, 1246, 1166, 1124-1079 (Si 0-), 1022, 962, 785, 715.

Example 2:

Preparation of 2- (4-thiocyanatomethyl) phenyl-ethane-1-thiol

The addition of triphenylsilanethiol to the double bond is carried out according to a procedure of B. Hache, Y. Gareau, Tetrahedron Lett. 35 (1994), 1837 and W.C. Black, B. Guay, Synthesis 1998, 1101 with triphenylsilathiane and azaisobutyronitrile as radical initiator. 4.118 g (14.08 mmol) of triphenylsilanethiol, 1.33 ml (9.39 mmol) of 4-vinylbenzyl chloride and 0.462 g (2.82 mmol) of azoisobutyronitrile are dissolved in 20 ml of benzene. The yellow clear batch is heated to reflux for one hour. The benzene is evaporated in vacuo (1 mbar). The residue is treated with a mixture of acetone / n-hexane (1:20), the white precipitate is centrifuged off and the solvent is evaporated off. The resulting oil is purified by chromatography on a silica gel column. The eluent used is a mixture of acetone and hexane (parts by weight: 1 part of acetone: 20 parts of hexane). Yield: 3.018 g of white powder [2- (4-chloromethylphenyl) ethylsulfanyl] triphenylsilane. 1 H-NMR (δ, 500 MHz, 20 ° C, CDCl 3): 7.68 (dd, 6H, ph 2 '2' x 2 'x 6' x 6 'x 6'), 7.46 to 7.44 ( m, 3H, Ph4 'x 4 "x 4"), 7.42 to 7.39 (m, 6H, ph3.3-, i -', 5.5 -5 ") i 7 24 (d 2H ph3.5 ) | 6 96 (dj 2Hj ph2.6) j 4 54 (Sj 2H] .o- ^ ciy 2,73-2,65 (m, 4H, -CH 2 S, CH 2 Ph) 107 mg (1.42 mmol) of ammonium thiocyanate are dissolved in 5 mL of methanol are dissolved and 573 mg (1.29 mmol) of [2- (4-chloromethylphenyl) ethylsulfanyl] triphenylsilane dissolved in 5 mL of CH 2 Cl 2 are added and the reaction is refluxed for 16 h with exclusion of light The solvent is evaporated in vacuo (1 mbar), the residue is taken up in CH 2 Cl 2 and filtered, the solvent is evaporated in vacuo and the remaining yellow oil is purified by column chromatography (mobile phase: 10% acetone / n-hexane, silica gel). Yield: 154 mg (57% of theory) of yellow crystals, since cleavage by trifluoroacetic acid is no longer necessary because the triphenylsilyl group is already cleaved under the chosen conditions (NH 4 SCN, heat) Spectroscopic data of the obtained 2- (4-thiocyanatomethyl) phenyl ethane-1-thiol: 1 H NMR (δ, 500 MHz, 20 ° C, CDCl 3 ): 7.27 (dd, 4H, aromatic protons) 4.15 (s, 2H, -CH2-SCN), 2.94 (t, 2H, -CH2-Ph), 2.79 (m, 2H, - CH2-SH), 1.38 (t, -SH); 13C {1H} -NMR (δ; 125 MHz, 20 ° C, CDCl 3): 140.9, 135.3, 130.3, 128.2, (6C, Ph) 112.2 (1C, -SCN), 40.0 ( 1C, HSCH2CH2-Ph), 38.2 (1C, CH2-SCN), 25.9 (1C, -CH2-SH) IR data (film on silicon wafer in transmission, cm'1): 3068-3011.2931 ( w, aliph vCh), 2565 (w, vSH), 2153 (m, vSCn), 1589 (w), 1513 (w), 1485 (w), 1428 (s), 1246 (w), 1186 (w), 1120 (s), 1027 (w), 998 (w), 837 (s), 738 (m), 713 (s), 699 (s), 668 (w), 636 (w), 514 (s). 9 AT 503 590 B1

Example 3:

Preparation of photoreactive monolayers and thin layers of 2- (4-thiocyanatomethyl) phenyl-ethane-1-thiol on gold and their reaction under UV irradiation

A freshly purified gold foil is immersed for 2 hours in a 2 mM solution of 2- (4-thiocyanatomethyl) phenyl-ethane-1-thiol (see Example 2) in toluene. The gold foil is removed and non-adherent 2- (4-thiocyanatomethyl) phenyl-ethane-1-thiol washed off with toluene. Infrared spectroscopy reveals the thiocyanate band at 2153 cm'1. Irradiation with UV light at 254 nm may induce photoisomerization as evidenced by the disappearance of the band at 2153 cm'1 (SCN) and the appearance of bands typical of NCS groups at 2180 cm'1 and 2105 cm'1 is.

