EP1478926A1

EP1478926A1 - Ultraphobic surface having a multitude of reversibly producible hydrophilic and/or oleophilic areas

Info

Publication number: EP1478926A1
Application number: EP03742574A
Authority: EP
Inventors: Joachim Engelking; Karsten Reihs; Eckhard Nordhoff; Martin Müller
Original assignee: Sunyx Surface Nanotechnologies GmbH; Scienion GmbH
Current assignee: Qiagen GmbH; Scienion GmbH
Priority date: 2002-02-22
Filing date: 2003-02-24
Publication date: 2004-11-24
Also published as: AU2003215589A1; WO2003071275A1; US20060013735A1

Abstract

The invention relates to a planar structure, particularly a plate, having an ultraphobic surface on which the hydrophilic and/or oleophilic areas can be reversibly produced. The invention also relates to a planar structure comprising an ultraphobic surface provided with hydrophilic and/or oleophilic areas that are each completely surrounded by ultraphobic areas. The invention additionally relates to methods for reversibly producing hydrophilic and/or oleophilic areas on ultraphobic surfaces, to the deposition of liquid drops onto the inventive planar structure, and to the use of the inventive planar structure for conducting mass spectroscopic and/or optical analysis of aqueous liquids. .

Description

Ultraphobic surface with a large number of reversible hydrophilic and / or oleophilic areas

The present invention relates to a flat structure, in particular a flat plate, with an ultraphobic surface on which hydrophilic and / or oleophilic areas can be reversibly generated. Furthermore, the present invention relates to a flat sheet-like structure with an ultraphobic surface with hydrophilic and / or oleophilic areas, each of which is completely enclosed by ultraphobic areas. The present invention further relates to methods for the reversible generation of hydrophilic and / or oleophilic regions on ultraphobic surfaces, the deposition of liquid drops on the flat structures according to the invention and the use of the flat structures according to the invention for mass spectrometric and / or optical analysis of samples.

In the field of active ingredient chemistry, but also in biological research and production, serial tests are increasingly being carried out today. For example, a large number of the smallest, liquid samples are mixed with different active substances in order to test their reaction to the respective active substance.

For such experiments, so-called microtiter plates or sample carriers are known from the prior art which, for example, have a large number of depressions at regular intervals. Sample carriers are known from WO 98/45406 and DE 19628 928, the surface of which is hydrophobic and the hydrophilic recesses are incorporated into them. These sample carriers have the disadvantage that the depressions are already arranged at predetermined locations, so that the sample carriers cannot be individually adjusted to the particular experiment. Furthermore, these sample carriers have the disadvantage that the comparatively large depressions can only be incorporated into the hydrophobic surface with a relatively high outlay. A sample carrier with a hydrophobic surface is known from German published patent application DE 197 54 978. Hydrophilic anchor areas are incorporated into this hydrophobic surface. This prior art also has the disadvantage that the hydrophilic anchor areas cannot be adapted to the respective experiment and are comparatively complex to manufacture. It is therefore the task of providing a flat structure which does not have the disadvantages of the prior art.

The object is achieved according to the invention with a flat structure which has an ultraphobic surface on which hydrophilic and / or oleophilic areas can be reversibly generated.

A flat structure in the sense of the invention is any shaped body with an arbitrarily designed surface. However, the fabric is preferably a plate with a flat surface, very particularly preferably a sample carrier, which, however, preferably has no indentations. Most preferably, the fabric according to the invention is a film which has an ultraphobic surface. The surface of the fabric according to the invention is preferably essentially flat; i.e. however, the topography required for an ultraphobic surface does not have any micro-volumes in which liquid can be collected.

According to the invention, the fabric has an ultraphobic surface. An ultraphobic surface in the sense of the invention is characterized in that the contact angle of a drop of water and / or oil lying on the surface is more than 150 ^° , preferably more than 160 ^° and very particularly preferably more than 170 ° and / or the roll angle does not exceed 10 ^° . The roll angle is understood to be the angle of inclination of a basically flat but structured surface against the horizontal, in which a standing water and / or oil drop with a volume of 10 μl is moved due to the force of gravity when the surface is inclined. Such ultraphobic surfaces are described, for example, in WO 98/23549, WO 96/04123, WO 96/21523, WO 99/10323, WO 00/39368, WO 00/39239, WO 00/39051, WO 00/38845 and WO 96 / 34697, which are hereby introduced as a reference and are therefore considered part of the disclosure.

