JPS63221184A - Cumurative film and cumurative polymerized film and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain an artificial cumurative film having functional char acteristics as observed in natural phospholipid, by laminating monomolecular layers of a specified compound having a structure similar to that of phospholip id, formed on the surface of water, one after the other on a solid base. CONSTITUTION:A compound (A) of formula I is reacted with a compound (B) of formula II (wherein n is 27-39) in a solvent (e.g., diethyl ether) in the presence of a tertiary amine (C) (e.g., triethylamine) at -50-0 deg.C for 30min to several hours to give a compound of formula III. The compound of formula III is then reacted with the above-mentioned tertiary amine in a solvent (e.g., dimethylformamide)at a temperature of room temperature to 40 deg.C for several hours to 10hr to give a compound of formula IV wherein R<1-3> are each alkyl, and R<1> may be linked to R<2> to form a ring) having a structure similar to that of phospholipid. This compound is floated on the surface of water; a pressure is applied horizontally to form a monomolecular layer of this compound; a solid base is immersed in this monomolecular layer and then withdrawn therefrom. This procedure is repeated to accomplish the laminating of the monomolecular layers one after the other on the solid base.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a cumulative film and a cumulative polymerized film of a compound having a phospholipid-like structure, and a method for producing the same.

(Prior Art) Living organisms contain many types of phospholipids, and it is clear that these phospholipids play an important role in maintaining life.

For example, phospholipids are components of cytoplasm such as cell membranes,
It is closely related to various metabolic processes in living organisms, and
It also plays a very important role in the energy source of the brain tissue, the transport and absorption of fat, blood coagulation, food taste perception, etc.

Since phospholipids have many functions in supporting overall life, many attempts have been made to apply them to various artificial organs, cell fusion, enzyme immobilization, artificial cultivation, biosensors, etc.

Therefore, in order to be used in the above-mentioned fields such as humidity sensors, gas sensors, ion-permeable membranes, artificial organs, cell fusion, enzyme immobilization, biosensors, and artificial cultivation, these must be obtained from relatively high polymers and must be strong. There is an extremely high demand for materials that can be formed into films and that they are highly economical.

On the other hand, in biological tissues, molecules form a highly ordered system, and several molecules constitute a functional unit and work cooperatively (Reference: "Surface Science" Vol. 6. No. ,2
．． 1985-6-1. pages 16 to 29), that is,
They express characteristics unique to their molecular arrangement. Recently, ultra-thin films made by stacking monomolecular films have attracted attention as a method for expressing various functions of organic molecules, and in particular, monomolecular stacked films and their fabrication technology have the potential to realize molecular electronic devices, bioelectronic devices, etc. considered indispensable.

(Problems to be Solved by the Invention) However, even in the case of phospholipid-like compounds, by accumulating their monomolecular films, that is, forming ultra-thin films, new functions can be expressed and conventionally known properties can be improved. However, the formation of these artificial cumulative films has not yet been realized.

An object of the present invention is to provide a monomolecular cumulative film of molecules having a phospholipid-like structure, a cumulative polymerized film whose strength is improved by polymerizing the same, and a method for producing the same.

(Means for Solving the Problems) The present invention solves the above problems, and the first invention is based on the following general formula (in formula (I), n is 27 to 39, R+, R2 and R3 represents an alkyl group, however, R1 and 2 may be linked to form a ring. The present invention relates to a characteristic cumulative film.

Next, the second aspect of the present invention is the following general formula (Formula (II)), where n is 27 to 39, R1, R2 and 3 are alkyl groups, and 0m is the degree of polymerization, provided that R1 and R2 are The present invention relates to a cumulative polymer membrane characterized in that a plurality of monomolecular layers of a polymer having a phospholipid-like structure represented by (which may be connected to form a ring) are laminated.

A third aspect of the present invention relates to a method for producing a cumulative film formed by stacking a plurality of monomolecular layers of the compound of formula (I). It is characterized by being formed on the water surface and laminating monolayers one by one on a solid substrate.

Furthermore, a fourth aspect of the present invention is to form a monomolecular layer of the compound of formula (1) on a water surface, and to stack the monomolecular layer layer by layer on a solid substrate to form a monomolecular cumulative film of the compound. Formation (c) A cumulative polymer film of the compound is formed by irradiating the monomolecular cumulative film with radiation.

The compound having a phospholipid-like structure represented by formula (I) used in the present invention is produced by the following method.