Example 4:

Preparation of photoreactive monolayers and thin films of [4- (thiocyanatomethyl) phenyl] trimethoxysilane on silica surfaces

A freshly oxidized silicon wafer (Caro's acid, 10 min, 30% H 2 O 2 in concentrated H 2 SO 4, then rinsed several times with double-distilled water and dried at 120 ° C.), which has a silicon dioxide surface after this treatment, is converted to a 0, 5% solution of [4- (thiocyanatomethyl) phenyl] trimethoxysilane (see Example 1) in toluene for 24 hours. Unreacted educt is rinsed by rinsing with toluene. The infrared spectrum reveals the band at 2153 cm'1. By irradiation with UV light of 254 nm, photoisomerization can be induced, as evidenced by the disappearance of the SCN band at 2153 cm -1 and the appearance of the NCS bands at 2180 cm -1 and 2105 cm -1.

Example 5:

Preparation and UV activation of thiocyanate-containing photoreactive coatings for glass and oxidic materials

One part by weight of [4- (thiocyanatomethyl) phenyl] trimethoxysilane (see Example 1) is mixed with four times the amount of tetraethoxysilane in 10 parts of ethanol. By dip coating or spin coating (1000 revolutions / min, 60 seconds) are applied to silicon or glass surfaces transparent layers (layer thickness about 1 pm) and then dried at 80 ° C to 100 ° C. The resulting layer is then irradiated by means of UV light (Hg high-pressure lamp) for 10 min. As a result, the refractive index of the coating is increased by the value + 0.025 (at the wavelength 500 nm). Upon irradiation with UV light, the bands of the SCN groups decrease at 2153 cm'1, whereas the NCS bands are formed at 2104 cm'1 and 2179 cm'1.

Example 6:

Reaction of a UV-activated coating on silica surfaces with amines

Silica surfaces are coated according to Example 4 with [4- (thiocyanatomethyl) phenyl] trimet-hoxysilane and irradiated with ultraviolet light. Subsequently, the activated coating is vaporized with gaseous propylamine, whereby the isothiocyanate group (NCS) reacts with the propylamine to form a thiourea derivative. In the IR spectrum of the activated coating, the bands disappear at 2180 cm'1 and 2105 cm'1 (NCS), and at the same time, the bands typical for thiourea derivatives become 3363 cm'1 and 3260 cm'1 (NH oscillations) and at 1554 cm'1 (C = S oscillation) visible.

Claims (16)

