JP2788286B2 - Bilayer film fabrication substrate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention relates to a bilayer film-forming substrate.

(Prior art) To date, transistors, ICs, LSIs, and ultra LSIs have been developed using silicon-based semiconductor technology.
This has laid the foundation for today's electronics. On the other hand, with the elucidation of life or biological phenomena, expectations for development of new materials and elements based on a concept unique to biological phenomena are increasing. This is based on the idea of imitating biological phenomena and taking on electronics technology based on principles different from the conventional ideas in terms of information processing, recognition, memory, and the like.

By the way, a biological membrane as a place where biological functions are expressed,
It plays various important roles such as recognition of information from outside and transmission into the membrane, conversion and transport of substances. Therefore, the development of artificial membranes is extremely important for the production of materials and devices that imitate biological systems. As such artificial membrane, polymer cast membrane, Langmuir-Blodgett (LB)
Various types such as membranes have been considered, but as a biological membrane model, a bilayer membrane system is the form closest to the biological membrane. The bilayer is an ultrathin film in which amphipathic molecules such as phospholipids are arranged in bilayers with pores formed in a substrate so that the alkyl chains in the hydrophobic part are directed toward each other.

Conventionally, as a substrate for producing this bilayer film,
A thin Teflon sheet or the like in which small holes of several tens to several hundreds of micrometers are formed has been used. In this case, as a method of forming a small hole in a Teflon sheet or the like, a method of punching the sheet with a syringe needle or high-pressure discharge has been adopted (for example, Cell Engineering, 7 , 69 (1988)). Then, using such a substrate, a bilayer film is formed in the small holes by a laminating method (Montal method) or a brush coating method.

However, in the above-described conventional substrate, since the small holes are formed by punching out a Teflon sheet or the like with a syringe needle or high-pressure discharge, it is difficult to control the size and shape of the small holes. In addition, since the sheet surface around the small holes is rough after the small holes are formed, an end face treatment is required, and even if the end surface processing is performed, the sheet surface does not become sufficiently smooth around the small holes. Further, a thin Teflon sheet is weak in strength. All of these factors have made the formed bilayer unstable, and have also caused poor reproducibility of the bilayer preparation.

Therefore, if a bilayer membrane production substrate made of a thin metal plate having small holes penetrated and having a hydrophobic surface is adopted,
The above-mentioned problem can be solved. That is, when a thin metal plate is used, small holes are formed thermally using a laser or the like, or the small holes are patterned by an electrolytic deposition method, and the surface thereof is made hydrophobic by an appropriate method. Since the molecular film forming substrate can be manufactured, the size and shape of the small holes are controlled, the metal sheet surface around the small holes is smooth, and the strength of the substrate itself is high. Therefore, by using such a bilayer film production substrate, a stable bilayer film can be produced with high reproducibility as compared with a conventionally used Teflon substrate.

By the way, in order to develop a functional device using a bilayer film, not only can a stable and reproducible bilayer film be produced, but also two or more small holes two-dimensionally arranged on the same substrate. It is necessary that a bilayer is formed and only the bilayer in a specific region arbitrarily selected exhibits a predetermined function. For this purpose, it is desired to control the interaction of a bilayer film formed in two or more small holes on the substrate.

However, according to the study of the present inventors, when a bilayer film is formed using a substrate having two or more penetrated pores and the surface of which is all subjected to hydrophobization treatment, it is formed in each pore. It has been found that an interaction between all the molecules constituting the bilayer thus formed works through the monolayer transferred to the substrate except for the pores. Therefore, in this case, it is difficult to control the interaction between the prepared bilayers. As described above, up to now, there has been no known bilayer film-forming substrate capable of realizing the above-mentioned demand.

(Problems to be Solved by the Invention) As described above, in the conventional bilayer film forming substrate, the bilayer film to be formed is often unstable and the reproducibility is poor. Further, even when a bilayer film can be produced stably and with good reproducibility, it has been difficult to control the interaction between the bilayer films formed in two or more small holes of the substrate.

