JP4192235B2 - Mesoporous inorganic material with sustained release function - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel mesoporous inorganic material modified with a functional group, a method for producing the same, and a method for using the same.
[0002]
[Prior art]
A technique that uses a function of containing a chemical substance in a solid material and gradually releasing the substance from the inside to the outside is called a control release system, and has attracted attention in recent years. For example, in such fields as pharmaceuticals, agricultural chemicals, cosmetics, various catalysts, fertilizers, and fragrances, such technology supplies chemical substances that perform various functions in a necessary amount according to a given environment. This technology can be used industrially. Such technologies are directly linked to advanced technologies such as reducing the risk to the environment (contamination by chemical substances) and suppressing side effects in medicine (drug delivery systems) as well as the efficient use of chemical substances. Yes.
[0003]
Conventionally, control release system technology has been proposed mainly by means of mixing a chemical substance in a polymer gel or making a composite of a chemical substance and a polymer material. In such a controlled release system, chemical substances are released continuously, so that the slow release rate of chemical substances can be slowed down, but the chemical substances are released as much as needed when needed. There was no on-off control.
[0004]
As a control release system having on-off control, a device using an electrode or the like has been proposed (see Patent Documents 1 to 6). However, in these systems, since chemical substances are released slowly by electric field signals, it is necessary to construct a power source / electrode and a system that connects them. When such a system cannot be constructed, for example, in vivo applications Have difficulty. Therefore, it is required to make an independent control / release system with a minute system that has on / off control and is not connected to a power source or the like.
[0005]
Silica (gel) is a harmless compound that has little risk to the environment and living organisms, and is therefore a material that has been widely put into practical use. One of the features is that the material has large pores, thereby allowing various chemical substances to be adsorbed and encapsulated therein. The sustained release of encapsulated chemicals using silica (gel) is expected to be applicable to a control release system, but when used as it is, there is no sustained release on / off control function. . In recent years, a technique has been proposed in which silica gel or capsule-like silica is provided with an on / off control function for sustained release (see Patent Documents 7 to 9). Control of release is not sufficient, and it is required to use a material having a more uniform access to the outside, that is, an exit to the outside.
[0006]
Examples of such a material include hexagonal mesoporous silica such as MCM-41 having a regular pore diameter and regular arrangement structure. Recently, there has been a report on the characteristics of sustained release by spontaneous diffusion of drugs contained in MCM-41 (see Non-Patent Document 1), but there is no on-off control technology for sustained release.
[0007]
[Patent Document 1]
JP 05-269373 A
[0008]
[Patent Document 2]
Japanese Patent Laid-Open No. 05-261278
[0009]
[Patent Document 3]
Japanese Patent Laid-Open No. 05-231560
[0010]
[Patent Document 4]
Japanese Patent Laid-Open No. 05-221469
[0011]
[Patent Document 5]
Japanese Patent Laid-Open No. 05-221468
[0012]
[Patent Document 6]
Japanese Patent Laid-Open No. 05-212277
[0013]
[Patent Document 7]
JP 2000-279817 A
[0014]
[Patent Document 8]
JP 2001-131249 A
[0015]
[Patent Document 9]
Japanese Patent Laid-Open No. 2001-213992
[0016]
[Non-Patent Document 1]
M.M. Vallet-Regi et al., Chem. Mater. Vol. 13, 308 pages, 2001
[0017]
[Problems to be solved by the invention]
The main object of the present invention is to provide a novel mesoporous inorganic material having a useful function such as controlled release of encapsulated substances and a method for producing the same.
[0018]
[Means for Solving the Problems]
The present inventor introduced a functional group that reversibly binds to the pore opening of a mesoporous inorganic material having a structure in which one-dimensional pores are regularly arranged, and the pores formed by reversible bonding and cleavage of the functional groups are introduced. It has been found that the release of inclusions in the pores can be controlled by opening and closing, and the present invention has been completed through further intensive studies.