In a preferred embodiment, the ultraphobic surface has a surface topography in which the spatial frequency of the individual Fourrier components and their amplitude a (f) are expressed by the integral S (log (f)) = a (f). f calculated between the integration limits log (fi / μm ^"1 ) = -3 and log (f ₂ / μm ^{" 1} ) = 3 is at least 0.3 and which consists of a hydrophobic or in particular oleophobic material or with a durable hydrophobic and / or in particular are provided with a durable, oleophobic material coating. Such an ultraphobic surface is described in international patent application WO 00/39240, which is hereby introduced as a reference and is therefore considered part of the disclosure.

Also according to the invention, hydrophilic and / or oleophilic areas can be reversibly generated on the ultraphobic surface. Hydrophilic and / or oleophilic areas within the meaning of the invention are areas on which a drop of water or oil can be deposited; i.e. a drop of water or oil, which is brought into contact with the hydrophilic and / or oleophilic area on a pipetting system, remains attached to it and thus detaches from the pipetting system. A drop of water or oil with a volume of 10 μl on the hydrophilic and / or oleophilic areas preferably has a contact angle <120 °, preferably <110 °, very particularly preferably <90 ° and / or the roll angle of this drop exceeds 10 °. Furthermore, according to the invention, these hydrophilic and / or oleophilic areas can be generated reversibly, so that they can be removed again easily and quickly after the respective application, for example measurement, and the corresponding flat structure can be reused and the hydrophilic and / or oleophilic areas can be redefined. The hydrophilic and / or oleophilic areas can be removed, for example, by washing the ultraphobic surface with an appropriate solvent and / or heating the ultraphobic surface.

It was extremely surprising for the person skilled in the art that with the flat structure according to the invention it is possible to provide ultraphobic flat structures with hydrophilic and / or oleophilic areas, in which the hydrophilic and / or oleophilic areas can be configured several times for the respective application. The fabrics according to the invention are particularly easy to manufacture. With the sheet-like structures according to the invention, it is possible to carry out high-quality mass spectrometric and / or optical analyzes, for example of biological material. Interfering background signals in particular are significantly reduced by the fabrics according to the invention compared to the prior art.

The hydrophilic and / or oleophilic areas are preferably completely enclosed by an ultraphobic area. This embodiment makes it possible to deposit a drop of liquid at a very specific location and anchor it there comparatively firmly.

Furthermore, the hydrophilic and / or oleophilic areas are preferably arranged according to a very specific pattern on the ultraphobic surface.

The hydrophilic and / or oleophilic areas can have any shape and size. However, they preferably have an area of 1 μm ² - 10 mm ² . A liquid drop with a diameter of preferably 5 nm - 5 mm can be deposited on such a surface and preferably anchored in such a way that it does not detach itself from the flat structure according to the invention when it hangs downwards.

The hydrophilic region is preferably at least one deposit on the ultraphobic surface. This deposit can be liquid or solid. In the case of a liquid deposit, the deposited substance must preferably be at least slightly volatile. The deposits can be generated, for example, by a corresponding temperature of the ultraphobic surface or by substances which are preferably applied in a solution and / or suspension to the ultraphobic surface, preferably in the form of drops, and in which the solvent or the liquid phase is then evaporated. The ultraphobic surface must be wettable by the solvent or the liquid phase.

In a preferred embodiment of the present invention, the fabric has at least one means for preferably locally cooling the ultraphobic surface. This cooling is preferably carried out in such a way that the temperature on the ultraphobic surface, preferably locally limited to <-5 ° C., particularly preferably <-15 ° C., and a solidifying substance forms on the ultraphobic surface at these points. The solidifying substance arises preferably by freezing at least one component of the gas phase which is in the vicinity of the ultraphobic surface. The solidifying substance is preferably ice. The locally limited cooling is preferably achieved in that the cooling means only directly or indirectly touches the ultraphobic surface from the underside.

Furthermore, the sheet-like structure according to the invention preferably has at least one means by which the vapor pressure of at least one component of the gas phase which is in the vicinity of the ultraphobic surface can be adjusted. This component is preferably water vapor. For example, the vapor pressure can be adjusted by means of a hood which is placed over the ultraphobic surface and under which, for example, the concentration of the component to be solidified is regulated.

A drop of water or oil that is placed on the solidified substance, for example the ice crystals, adheres to it, although it is usually <20% of the total, especially if the area covered by the solidified substance is very small below the liquid drop Drop diameter, not frozen. As soon as the temperature of the ultraphobic surface is raised again sufficiently, preferably to> -5 ° C, particularly preferably> 0 ° C, the surface in the hydrophilic and / or oleophilic areas becomes ultraphobic again. This temperature increase can take place either locally or over the entire area of the surface. The ultraphobic surface is then cleaned, for example by tilting, in which the liquid drops roll off the ultraphobic surface. The ultraphobic surface cleaned in this way can be used again.