First, a compound represented by the following formula (III) is converted into a compound represented by the following general formula (IV) CH2□C
H(Ctb+1r-OH(IV) (n in the formula is 27-
397a) in the presence of a tertiary amine, such as trimethylamine, triethylamine, etc., to form a compound represented by the following general formula (V) (in which n represents 27 to 39). Manufacture. In this case, the amounts of the reaction components and the tertiary amine used may be approximately equimolar, and the solvent used during the reaction is preferably one that can dissolve both components, the tertiary amine, and the reaction product, such as diethyl For the reaction involving ether, tetrahydrofuran, etc., both components and tertiary amine may be mixed in a solvent and reacted at -50'C to O'C for 30 minutes to several hours, and is expressed by the reaction formula below. The reaction yields a compound represented by formula (V) almost quantitatively.

(In) The by-product tertiary amine hydrochloride usually precipitates and can be easily separated.

Next, the compound represented by formula (V) is added to a tertiary amine represented by the following general formula (R2, R3 and R4 in formula (Vl) are the same as those in formula CI), such as trimethylamine. , triethylamine, N-methylpiperidine, etc., the compound of formula (I) can be obtained. In this case, the amount of the tertiary amine represented by formula (rV) to be used may be at least equimolar to the compound represented by formula (V).8 The solvent used in the reaction may be acetonitrile, methanol, dimethylformamide, etc. can be mentioned. The compound of formula (I) can be obtained in high yield by mixing the same components in a solvent and reacting at room temperature to 40'C for several hours to ten hours. The resulting formula (
The compound of I) is dissolved in chloroform or methanol,
It can be easily purified by adding one portion of this to a large amount of acetone and precipitating it.

Next, the compound represented by formula (I) is dissolved in a solvent and easily polymerized by irradiation with ultraviolet rays or radiation or heating in the presence of a reaction initiator to obtain a polymer represented by formula (II). It will be done.

(Function) The Langmuir-Blodgett method (LB method) is known as an effective method for producing a cumulative film. The details of this method are described in the above-mentioned document, but the main points are as follows.

When a molecule with a parent wood group and an elongated hydrophobic group in the same molecule is floated on the water surface and an appropriate pressure is applied from the side, the parent wood groups of this molecule come into contact with the water surface, forming a regularly arranged monomolecular film. Ru. A solid substrate is immersed in this monomolecular film and then pulled up again.The monomolecular film adheres to the substrate. Further, by repeating this operation, a monomolecular cumulative film can be obtained.

It is known that X-type, Y-type, and Y-type 3f1 exist in this cumulative film depending on the properties of the molecules and the substrate.

Figures 1 (A) to (C) schematically show these. In the case of Figure 1 (A), the substrate 1r & molecules on the water surface 4 when immersed have their hydrophobic groups 2 on the substrate side. However, when the substrate 1 is pulled up, the molecules do not stick to each other.By repeating this operation, a cumulative film as shown in FIG. 1(A) can be obtained. This is called an X-type cumulative film. In the case of Figure 1 (8), when the substrate 1 is pulled up, the hydrophilic groups 3 of the molecules come into contact with the substrate and adhere to it, and when the substrate is immersed, the hydrophobic groups 2 of the molecules floating on the water surface 4 are already attached to the substrate. It attaches in a form that comes into contact with the hydrophobic group 2 of the molecule attached to 1. When this operation is repeated, the molecules accumulate one by one, tail-to-head, head-to-tail, and tail-to-head. This is called a Y-type cumulative film. In the case of Fig. 1 (C), when the substrate 1 is pulled up, the molecules on the water surface 4 attach with their hydrophilic groups 3 facing the substrate, but when the substrate 1 is immersed, they do not attach. The accumulation is called Y-shaped.

As explained above, whether or not a cumulative film can be obtained by the LB method, and what type of film can be obtained, depends on the balance between hydrophobic groups and parent groups in the molecule, the pH of the water, the temperature, etc. do.

Therefore, it is not easy to find molecules and conditions that form a cumulative film.

According to the present invention, in the following general formula (formula CL), n is 27 to 39, day 1, day 2, and day 3 represent an alkyl group, provided that R2 and R3 are connected to form a ring. Since a compound having a phospholipid-like structure represented by The strength of the membrane can be improved.

(Example) This invention will be explained by examples.

The phospholipid analog compound used here was synthesized by the following method. 2-chloro-1,3,2-dioxaphosphorane 0.
4 mol was dissolved in 100 mff of dry benzene, and dry oxygen gas was passed through it for 8 hours. After the oxidation reaction shown in the following reaction formula was completed, it was purified by distillation to obtain 2-chloro-2-oxo-1,
3,2-dioxaphosphorane (III)': Obtained.

Next, 0.2 mol of ω-nonacosenol (IV') and 0.21 mol of triethylamine were added to 30 mol of dry diethyl ether.
In addition to 0 mff, the compound (
2 drops.