[0019]
That is, the present invention relates to the invention shown in the following items.
[0020]
1. A mesoporous inorganic material having a structure in which one-dimensional pores are regularly arranged, and having a functional group bonded by a chemical reaction caused by an external stimulus at a pore opening.
[0021]
2. The inorganic material is silica, titania, zirconia, alumina, silica-alumina, silica-titania, tin phosphate, niobium phosphate, aluminum phosphate, titanium phosphate, and oxides, nitrides, sulfides, selenides thereof, Item 2. The mesoporous inorganic material according to Item 1, which is any one selected from the group consisting of tellurides, composite oxides, and composite salts.
[0022]
3. Item 2. The mesoporous inorganic material according to Item 1, wherein the external stimulus is at least one selected from the group consisting of light, heat, radiation, acid, alkali, crosslinking agent, magnetism, and ions.
[0023]
4). Item 2. The mesoporous inorganic material according to Item 1, wherein the chemical reaction is at least one selected from the group consisting of a dimerization reaction, a multimerization reaction, a polymerization reaction, a condensation reaction, an addition reaction, and a complex formation reaction.
[0024]
5. Item 2. The mesoporous inorganic material according to Item 1, wherein the functional group is at least one selected from the group consisting of an unsaturated group, a carboxyl group, a hydroxyl group, an amino group, an amide group, an ether group, an ester group, a carbamate group, and a silanol group.
[0025]
6). Item 2. The mesoporous inorganic material according to Item 1, wherein the functional group is a functional group derived from a coumarin derivative.
[0026]
7. Item 2. The mesoporous inorganic material according to Item 1, wherein the pores are filled with a functional substance.
[0027]
8). Item 8. The mesoporous according to Item 7, wherein the functional substance is at least one selected from the group consisting of steroid compounds, vitamin compounds, hormone compounds, pharmacologically active compounds, agricultural chemical compounds, physiologically active compounds, amino acids, sugars, fatty acids and nucleic acid compounds. Inorganic material.
[0028]
9. A method for producing a mesoporous inorganic material,
(1) A step of preparing a mesoporous inorganic material having a structure in which one-dimensional pores are regularly arranged using a surfactant as a template in an aqueous solution,
(2) before removing the surfactant contained in the mesoporous inorganic material obtained in step (1), introducing a functional group bonded by a chemical reaction by external stimulation into the pore opening of the mesoporous inorganic material; and
(3) a step of removing the surfactant;
Manufacturing method.
[0029]
10. Item 10. The method according to Item 9, wherein an acid treatment is performed between the step (1) and the step (2).
[0030]
11. A method for producing a mesoporous inorganic material in which a functional substance is filled in pores,
(1) A step of preparing a mesoporous inorganic material having a structure in which one-dimensional pores are regularly arranged using a surfactant as a template in an aqueous solution,
(2) before removing the surfactant contained in the mesoporous inorganic material obtained in step (1), a step of introducing a functional group bonded by a chemical reaction by external stimulation into the pore opening of the mesoporous inorganic material;
(3) a step of removing the surfactant;
(4) filling the functional substance into the pores of the mesoporous inorganic material; and
(5) A production method comprising a step of bonding the functional group introduced in (2) by a chemical reaction by external stimulation.
[0031]
12 Item 12. The method according to Item 11, wherein an acid treatment is performed between the step (1) and the step (2).
[0032]
13. A method for incorporating and / or removing a chemical substance, the method comprising incorporating a chemical substance into the pores of the mesoporous inorganic material according to Item 1, and then bonding a functional group by external stimulation.
[0033]
14 A method for controlling the release of a functional substance, comprising: (1) applying an external stimulus to the mesoporous inorganic material according to claim 7 to cleave a functional group to release the functional substance; and (2 ) A method for controlling the release of a functional substance comprising the step of binding a functional group by external stimulation to stop the release of the functional substance in (1).