The present invention has been made in order to solve the above-mentioned problems, and can produce a stable bilayer film with good reproducibility, and furthermore, has a mutual interaction between the bilayer films formed in two or more small holes. It is an object of the present invention to provide a bilayer film forming substrate capable of controlling the action.

[Constitution of the Invention] (Means for Solving the Problems) The bilayer film forming substrate of the present invention has two or more penetrated small holes, and the inner wall of the small hole and the surface around the small hole are selectively formed. It is characterized by being made of a metal sheet that has been made hydrophobic.

In the present invention, the material of the metal thin plate is not particularly limited, and various materials such as iron, nickel, copper, platinum, gold, silver, a pure metal such as titanium, or a metal alloy such as stainless steel can be used. . The thickness may be any thickness that can maintain the strength as a plate, for example, several μm.
Various types of m to several hundred μm can be used.

In the present invention, as a method of forming small holes in a thin metal plate, a thermal method using a laser or the like, in addition to a normal method such as etching, in addition to a resist to obtain a small hole of a more controlled shape. A method by microlithography used, a method of depositing a metal sheet having small holes patterned by an electrolytic deposition method, and the like can also be used.

In the present invention, the method of selectively hydrophobizing the inner wall of the pores and the surface around the pores of the metal thin plate is not particularly limited as long as the lipid constituting the bilayer membrane can form a membrane. For example, surface treatment of substrates with monoalkyltrichlorosilanes such as hexamethyldisilazane and hexadecyltrichlorosilane, dialkyldichlorosilanes, and trialkylmonochlorosilanes, and monomolecular films such as cadmium stearate by the LB method. A method of accumulating on a substrate, a method of masking a predetermined area of a thin metal sheet with, for example, a tape, or a method of selectively forming a pattern on a part of the thin metal sheet by photolithography and then making the other part hydrophobic. Are combined. When performing the above-described surface treatment with various silanes, a film such as SiO ₂ may be formed on the surface of the thin metal plate in advance. The region to be selectively hydrophobized can have various pattern shapes.

As a method for producing a bilayer film on the substrate having the above-described structure, any of a well-known laminating method (Montal method) and a brush coating method can be used.

(Function) The bilayer film forming substrate of the present invention is formed by thermally forming small holes in a thin metal plate by using a laser or the like, or depositing a thin metal plate in which the small holes are patterned by an electrolytic deposition method. Therefore, the size and shape of the small holes are controlled, the surface of the thin metal plate around the small holes is smooth, and the strength of the substrate itself is high. Therefore, by using the bilayer film forming substrate of the present invention, a stable bilayer film can be prepared with high reproducibility as compared with a conventionally used Teflon substrate.

Further, the inner wall and the surrounding surface of two or more through-holes formed in the metal sheet are selectively hydrophobized,
Since the monolayer is transferred only to the hydrophobic area,
There is no interaction between the bilayers in the regions that have been separated and hydrophobized. Also, if all pores are divided into several holes and their surroundings are selectively patterned and hydrophobized, an interaction acts between the bilayers in one hydrophobized region, Since the interaction does not work between the bilayer in the region and the other region, the range and direction of the interaction between the bilayers can be freely controlled.

(Example) Hereinafter, an example of the present invention will be described.

Example 1 A bilayer film production substrate shown in FIG. 1 was produced as follows. A nickel thin plate 1 having a thickness of 10 μm in which small holes 2 having a diameter of 150 μm were formed vertically and horizontally by an electric field deposition method. A 0.3 μm thick SiO ₂ film was formed on both surfaces of the nickel thin plate 1 by high frequency sputtering. This nickel sheet 1
After masking the boundary region so that each small hole is formed into a mesh shape one by one on both surfaces of the nickel thin plate 1, both surfaces of the nickel thin plate 1 were not masked. The surface of the region was hydrophobized (hydrophobized region 3) to obtain a bilayer film forming substrate.

Using this bilayer film production substrate, a bilayer film was produced as follows. At room temperature of 29 ° C., a 15 cm × 50 cm trough is filled with pure water and maintained at 24 ° C., and N-
(7-nitrobenz-2-oxa-1,3-diazole-
4-yl) L-α-dipalmitoyl phosphatidylethanolamine (NBD-DPPE) in chloroform solution was developed. After evaporating the solvent, the monomolecular film was compressed by a barrier to a surface pressure of 40 mN / m. The monolayer was transferred to the hydrophobized region 3 of the substrate by immersing the bilayer-formed substrate perpendicularly to the water surface in the same manner as in the LB method.
A bilayer film was prepared.