In another preferred embodiment of the present invention, the deposit is a solid or liquid substance, which is preferably applied in solution and / or suspension to the ultraphobic surface, preferably in the form of drops, and the solvent and / or liquid phase is then evaporated off. This substance is then preferably present in crystalline form on the ultraphobic surface. The solvent must be selected so that it wetted ultraphobic surface and that the substance to be deposited is detachable, at least suspendable therein.

Preferably the substance to be deposited is i.e. the hydrophilic areas a MALDI matrix for performing the so-called MALDI mass spectrometry, which is described, for example, in Nordhoff et. al. "MALDI-MS as a new method for the analysis of nucleic acid (DNA and RNA) with molecular masses up to 150,000 Dalton, Application of modern mass spectrometric methods to plant science research, Oxford University press, (1966) page 86-101 is. This publication is hereby introduced for reference and is therefore considered part of the disclosure. Preferred MALDI matrices are 3-hydroxypicolinic acid, cyano-4-hydroxycinnamic acid, 2.5 dihydroxybenzoic acid, sinapic acid, 2, 4, 6 trihydroxyacetophenone nitrobenzyl alcohol, nicotinic acid, ferulic acid, caffeic acid, 2-aminobenzoic acid, picolinic acid, 3-aminobenzoic acid , 4-trihydroxyacetophenone, 6-aza-2-thiothymidine, urea, succinic acid, adipic acid, malonic acid or a mixture thereof. These MALDI matrices are dissolved, for example, in acetonitrile or an acetonitrile / water mixture with a mixing ratio of preferably 50:50 - 60:40, and applied as a liquid, preferably as a drop of liquid, to the ultraphobic surface and the solvent is evaporated there, so that the MALDI matrix is preferably present as a crystalline structure at certain points on the ultraphobic surface and thus represents the hydrophilic and / or oleophilic areas to which the samples to be analyzed can be dosed.

The samples to be analyzed, which do not wet the ultraphobic surface, are generally metered as a liquid onto the preferably crystalline MALDI matrices and preferably at least partially dissolve them. As the solvent evaporates again, the MALDI matrix crystallizes again and the samples to be analyzed are built into the MALDI matrix. These samples can then be analyzed with a mass spectrometer.

In a further preferred embodiment, the deposit on the ultraphobic surface is liquid, the liquid having to wet the ultraphobic surface or to be dissolved in a solvent which is the ultraphobic Surface wetted. The liquid deposit is preferably at least slightly volatile, at least at room temperature. This liquid is preferably also a MALDI matrix, for example glycerin, onto which the sample to be analyzed is then metered.

The fabric according to the invention is suitable for the analysis of any liquid, such as are known for example from active ingredient research. The method according to the invention is also preferably suitable for the analysis of biomolecules and / or biological material, in particular nucleic acids, nucleic acid analogs, Spiegelmers, aptamers, ribozymes, polypeptides, peptides or proteins. The method according to the invention is particularly suitable for mass-spectroscopic and / or optical analysis of biomolecules. These uses are also the subject of the present invention.

A biomolecule in the sense of the present invention is any molecule that is produced by any virus or single or multicellular organism in the course of the life cycle. Biomolecules contain at least one oxygen, nitrogen, sulfur, and / or phosphorus atom. Examples of biomolecules are: play gelers, aptamers, ribozymes, peptides, polypeptides, proteins, antibodies, nucleic acids, nucleic acid analogues, DNA, double-stranded DNA, RNA, double-stranded RNA / DNA, vitamins, carbohydrates, hormones, glycopeptides, glycoproteins, lipids, Fatty acids and cholesterol.

Biological material in the sense of the inventions contains at least one biomolecule. However, this can also involve large amounts of the same or different biomolecules. These can exist side by side unorganized or build functional units due to interactions. Examples of this are protein complexes, genomes, cell nuclei, ribosomes, cells, cell assemblies, tissues or complete organisms.

An optical analysis in the sense of the present inventions is described in the German parallel application filed with the German Patent and Trademark Office with the internal file number SY0028, which is hereby introduced as a reference and is therefore considered part of the disclosure. Another object of the present invention is a flat surface structure with an ultraphobic surface with hydrophilic and / or oleophilic areas, each of which is completely enclosed by ultraphobic areas.