[0034]
15. A mesoporous silica having a hexagonal structure and having an organic functional group bonded to the pore by a dimerization reaction with light.
[0035]
16. Item 16. The mesoporous silica according to Item 15, wherein the organic functional group is an unsaturated group.
[0036]
17. Item 16. The mesoporous silica according to Item 15, wherein the organic functional group is derived from a coumarin derivative.
[0037]
18. A mesoporous silica having a hexagonal structure, in which pores are filled with a functional substance, and pores are blocked by dimerized organic functional groups.
[0038]
19. Item 19. The mesoporous silica according to Item 18, wherein the organic functional group is an unsaturated group.
[0039]
20. Item 19. The mesoporous silica according to Item 18, wherein the organic functional group is derived from a coumarin derivative.
[0040]
21. A method for producing mesoporous silica having an organic functional group bonded by a dimerization reaction with light at a pore opening,
(1) A step of preparing a mesoporous silica having a hexagonal structure using a surfactant capable of forming a hexagonal structure in an aqueous solution as a template,
(2) before removing the surfactant contained in the mesoporous silica obtained in step (1), introducing an organic functional group to be bonded to the mesoporous silica having a hexagonal structure by a dimerization reaction with light; and
(3) Step of removing the surfactant using a solvent
Manufacturing method.
[0041]
22. Item 22. The method according to Item 21, wherein an acid treatment is performed between step (1) and step (2).
[0042]
23. A method for producing a mesoporous silica having a hexagonal structure in which a functional substance is filled in pores,
(1) A step of preparing a mesoporous silica having a hexagonal structure using a surfactant capable of forming a hexagonal structure in an aqueous solution as a template,
(2) before removing the surfactant contained in the mesoporous silica obtained in the step (1), a step of introducing an organic functional group that can be dimerized by light into the mesoporous silica having a hexagonal structure;
(3) removing the surfactant using a solvent;
(4) a step of filling a functional substance into pores of mesoporous silica; and
(5) Step of dimerizing organic functional groups with light
Manufacturing method.
[0043]
24. Item 24. The method according to Item 23, wherein an acid treatment is performed between step (1) and step (2).
[0044]
25. 16. A method for incorporating and / or removing a chemical substance, comprising a step of dimerizing an organic functional group with light after incorporating the chemical substance into pores of the mesoporous silica according to Item 15.
[0045]
26. 19. A method for controlling release of a functional substance, wherein the functional substance is released by cleaving a dimerized organic functional group of the mesoporous silica according to Item 18.
[0046]
27. 19. A method for controlling release of a functional substance, wherein the functional substance is released by irradiating light having a wavelength at which a dimerized organic functional group is cleaved on the mesoporous silica according to Item 18.
[0047]
28. A method for controlling the release of a functional substance, wherein the mesoporous silica according to Item 18 is irradiated with light having a wavelength at which a bond of a dimerized organic functional group is cleaved to release the functional substance. A method of controlling the release of a functional substance by stopping the release of the functional substance by irradiating light having a wavelength at which the group dimerizes.
[0048]
DETAILED DESCRIPTION OF THE INVENTION
The mesoporous inorganic material of the present invention is a mesoporous inorganic material having a structure in which one-dimensional pores are regularly arranged, and has a functional group reversibly bonded by a chemical reaction at the pore opening. Furthermore, the present invention also includes a mesoporous inorganic material in which a functional substance is filled in the pores of the mesoporous inorganic material.
[0049]
Structure with regularly arranged one-dimensional pores
The structure in which the one-dimensional pores are regularly arranged is not particularly limited as long as the structure has a uniform pore diameter and the one-dimensional pores are regularly arranged. Regularly arranged means that the pores are aligned with a uniaxial orientation. The uniform pore diameter means that the pore diameter of each pore is within a certain range. The size of the pore diameter can be appropriately set depending on the size of the compound enclosed or filled in the pore, but is usually 1 to 30 nm, preferably 1.5 to 15 nm. When a functional group derived from a coumarin derivative is used, the range of 1.5 to 5 nm, more preferably 2 to 4 nm is preferable. The size of the pores can be made differently by changing the surfactant.