When the transmission absorption spectrum of the bilayer membrane was measured in water, a stable bilayer membrane was formed in the small holes 2 and the reproducibility was good. When the reflection absorption spectrum of the monomolecular film transferred onto the nickel thin plate 1 was measured,
The monomolecular film was transferred only to the hydrophobic region 3. There is no interaction between such bilayers.

Example 2 A bilayer film production substrate shown in FIG. 2 was produced as follows. A nickel thin plate 1 having a thickness of 10 μm in which small holes 2 having a diameter of 150 μm were formed vertically and horizontally by an electric field deposition method. A 0.3 μm thick SiO ₂ film was formed on both surfaces of the nickel thin plate 1 by high frequency sputtering. This nickel sheet 1
On both sides, a positive type photoresist is applied, exposed and developed, and the photoresist is left in the boundary region so that a plurality of small holes arranged in one vertical line are separated, and a stripe-shaped photoresist is formed. The SiO ₂ pattern was exposed.
By treating in a gas phase of hexamethyldisilazane, the surface of the striped SiO ₂ pattern exposed on both sides of the nickel thin plate 1 was hydrophobized (hydrophobized region 4) to obtain a bilayer film forming substrate.

An NBD-DPPE bilayer film was prepared in the same manner as in Example 1 using this bilayer film preparation substrate.

The spectrum was measured in the same manner as in Example 1. As a result, a stable and reproducible bilayer film was formed in the small holes 2, and the monolayer film was transferred only to the hydrophobic region 4. In such a bilayer, an interaction acts between the bilayers contained in one hydrophobic region 4, but an interaction acts between the bilayers of the hydrophobic region 4 separated from each other. Absent.

Example 3 A bilayer film forming substrate shown in FIG. 3 was manufactured as follows. A nickel thin plate 1 having a thickness of 10 μm in which small holes 2 having a diameter of 150 μm were formed vertically and horizontally by an electric field deposition method. A 0.3 μm thick SiO ₂ film was formed on both surfaces of the nickel thin plate 1 by high frequency sputtering. This nickel sheet 1
On both sides, a positive photoresist is applied, exposed and developed, and the photoresist is left in the boundary region so that four small holes are separated from each other.
The SiO ₂ pattern was exposed. By treating in a gas phase of hexamethyldisilazane, the surface of the striped SiO ₂ pattern exposed on both sides of the nickel thin plate 1 was hydrophobized (hydrophobized region 5) to obtain a bilayer film forming substrate.

An NBD-DPPE bilayer film was prepared in the same manner as in Example 1 using this bilayer film preparation substrate.

The spectrum was measured in the same manner as in Example 1. As a result, a stable and reproducible bilayer film was formed in the small holes 2, and the monolayer was transferred only to the hydrophobic region 5. In such a bilayer, an interaction acts between the bilayers included in one hydrophobic region 5, but an interaction acts between the bilayers of the hydrophobic regions 5 separated from each other. Absent.

[Effects of the Invention] As described in detail above, the use of the bilayer film-forming substrate of the present invention makes it possible to prepare a bilayer film having a controlled pore size, stable and reproducible, Interaction can be controlled freely.

[Brief description of the drawings]

FIG. 1 is a partial plan view of a bilayer film forming substrate according to Example 1 of the present invention, FIG. 2 is a partial plan view of a bilayer film forming substrate according to Example 2 of the present invention, and FIG. FIG. 9 is a partial plan view of a bilayer film production substrate in Example 3. 1 ... nickel thin plate, 2 ... small hole, 3, 4, 5 ... hydrophobic area.

Claims (1)

(57) [Claims] 1. A bilayer membrane production substrate having two or more penetrated small holes, wherein the inner wall of the small holes and the surface around the small holes are made of a metal sheet selectively hydrophobicized. .