EXAMPLE 7 Deposition of Elemental Silver and Silver Salts on Activated Surfaces A coating prepared according to Example 5 on silica, which contains [4- (thiocyanatomethyl) phenyl] trimethoxysilane and tetraethoxysilane, is prepared by UV irradiation over a wide area (Medium pressure mercury lamp) activated, and then placed in a silver nitrate solution (1 weight percent AgNO 3 in water) for 24 hours. Thereafter, the surface is rinsed well with bidistilled water. It is discolored by silver salts and elemental silver. At the same time, in the IR spectrum of the exposed side, the absorption bands characteristic of the isothiocyanate compounds disappear at 2180 cm -1 and 2105 cm -1 (NCS). This deposition of silver does not occur if the coating has not previously been irradiated with UV light. Example 8: Patterned Deposition of Silver and Silver Salts on Activated Surfaces According to Example 6, a UV-reactive coating containing [4- (thiocyanatomethyl) phenyl] trimethoxysilane and tetraethoxysilane is applied to a silica surface. The UV exposure is now carried out by means of a medium-pressure mercury lamp through a lithographic contact mask, which contains a chromium pattern on quartz. Thereafter, the patterned exposed sample is placed in a silver nitrate solution (1 weight percent AgNO 3 in water) for 24 hours. Thereafter, the surface is rinsed well with bidistilled water. It can be seen in the exposed areas of the surface a brown coloration by silver salts and elemental silver. In Fig. 1, the sites which have been activated by the photochemical reaction and thereafter reacted with the silver nitrate solution are shown dark. Claims 1. A compound of the general formula ABC or AC, wherein the substructure A is a An anchor group, which allows a connection of the compound to a surface of an article, and the optionally provided substructure B is a spacer group, which the substructures A and C is covalently bonded to each other, wherein the partial structure C is -R3-SCN, -R3-SeCN or -R3-OCN, wherein the group R3 is an arylene group or an aralkylene group and the partial structure A is an organosilicon group -SiX (3.n) Yn with n = 0, 1 or 2, wherein Y is a straight-chain or branched Ci-Ci5-alkyl, preferably CrC5-alkyl, or an aryl group, for example phenyl, or an aralkyl group, for example benzyl, and wherein the substituent X is a halogen (CI, Br, J) or a hydroxy or an alkoxy group (-OR), where R may be a straight-chain or branched C 1 -C 15 -alkyl radical, preferably C 1 -C 5 -alkyl radical, or a phenyl radical and where the same or different alkoxy groups (-OR) in the partial structure -SiX (3.n) Yn or the partial structure A is selected from the group consisting of thiol -SH, selenol -SeH and silane -SiH. 2. A compound according to claim 1, wherein the partial structure A is selected from the group consisting of trichlorosilyl -SiCI3, tribromosilyl -SiBr3, Trialkoxysilyl -Si (OR) 3 with R = methyl, ethyl or propyl, dimethylchlorosilyl -SiCI (CH3) 2 and Methyldichlorosilyl -SiCl 2 CH 3. 3. A compound according to claim 1 or 2, wherein the partial structure B is a straight-chain or branched CrCarAlkylen, preferably a C2-Ci0-alkylene, optionally mono- or polysubstituted with one or more cycloalkyl, aryl, aralkyl, heteroaryl or Halogen groups is substituted, where as the halogen group fluorine, chlorine, bromine and iodine are to be understood. 1 1 AT 503 590 B1 4. A compound according to claim 1 or 2, wherein the partial structure B is selected from the group consisting of oligo- and polyoxymethylene - (0-CH2) n- with n between 1 and 30, oligo- and polyethylene glycol - (0-CH2-CH2 ) n with n between 1 and 30, oligo- and polypropyleneglycol - (O-CH2-CH2-CH2) n- with n between 1 and 30, oligo- and polybutylene glycol - (0-CH2-CH2-CH2-CH2) n - With n between 1 and 30, oligo- and polysiloxane - (SiR ^ -O) ,, -, wherein in the siloxane unit, the substituents Ri and R2 straight-chain or branched Ci-C5-alkylene radicals such as methylene, ethylene, propylene, butylene len , Pentylene or cyclohexylene or phenylene. A compound according to any one of claims 1 to 4, wherein the partial structure C is -R3-SCN, -R3-SeCN or -R3OCN and wherein the group R3 is an arylene group or an aralkyl group selected from the group consisting of Phenylene, naphthylene, phenanthrenylene, anthracenylene, phenylenemethylene, naphthylenemethylene, Phenanthreny-lenmethylen, anthracenylenemethylene, wherein in the substituent R3 to increase the light absorption and carbonyl groups may be included. 6. An article comprising a surface coating of a compound according to any one of claims 1 to 5, wherein the article consists of a metal, an oxide of a metal such as silica or germanium oxide or a plastic or a polymer. 7. A process for producing an article with an at least partially reactive surface coating, wherein an article is subjected according to claim 6 irradiation with high-energy radiation. 8. The method of claim 7, wherein the surface coating is subjected to a structured spatially resolved irradiation with high-energy radiation. 9. The method of claim 7 or 8, wherein the surface coating is subjected after irradiation of a chemical reaction. 10. The method of claim 7 or 8, wherein the surface coating is subjected to irradiation with high-energy radiation and at the same time a chemical reaction. 11. The method according to any one of claims 7 to 10, wherein ultraviolet light is used as high-energy radiation. 12. The method according to any one of claims 7 to 11, wherein the surface coating contains several different compounds of the general structure A-B-C or A-C. 13. The method according to any one of claims 7 to 12, wherein an immobilization of biomolecules, dyes, ionic compounds, metal salts, metals, metal compounds, nanoparticles and low molecular weight organic and inorganic compounds takes place during or after the irradiation with high-energy radiation. 14. Use of a compound according to any one of claims 1 to 5 for the production of surface coatings. 15. Use of a compound according to any one of claims 1 to 5 for the modification of nanoparticles and nanostructured materials. 16. Use of articles according to claim 6 for the production of optical, electronic, electrical, medical and pharmaceutical products. AT 503 590 B1 1 2 For 1 sheet of drawings