9. Stirring 11. The reaction mixture was further stirred in the dark for 30 minutes at room temperature. The reaction mixture was filtered to remove triethylamine hydrochloride as a by-product, diethyl ether was distilled off from the filtrate, and the compound (
V')! Obtained.

(V') Compound (V') 0.05 mol and trimethylamine 0.2
5 mol, dimethylformamide (DMF) 100ml12
After the reaction was completed, the contents were taken out and immediately concentrated under reduced pressure.

The obtained Shirombu was dissolved in chloroform and added to a large amount of acetone to precipitate crystals of the compound (C') for purification.

(rV) Next, compound (I') 10mgi8: benzene 10mf
Dissolved in f. The trough of Langmuir 70 jet membrane manufacturing equipment (Lauda Fi1m Balance) was filled with purified water purified by distillation using a non-boiling distillation equipment.
While maintaining the temperature at 0'C, a benzene solution of the above compound (1') was spread on the water surface using a microsyringe. After leaving it for a while to evaporate the benzene, the surface area was reduced with a bar and the surface pressure was adjusted to 37 dynes/cm, and the compound (
A monomolecular film was formed.

Next, set the silicon substrate on the lifter and
The substrate was raised and lowered across the water surface at a speed of in. At this time, the monomolecular film on the water surface adhered to the substrate when the substrate rose, but no adhesion was observed when it descended, indicating a Z-shaped cumulative film.

By repeating the top and bottom of the substrate 50 times, a thin film of compound (technique) having 50 layers was obtained.

When the cumulative film of compound (I') prepared in Mitate ± Yu Example 1 was irradiated with gamma rays at an irradiation dose of 128 megarads (Mrad), it turned into a white elastic film. When measuring the infrared absorption spectrum of this film, it was found that the vinyl group (H2C=C)-1-)
It was found that the absorption around 1640 cm-' derived from It was also confirmed that this film was insoluble in benzene, the solvent for the monomer, and was polymerized by γ-ray irradiation to form a strong cumulatively polymerized film.

East JE Example 3 Next, the following compound was synthesized in the same manner as in Example 1 except that ω-pentatriacontenol was used instead of ω-nonacosenol.

This compound is 10m9! When dissolved in 10 ml of Hensen and produced a cumulative film in the same manner as in Example 1, 50 layers of Z
A mold membrane was obtained.

When γ-rays were irradiated in the same manner as in Example 2, polymerization occurred and a strong polymer film was obtained.

(Effects of the Invention) As explained above in detail 1, the present invention (phosphorus tribute analogue compound) has a hydrophilic trialkylammonium ethyl phosphate group at the terminal of a linear long-chain alkyl chain. Because of this, a monomolecular film can be easily formed on the water surface, and a cumulative film with regularly arranged molecules can be obtained using the Langmuir-Prodgett method.Roughly, the other end of the compound has a polymerizable vinyl group. Therefore, by irradiating the cumulative film with ultraviolet rays or radiation, it easily polymerizes and becomes a strong film.

Therefore, it has the functional characteristics found in natural phospholipids,
The strong phospholipid-like substance membrane of the present invention can be used in a wide range of fields such as humidity sensors, gas sensors, enzyme immobilization, biosensors, and artificial organs, and its industrial value is extremely large. .

[Brief explanation of drawings]

FIGS. 1(A) to 1(C) are explanatory diagrams of the types of molecules when forming cumulative *V shadows in the Langmuir-Prodgett method, respectively. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Hydrophobic group 3... Hydrophilic group, 4... Water surface. LB5m12 Oh (Bulk fortification type Figure 1)

Claims (4)

[Claims] (1) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (I) (In formula (I), n is 27 to 39, R^1, R^2 and R^3 are alkyl groups (However, R^1 and R^2 may be connected to form a ring). cumulative film. (2) The following general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In formula (II), n is 27 to 39, R^1, R^2, and R^3 are alkyl group, m indicates the degree of polymerization. However, R^1 and R^2 may be connected to form a ring. A cumulative polymer film characterized by being formed by laminating layers. (3) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (I) (In formula (I), n is 27 to 39, R^1, R^2 and R^3 are alkyl groups (However, R^1 and R^2 may be linked to form a ring.) Form a monomolecular layer of a compound having a phospholipid-like structure on the water surface, and A method for producing a cumulative film, characterized by laminating molecular layers one by one on a solid substrate. (4) The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼... (I) (In formula (I), n is 27 to 39, R^1, R^2 and R^3 are alkyl groups (However, R^1 and R^2 may be connected to form a ring.) Form a monomolecular layer of a compound having a phospholipid-like structure represented by A monomolecular cumulative film of the compound is formed by laminating layers one by one on a solid substrate, and a cumulative polymer film of the compound is formed by irradiating the monomolecular cumulative film with radiation. A method for producing a cumulative polymer film.