[0050]
Specific examples of the structure in which the one-dimensional pores are regularly arranged include a hexagonal structure, an orthobic structure, and a monoclinic structure.
[0051]
Such a mesoporous inorganic material can be prepared using a surfactant capable of forming a regular pore structure as a template.
[0052]
Inorganic materials
As an inorganic material used as the material of the present invention, a desired material can be appropriately used. For example, silica, titania, zirconia, alumina, silica-alumina, silica-titania, tin phosphate, niobium phosphate, aluminum phosphate, titanium phosphate, and their oxides, nitrides, sulfides, selenides, tellurium A compound, complex oxide, complex salt, or the like can be used.
[0053]
Of these, silicon-containing oxides such as silica are particularly preferable in terms of excellent heat resistance, chemical resistance, and mechanical properties.
[0054]
Functional group
The functional group that the mesoporous inorganic material of the present invention has in the pore opening is not particularly limited as long as it forms a bond by a chemical reaction caused by an external stimulus. The bond by a chemical reaction due to an external stimulus is a reversible or irreversible bond, and refers to a bond that can form a bond and cleave the bond depending on the conditions of the external stimulus. Specifically, it refers to a substance that changes to a dimer / monomer by irradiation with light, or a substance that undergoes bond formation or cleavage by an oxidation-reduction reaction.
[0055]
Those that form a reversible bond are preferred when used as a material for temporarily storing a functional substance inside the pores. What forms an irreversible bond is preferable when it is used as a material for semipermanently storing a functional substance inside the pores.
[0056]
The type of external stimulus is not particularly limited, and examples thereof include light, heat, radiation, acid, alkali, cross-linking agent, magnetism, and ions. Such external stimulation is given by light irradiation, heating, cooling, radiation irradiation, change in pH value, addition of acid and / or alkali, change in coexisting ions, change in coexisting chemical substances, change in external magnetic field, and the like.
[0057]
The type of chemical reaction is not particularly limited, and examples thereof include dimerization reaction, multimerization reaction, polymerization reaction, condensation reaction, addition reaction, and complex formation reaction. Specifically, dimerization reaction with light and the like can be mentioned.
[0058]
The type of bond is not particularly limited, and examples thereof include a hydrogen bond, an ionic bond, a covalent bond, a coordination bond, and a van der Waals bond.
[0059]
Examples of the functional group that is bonded by an external stimulus include an unsaturated group, a carboxyl group, a hydroxyl group, an amino group, an amide group, an ether group, an ester group, a carbamate group, and a silanol group. Examples of unsaturated groups include vinyl groups, α, β unsaturated ketone groups, and the like. Examples of the ether group include —O—R (R is an alkyl group having 1 to 6 carbon atoms). Examples of the ester group include -COOR (R is an alkyl group having 1 to 6 carbon atoms). Specific examples include α, β-unsaturated ketone groups derived from coumarin derivatives.
[0060]
Examples of the bond formed by these functional groups include a carbon-carbon bond, an ester bond, an ether bond, an amide bond, an acetal bond, and a carbamate bond.
[0061]
In the present invention, such a functional group is introduced into the pore opening of the mesoporous inorganic material having a structure in which the one-dimensional pores are regularly arranged. More specifically, the pore opening is in the vicinity of the outlet or the inlet of the pore, and is generally in the range of about 1 to 5 nanometers from the external surface.
[0062]
Examples of the method for introducing a functional group include those introduced after synthesizing a mesoporous inorganic material and those introduced simultaneously with synthesis. Among these, what is introduced after the synthesis is preferable in that a functional group is preferentially introduced into the pore outlet.