A flat structure in the sense of the invention is any shaped body with an arbitrarily designed surface. However, the fabric is preferably a plate with a flat surface, very particularly preferably a sample carrier. Most preferably, the fabric according to the invention is a film which has an ultraphobic surface. According to the invention, the surface of the fabric according to the invention is flat; i.e. however, the topography required for an ultraphobic surface does not have any micro-volumes in which liquid can be collected.

In a preferred embodiment, the ultraphobic surface has a surface topography in which the spatial frequency of the individual foyer components and their amplitude a (f) are expressed by the integral S (log (f)) = a (f). f calculated between the integration limits log (fι / μnrϊ ¹ ) = -3 and log (f ₂ / μm ^"1 ) = 3 is at least 0.3 and which consists of a hydrophobic or in particular oleophobic material or with a durable hydrophobic or particularly durable is provided with an oleophobic coating ultraphobic surface is described in international patent application WO 00/39240, which is hereby introduced as a reference and is therefore considered part of the disclosure.

Hydrophilic and / or oleophilic areas within the meaning of the invention are areas on which a drop of water or oil can be deposited; i.e. a drop of water or oil, which is brought into contact with the hydrophilic and / or oleophilic area on a pipetting system, remains attached to it and thus detaches from the pipetting system. A drop of water or oil with a volume of 10 μl on the hydrophilic and / or oleophilic areas preferably has a contact angle <120 °, preferably <110 °, very particularly preferably <90 ° and / or the roll angle of this drop exceeds 10 °.

It was extremely surprising for the person skilled in the art and it was not to be expected that the flat structure according to the invention would succeed in depositing liquid drops comparatively firmly on, for example, a sample carrier. Because the fabric is flat, it is easy to manufacture. Flat surfaces have the advantage that the surface with which the liquid drop contacts the fabric is small, so that the contamination of the liquid drops by substances on the surface and the measurement errors caused thereby are reduced.

According to the invention, the hydrophilic and / or oleophilic areas are each completely enclosed by an ultraphobic area. This embodiment makes it possible to deposit a drop of liquid at a very specific location and anchor it there comparatively firmly.

The hydrophilic and / or oleophilic areas can have any shape and size. However, they preferably have an area of 1 μm ² - 10 mm ² . A liquid drop with a diameter of preferably 5 nm - 5 mm can be deposited on such a surface and preferably anchored in such a way that it does not detach itself from the fabric according to the invention when hanging downwards.

The hydrophilic and / or oleophilic regions are preferably produced by modifying the uppermost molecular layer of the ultraphobic surface. This modification is preferably a mechanical and / or thermal ablation, in which, however, preferably only a maximum of one molecular layer of the ultraphobic surface is removed. Furthermore, the modification is preferably carried out by the thermal or chemical change in the ultraphobic surface, but without removal, as described, for example, in DE 199 10809 A1, which is hereby introduced as a reference and is therefore considered part of the disclosure. With this modification of the ultraphobic surface, its layer thickness remains essentially unchanged.

The fabric according to the invention is suitable for the analysis of any liquid, such as are known for example from active ingredient research. The method according to the invention is also preferably suitable for the analysis of biomolecules and / or biological material, in particular nucleic acids, nucleic acid analogs, Spiegelmers, aptamers, ribozymes, polypeptides, peptides or proteins. The method according to the invention is particularly suitable for mass spectrometric and / or optical analysis of biomolecules and / or biological material. These uses are also the subject of the present invention.

In a preferred embodiment of both fabrics according to the invention, the ultraphobic surface is designed as a disposable article.

A multilayer sheet with a first layer with an ultraphobic surface and a carrier layer is particularly suitable for this embodiment, the first layer being reversibly applied to the carrier layer and the maximum local deviation of the sheet from the flatness being 100 μm, particularly preferably <20 μm , This flat structure has the advantage that the first layer with the ultraphobic surface can be detached from the carrier layer after one or more uses and can be replaced by a new first layer, so that it is impossible for this first layer to have been contaminated by previous previous experiments is. The first layer with the ultraphobic surface is particularly cheap to produce as a disposable item. The flatness defined according to the invention ensures that the flat structure can be used in all common mass spectrometric and / or optical analysis devices.

In a preferred embodiment of the fabric, the first layer is glued to the carrier layer.

Furthermore, there is preferably an electrical contact between the first layer and the carrier layer. This embodiment is particularly advantageous in the case of mass spectroscopic analyzes.

The preferred sheet can be used in a variety of ways, but is preferably suitable for mass spectroscopic and / or optical analyzes.