[0063]
Such a functional group has a function like a “door” that opens and closes pores according to a change in external stimulation conditions. This door can be closed by, for example, one wavelength of ultraviolet light and opened by another wavelength of ultraviolet light. If a chemical substance is put in the mesoporous inorganic material having the “door” in advance and the “door” at the outlet of the pore is closed, the chemical substance is not released to the outside but stored. I can do things. And when this chemical is needed, it can be released out of the material by cleaving the bond.
[0064]
Hereinafter, a specific method for producing the mesoporous inorganic material of the present invention having a functional group in the pore opening will be described by taking the case of mesoporous silica as an example.
[0065]
(i) Preparation of one-dimensional pore structure mesoporous silica with template surfactant
First, a crude product of a one-dimensional pore structure mesoporous silica prepared using a surfactant as a template before removing the template is obtained. Such a crude product can be obtained by, for example, a conventionally known method using a surfactant that forms a hexagonal structure in an aqueous solution and a silica source as raw materials.
[0066]
The surfactant is not particularly limited as long as it forms a structure in which one-dimensional pores are regularly arranged in an aqueous solution, and is generally used when producing mesoporous silica. Can be used. Specifically, aliphatic quaternary such as hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, hexadecyldimethylethylammonium bromide, etc. Examples include ammonium salts, aliphatic amine salts such as hexadecylamine, and alkyl sulfates such as sodium dodecyl sulfate.
[0067]
The silica source is not particularly limited as long as mesoporous silica having a structure in which one-dimensional pores are regularly arranged can be obtained. For example, sodium silicate, potassium silicate, calcium silicate, tetraethoxysilane, tetramethoxysilane, tetra-n-propylsilane, or the like can be used.
[0068]
These surfactant and silica source are both used as aqueous solutions, but the aqueous solutions are prepared separately.
[0069]
The concentration of the surfactant in the aqueous solution may be a concentration that forms a structure in which the one-dimensional pores are regularly arranged, and can be appropriately set according to the type of the surfactant. It is about 0.2-2M.
[0070]
An alkaline agent (for example, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide) may be added to the surfactant aqueous solution as necessary. The amount of the alkali agent used is preferably about 1 to 1.5 equivalents relative to the surfactant.
[0071]
Although the density | concentration of the silica source in aqueous solution is not specifically limited, Usually, it is about 0.5-4M.
[0072]
These aqueous solutions are mixed, for example, at room temperature to about 40 ° C. with stirring for about 0.5 to 5 hours.
[0073]
In this case, the mixing ratio of the surfactant aqueous solution and the silica source aqueous solution is such that the silica source is sufficiently filled in a template having a structure in which the one-dimensional pores formed by the surfactant are regularly arranged. There is no particular limitation as long as it is an amount. Usually, in the case of a hexagonal structure, the amount is such that the surfactant aqueous solution (vol): silica source aqueous solution (vol) = 1: 4 to 1: 1. In the case of a cubic structure, an aqueous solution of a surfactant (vol): an aqueous solution of a silica source (vol) = 1: 1 to 1.5: 1, and in the case of a lamellar structure, an aqueous solution of a surfactant (vol): silica Source aqueous solution (vol) = 1.5 or more: about 1.
[0074]
Thereafter, an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid or hypochlorous acid is added to adjust the pH of the mixed solution to about 9 to 12, preferably about 10 to 11, and the temperature is about 0 to 80 ° C. Stir for about 5-6 hours. The concentration and amount of the inorganic acid to be added are not particularly limited as long as the pH is about a desired value within the above range, but the concentration is about 0.5 to 4M, preferably about 1 to 3M. However, it is about 20-100 mL with respect to 100 mL of liquid mixture of surfactant and a silica source, Preferably it is about 50-70 mL.
[0075]
After the precipitate is formed, the precipitate is filtered off and washed with water, and then dried at about 80 to 130 ° C., preferably about 90 to 110 ° C., for about 10 to 40 hours, preferably about 12 to 26 hours. Thus, mesoporous silica having a one-dimensional pore structure containing a template surfactant can be obtained.
[0076]
After the precipitate is generated as described above, the precipitate may be filtered and dried as it is, but may be subjected to an acid treatment before being filtered.
[0077]
Examples of the acid treatment include the following methods.
[0078]
First, the liquid mixture containing the precipitate is allowed to stand at about 80 to 120 ° C. for 20 to 30 hours. Next, when a neutral salt (for example, sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, etc.) is defined as 100% of silicon atoms contained in the silica source, It is added so as to be about 60 to 90 mol%, preferably about 70 to 80 mol%. At this time, the salt is dissolved in a small amount of water.
[0079]
Thereafter, an inorganic acid (for example, an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid or hypochlorous acid) is added so that the pH of the liquid is about 9 to 12, preferably about 10 to 11. The concentration of the inorganic acid is not particularly limited as long as the pH becomes a desired value within the above-described range, but is about 0.5 to 4M, preferably about 1 to 3M.
[0080]
After adding the inorganic acid, the solution containing the precipitate is allowed to stand at 80 to 120 ° C. for 20 to 30 hours.
[0081]
After performing such acid treatment, an inorganic acid is added again so that the pH of the mixed solution is about 9 to 12, preferably about 10 to 11, and the solution containing the precipitate is heated at about 80 to 120 ° C. You may repeat operation to leave still for 20 to 30 hours. When adding an acid, it is not necessary to add a salt after the 2nd time.
[0082]
The acid treatment may be repeated any number of times, but usually it is preferably about 1 to 5 times, preferably about 2 to 3 times. After finishing the acid treatment for a predetermined number of times, the precipitate may be filtered off and dried in the same manner as described above.
[0083]
By performing such an acid treatment, the thermal stability of the obtained mesoporous silica is improved.
[0084]
In this way, mesoporous silica having a structure in which one-dimensional pores are regularly arranged can be obtained. At this point, the surfactant is in the state of entering the pores of mesoporous silica. By introducing the dimerizable organic functional group while encapsulating the surfactant, the organic functional group does not enter the pores of the mesoporous silica, and mesoporous silica having excellent sustained release properties can be obtained.
[0085]
(ii) Introduction of organic functional groups
The introduction of an organic functional group will be described by taking as an example the case of introducing a functional group that dimerizes by light irradiation.
[0086]
A compound having an organic functional group that can be dimerized (hereinafter referred to as “dimerizable compound”) in order to introduce an organic functional group that is dimerized by light (hereinafter sometimes referred to as “dimerizable functional group”) into mesoporous silica. Is sometimes used). Such a compound may be either a compound that reversibly dimerizes by irradiation with light such as ultraviolet rays or a compound that dimerizes irreversibly by irradiation with light such as ultraviolet rays. In the case of controlling the sustained release of a substance, it is preferable to dimerize reversibly by light irradiation.
[0087]
An example of such a compound is α, β-unsaturated ketone. Specifically, examples of the compound having an organic group that reversibly dimerizes by light irradiation include hydroxyl groups such as 7-hydroxycoumarin, 3,4-dihydroxycoumarin, 4-hydroxycoumarin, and 7-amino-4-methylcoumarin. Amino group, carboxyl group, ester group [for example, -CO-OR¹(R¹Is, for example, an alkyl group having about 1 to 6 carbon atoms. )] And the like, and a coumarin derivative having at least 1, preferably 1 to 2, substituents can be presented.
[0088]
Examples of the compound having an organic group that irreversibly photodimerizes include hydroxyl groups such as 4-hydroxychalcone, 4′-hydroxychalcone, and 4,4′-hydroxychalcone, amino groups, carboxyl groups, ester groups [ For example, -CO-OR¹(R¹Is, for example, an alkyl group having about 1 to 6 carbon atoms. )] And other chalcones having at least one substituent, preferably 1-2.