Another object of the present invention is a method for depositing a drop of liquid on a fabric according to the invention with an ultraphobic surface, which is cooled at least locally so that a substance is deposited at least locally on the ultraphobic surface by cooling and that the liquid drop is deposited on the surface Substance is deposited.

Deposition in the sense of the invention includes the manner in which the person skilled in the art applies a liquid to a corresponding flat structure. As an example, but not by way of limitation, pipetting and dispensing, for example with a pump, are listed. Preferably, several drops are deposited at one point, so that a larger drop is formed. The deposited substance is preferably ice, which is formed from water vapor which is in the vicinity of the ultraphobic surface.

This cooling is preferably carried out in such a way that the temperature on the ultraphobic surface, preferably locally limited to <-5 ° C., particularly preferably <-15 ° C., and deposits form on the ultraphobic surface due to the cooling. The locally limited cooling is preferably achieved in that the cooling means only directly or indirectly touches the ultraphobic surface from the underside.

In the method according to the invention, the vapor pressure of at least one component of the gas phase, which is located in the vicinity of the ultraphobic surface, is further preferably set. This component is preferably water vapor. For example, the vapor pressure can be set by a hood, which is placed over the ultraphobic surface and under which, for example, the concentration of the component to be solidified is regulated.

The method according to the invention is suitable for the analysis of any liquid, as is known, for example, from active substance research. The method according to the invention is also preferably suitable for the analysis of biomolecules and / or biological material, in particular nucleic acids, nucleic acid analogs, Spiegelmers, aptamers, ribozymes, polypeptides, peptides or proteins. The method according to the invention is particularly suitable for mass spectrometric and / or optical analysis of biomolecules and / or biological material. These uses are also the subject of the present invention.

The process is simple and inexpensive to carry out. The fabrics can be reused. It is extremely surprising to the person skilled in the art that the droplets on the surface do not generally freeze.

Another object of the present invention is a method for depositing an aqueous drop of liquid on the fabric according to the invention, in which a substance in the ultraphobic surface preferably dissolved and / or suspended form, preferably metered in drops, and the liquid phase wetting the ultraphobic surface or the solvent is then evaporated. A drop of liquid that does not wet the ultraphobic surface can be deposited on the remaining hydrophilic deposit.

Preferably the substance to be deposited is i.e. the hydrophilic areas a MALDI matrix for performing the so-called MALDI mass spectrometry, which is described, for example, in Nordhoff et. al. "MALDI-MS as a new method for the analysis of nucleic acid (DNA and RNA) with molecular masses up to 150,000 Dalton, Application of modern mass spectrometric methods to plant science research, Oxford University press, (1996) pp. 86-101 is.

Preferred MALDI matrices are 3-hydroxypicolinic acid, α-cyano-4-hydroxycinnamic acid, 2.5 dihydroxybenzoic acid, sinapic acid, 2, 4, 6 trihydroxyacetophenone nitrobenzyl alcohol, nicotinic acid, ferulic acid, caffeic acid, 2-aminobenzoic acid, picolinic acid, 3-aminobenzoic acid 3,4-trihydroxyacetophenone, 6-aza-2-thiothymidine, urea, succinic acid, adipic acid, malonic acid or a mixture thereof. These MALDI matrices are, for example, dissolved in acetonitrile and applied as a liquid, preferably as a drop of liquid, to the ultraphobic surface and the solvent is evaporated there, so that the MALDI matrix is preferably present as a crystalline structure on the ultraphobic surface and thus the hydrophilic and / or represent oleophilic areas to which samples to be analyzed can be dosed.

The samples to be analyzed, which do not wet the ultraphobic surface, are generally dosed as a liquid onto the crystalline MALDI matrices and preferably at least partially dissolve them. As the solvent evaporates again, the MALDI matrix crystallizes again and the samples to be analyzed are built into the MALDI matrix.

Likewise preferably suitable as the substance to be deposited are substances for the specific or non-specific binding of biological material. Another object of the present invention is a method for depositing a liquid drop on a flat structure according to the invention having an ultraphobic surface, in which a liquid wetting it is deposited on the ultraphobic surface and at least one liquid drop not wetting the ultraphobic surface is deposited thereon.

For surfaces on which a drop of water has a contact angle> 150 °, a liquid is preferably used as the wetting liquid which has a lower surface tension than water and which is preferably at least partially miscible with water. The wetting liquid is very particularly preferably acetone, acetonitrile or alcohol, preferably isopropanol, or a mixture thereof. These wetting liquids preferably have a water content of <50% by volume, particularly preferably <30% by volume and very particularly preferably <10% by volume.

For surfaces on which an oil drop has a contact angle> 150 °, a liquid is preferably used as the wetting liquid which has a lower surface tension than oil. Acetone is very particularly preferably used.

The wetting liquid is preferably metered as drops onto the ultraphobic surface, the number of wetting drops being <the number of drops to be deposited on the ultraphobic surface. Preferably, the volume of the wetting drop is 10 ^" 1-10 ^{" 9} times the volume of the drop to be deposited, the ratio immediately before the drop is set being critical, especially since many liquids wetting an ultraphobic surface have a high vapor pressure at room temperature and thus evaporate quickly.

The ultraphobic surface can be cleaned and reused by removing all liquid components. The ultraphobic surface then no longer has any hydrophilic and / or oleophilic areas. The method according to the invention is suitable for the analysis of any liquid, as is known, for example, from active substance research. The method according to the invention is also preferably suitable for the analysis of biomolecules and / or biological material, in particular nucleic acids, nucleic acid analogs, Spiegelmers, aptamers, ribozymes, polypeptides, peptides or proteins. The method according to the invention is particularly suitable for mass-spectroscopic and / or optical analysis of biomolecules or biological material. These uses are also the subject of the present invention.

It was not to be expected extremely surprising for the skilled person that it is possible with the present process to immobilize a drop of water with a solvent droplets at an ultraphobic surface, even if the volume of the water droplet that of the solvent droplet to the 10 ¹ - ιo ⁹ - fold exceeds.

The invention is explained below with reference to FIGS. 1-5. These explanations are only examples and do not limit the general idea of the invention.

Figure 1 shows an embodiment of the fabric according to the invention with cooling.

Figure 2 shows an embodiment of the method according to the invention with a wetting liquid.

Figure 3 shows the creation of a hydrophilic region by crystallization.

FIG. 4 shows an ultraphobic surface with a large number of hydrophilic areas.

FIG. 5 shows a flat structure with an ultraphobic surface as a single-use article.

Figure 1 shows a fabric according to the invention with cooling. In the present case, the fabric is a film 4 with an ultraphobic Surface on which a drop of water has a contact angle of 174 ° at room temperature and the roll angle is <10 °. The film 4 is cooled with a Peltier element 5 and a flow cooler 6. The Peltier element is connected to a temperature sensor (not shown) with which the temperature of the ultraphobic surface is regulated to a value <-16 ° C. At these temperatures, a thin layer of frost 7 forms. A drop of water 8, which is metered onto the ultraphobic surface at a speed of <4 m / s, remains attached to it and does not bounce off. In the present case, a plurality of drops 8 are metered onto a location on the ultraphobic surface, so that a larger drop 9 is formed. With a thin layer of frost, this drop does not freeze and has a contact angle of approx. 120 °.

Figure 2a shows an embodiment of the method according to the invention with a wetting liquid. The wetting liquid 1 is metered in the form of a drop onto an ultraphobic surface 4, on which a water drop, in the absence of a wetting liquid, has a contact angle of 174 ° and the roll angle is <10 °. As is known, ultraphobic surfaces have a certain topography, which is schematically symbolized with the bulges 10 and the recesses 11 lying between them. The ultraphobic surface is wetted by the wetting liquid 1, in the present case acetone. A drop of water 2 is then metered onto this wetted part of the ultraphobic surface 4 (see FIG. 2b), which is much larger than the drop 2 with which the ultraphobic surface was wetted. The drop of water is thus firmly deposited on the ultraphobic surface. The arrows in FIG. 2b indicate the diffusion between the wetting liquid 1 and the water drop 2. Figure 2c shows the state after some time. The water has mixed with the acetone, so that the ultraphobic surface is wetted at certain points by this mixture. However, this wetting remains limited to the area originally wetted by acetone.

FIG. 3 shows the generation of hydrophilic and / or oleophilic areas on an ultraphobic surface by deposition. A section of the flat surface 12 of a sample carrier 13 is shown in FIG. 3a. The surface is ultraphobic, so that a 10 μl drop of water has a contact angle of> 174 ° and one Rolling angle of <10 ° on it. A drop of liquid 14 is placed on the ultraphobic surface, which wets it and in which a substance X is dissolved or suspended. After the drop 14 has been applied, the solvent is evaporated and the crystalline deposit 15 (FIG. 3b) is formed, which essentially consists of substance X and any residues of the solvent. Substance X can be a MALDI matrix, for example. The area of the deposit 15 results from the size of the drop 14 and the chosen solvent and can therefore be adjusted very precisely. A person skilled in the art will recognize that the ultraphobic surface will generally have a plurality of deposits 15 which are arranged at a certain lateral distance from one another and preferably in a certain grid on the ultraphobic surface. The deposit 15 represents a hydrophilic and / or oleophilic area which is completely enclosed by ultraphobic areas. The deposit 15 can be removed from the ultraphobic surface after the respective experiment, so that it can be reused. The ultraphobic surface can be cleaned, for example, with a solvent.

FIG. 3 c shows the further use of the deposit 15, which represents a hydrophilic and / or oleophilic area. A drop 16, which does not wet the ultraphobic surface 12 and which hangs on a pipette or on a rod, is brought into contact with the hydrophilic region 15. The drop 16 has, for example, biological material. Due to the ultraphobicity of the surface 12, which completely surrounds the hydrophilic region 15, the contact angle of the drop 16 is so large that it only touches the hydrophilic region 15 and not the ultraphobic region 12. This configuration has the advantage that the drop 16 is not contaminated by the ultraphobic surface 12 or substances from the drop 16 are transported to the ultraphobic surface, for example by adsorption, and are therefore no longer available for the subsequent analysis. FIG. 4d shows the situation after the drop 16 has been lifted off the hydrophilic area 15. A small part 17 of the drop 16 remains on the hydrophilic area 15. The volume of the liquid 17 that adheres to the hydrophilic region 15 depends on its respective area and is much smaller than the volume of the drop 16, so that the dosing process with a drop 16 can be repeated several times. If the area of the hydrophilic areas 15 and the same liquid 16 are identical in size, the same amount of liquid 17 always adheres to the hydrophilic areas 15, with the exception of a small error. Since the liquid 17 likewise never comes into contact with the ultraphobic area, it also becomes of the latter not contaminated or no substances are transferred from the liquid 17 to the ultraphobic surface 12. The liquid 17 can then be analyzed optically and / or mass spectrometrically. For this purpose, 17 additional reagents can be added to the liquid. Furthermore, the liquid can also be evaporated and then analyzed optically and / or mass spectrometrically. This process is shown in Figure 3e.

The device according to the invention has the advantage that the samples 17 to be analyzed are not contaminated when they are analyzed, so that, for example, mass spectra or fluorescence recordings or fluorescence spectra of high quality can be recorded by the samples 17 with a low background signal.

FIG. 4 shows an ultraphobic surface 18 with a multiplicity of hydrophilic regions 19 which are completely enclosed by the ultraphobic regions.

FIG. 5 shows the flat structure 101 that consists of a first layer 201 with an ultraphobic surface 301 and a carrier layer 401. The first layer 201 is fixed on the carrier layer by means of an adhesive layer 501. Those skilled in the art will recognize that the adhesive layer 501 need not necessarily be present. The adhesive layer 501 consists of an electrically conductive material, so that there is an electrical contact between the first layer 201 and the carrier material.

Claims

claims:

1. Flat structures, in particular plate, with an ultraphobic surface on which hydrophilic and / or oleophilic areas can be reversibly generated.

2. Flat structure according to claim 1, characterized in that the hydrophilic and / or oleophilic areas are each completely enclosed by ultraphobic areas.

3. Flat structure according to one of the preceding claims, characterized in that the hydrophilic and / or oleophilic areas are at least partially distributed on the surface according to a certain pattern.

4. Flat structure according to one of the preceding claims, characterized in that the ultraphobic surface has a surface topography in which the spatial frequency f of the individual Fourier components and their amplitudes a (f) expressed by the integral S (log (f)) = a (f ) • f calculates between the integration limits log (fi / μm ^"1 ) = -3 and log (f ₂ / μm ^{" 1} ) = 3, at least 0.3 and which consists of ultraphobic polymers or durable ultraphobic materials and / or with a coating of a hydrophobic and / or oleophobic material is provided.

5. Flat structure according to one of the preceding claims, characterized in that the hydrophilic and / or oleophilic areas each have an area of 1 μm ² - 10 mm ² .

6. Flat structure according to one of the preceding claims, characterized in that the hydrophilic region is at least one deposit, preferably a solidified substance on the surface.

7. Flat structure according to one of the preceding claims, characterized in that it has means for preferably local cooling of the ultraphobic surface.

8. The flat structure according to claim 7, characterized in that the ultraphobic surface can be cooled to temperatures <-5 ° C, preferably <-15 ° C.

9. The sheet material as claimed in claim 7 or 8, characterized in that the solidified substance is at least one component of the gas phase which is in the vicinity of the ultraphobic surface and which freezes on the ultraphobic surface.

10. Flat structure according to one of claims 6-9, characterized in that the solidifying substance is at least ice, preferably ice crystals, and the component of the gas phase is at least water vapor.

11. The sheet material according to claims 6-10, characterized in that it has means for adjusting the vapor pressure of at least one component of the gas phase which is in the vicinity of the ultraphobic surface.

12. The sheet material according to claim 6, characterized in that the deposit is a substance which is dosed in dissolved and / or suspended form on the ultraphobic surface and whose liquid phase or solvent has been evaporated.

13. A flat structure according to claim 12, characterized in that the liquid phase or the solvent wets the ultraphobic surface.

14. Flat structure according to one of claims 6, 12 or 13, characterized in that the solidified substance is a MALDI matrix and / or biological material.

15. Flat surface structure with an ultraphobic surface with hydrophilic and / or oleophilic areas, each of which is completely enclosed by ultraphobic areas.

16. The flat structure according to claim 15, characterized in that the hydrophilic and / or oleophilic areas are at least partially distributed on the surface according to a certain pattern.

17. The flat structure according to one of claims 15 or 16, characterized in that the ultraphobic surface has a surface topography in which the spatial frequency f of the individual Fourier components and their amplitudes a (f) expressed by the integral S (log (f)) = a (f) • f calculates between the integration limits log (fι / μm ^_1 ) = -3 and log (fi / μm ^"1 ) = 3, at least 0.3 and which consists of ultraphobic polymers or durable ultraphobic materials and / or with a coating of a hydrophobic and / or oleophobic material is provided.

18. Flat structure according to one of claims 15 - 17, characterized in that the hydrophilic and / or oleophilic areas each have an area of 1 μm ² - 10 mm ² .

19. Flat structure according to one of claims 15 - 18, characterized in that the surface thereof is essentially ultraphobic and that the hydrophilic and / or oleophilic regions have been produced by a modification of the uppermost molecular layer of the ultraphobic surface.

20. Flat structure (101) according to one of the preceding claims with a first layer (201) with an ultraphobic surface (301) and with a carrier layer (401), characterized in that the first layer (201) on a carrier layer (401) is reversible is applied and the maximum local deviation of the fabric from the flatness is <100 μm.

21. Flat structure according to claim 20, characterized in that the first layer (201) is glued to the carrier layer (401).

22. The flat structure according to claim 20 or 21, characterized in that there is an electrical contact between the first layer (201) and the carrier layer (401).

23. Flat structure according to one of claims 20 - 22, characterized in that the ultraphobic surface (3) has at least one hydrophilic area.

24. Flat structure according to one of claims 20 - 23, characterized in that the layer (2) is a disposable article.

25. A method for depositing a drop of liquid on a flat structure according to one of claims 6 to 11, characterized in that the ultraphobic surface is cooled at least locally in such a way that a substance solidifies on the ultraphobic surface at least locally and that the liquid drop on the solidified substance is deposited.

26. The method according to claim 20, characterized in that the solidified substance is ice.

27. The method according to claim 20 or 21, characterized in that several liquid drops are deposited at one point and thus a larger liquid drop is generated.

28. A method for producing a flat structure according to one of the claims 6 and 12-14, characterized in that a substance in preferably dissolved and / or suspended form is preferably metered in droplets onto the ultraphobic surface and the liquid phase or the solvent wetting the ultraphobic surface is then evaporated.

29. The method according to claim 23, characterized in that the substance is a MALDI matrix.

30. The method according to claim 23 or 24, characterized in that the substance is suitable for the specific or non-specific binding of biological material.

31. A method for depositing a liquid drop (2) on a flat structure according to one of the claims 1 - 5, characterized in that a liquid (1) wetting it on the ultraphobic surface and before it evaporates there is at least one liquid drop not wetting the ultraphobic surface thereon (2) is filed.

32. The method according to claim 26, characterized in that the wetting liquid (1) is deposited in the form of a drop (3) on the ultraphobic surface.

33. The method according to claim 27, characterized in that the volume of the drop (3) is very much smaller than the volume of the drop (1).

34. The method according to any one of claims 26-28, characterized in that the liquid (1) has a lower surface tension than water and is preferably soluble in the liquid of the drop (2)

35. The method according to any one of claims 26-29, characterized in that the liquid (1) is acetone, acetonitrile, alcohol, particularly preferably isopropanol.

36. The method according to any one of claims 26-29, characterized in that the liquid drop (2) comprises biological material.

37. Use of the fabrics according to any one of claims 1-24 and the methods 25-36 for mass spectroscopic and / or optical analysis or for DNA sequencing using the peptide nucleic acid (PNA) method.