[0089]
In order to introduce the dimerizable compound into mesoporous silica, for example, after introducing an olefin group into the dimerizable compound, hydrosilanes are reacted to synthesize a dimerizable group-containing silane compound.
[0090]
The introduction of the olefin group into the dimerizable compound is, for example, by reacting an organic halide having an olefin group with a functional group such as a hydroxyl group of the dimerizable compound according to a conventional method, for example, in a solvent in the presence of a base. Can be performed. Although it does not specifically limit as an organic halide which has an olefin group, C3-C8 olefin groups, such as allyl chloride, allyl bromide, allyl iodide, 3-bromide cyclohexene, 6-bromide-1-hexene, etc. Examples thereof include organic halides. The type (number of carbon atoms) of the organic halide having an olefin group is such that, depending on the type of the compound having an organic group that can be dimerized, the inlet of the pores of the mesoporous inorganic material can be blocked after dimerization. A thing can be selected suitably.
[0091]
Examples of the solvent include acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, 1,4-dioxane and the like. In particular, acetone is preferable. Examples of the base include sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, potassium hydroxide, cesium carbonate, sodium methoxide, potassium t-butoxide and the like. The usage-amount of a base should just be 1-3 equivalent with respect to dimerizable compounds, such as 7-hydroxycoumarin, for example. The reaction temperature should just be about 40-100 degreeC, for example, Preferably, it is 60-80 degreeC. The reaction time is, for example, about 3 to 24 hours.
[0092]
The olefin-containing dimerizable compound thus obtained is reacted with an alkoxysilane according to a conventional method to obtain a dimerizable group-containing silane compound. The alkoxysilane used here is not particularly limited as long as it can react with a silanol group of mesoporous silica having a one-dimensional pore structure to introduce a dimerizable functional group into the mesoporous silica. For example, at least one alkoxysilane is used. Group-containing compounds, preferably HSiR_Three(In the formula, R may be the same or different and represents an alkyl group having about 1 to 4 carbon atoms or an alkoxy group having about 1 to 3 carbon atoms, and at least one of R is an alkoxy group having about 1 to 3 carbon atoms. The alkoxysilane represented by this is mentioned. Specific examples include triethoxysilane, trimethoxysilane, diethoxymethylsilane, ethoxydimethylsilane, and the like.
[0093]
This reaction can be carried out by reacting in the presence of a solvent in the presence of a catalyst. Examples of the solvent include toluene, xylene, tetrahydrofuran, dioxane, benzene, hexane, dichloromethane, chloroform and the like. In particular, toluene and xylene are preferable. As the usage-amount of an olefin containing dimerization compound, about 1-1.5 equivalent is preferable with respect to alkoxysilane, for example, about 1-1.2 equivalent is especially preferable. Examples of the catalyst include platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, platinum-2,4,6,8-tetramethyl-2,4,6,8-tetra. Platinum catalyst such as vinyl-cyclotetrasiloxane complex, chloroplatinic acid, platinum supported on activated carbon, platinum supported on alumina, Wilkinson complex (RhCl (PPh_Three)_Three), Rhodium catalysts such as activated carbon supported rhodium and alumina supported rhodium, and palladium catalysts such as tetrakistriphenylphosphine palladium and activated carbon supported palladium. The usage-amount of the said catalyst should just be about 0.005-0.5 mol% with respect to alkoxysilane, for example, Preferably it is about 0.02-0.1 mol%. The reaction temperature may be, for example, about 0 to 80 ° C., preferably about room temperature (around 25 ° C.) to about 30 ° C. The reaction time is, for example, about 10 minutes to 4 hours.
[0094]
When introducing the dimerizable group-containing silane compound thus obtained into a mesoporous silica having a one-dimensional pore structure, the mesoporous silica having a one-dimensional pore structure in which the surfactant as a template is removed by baking or extraction is used. Instead of using, it is preferable to use mesoporous silica in which the pores are filled with the template surfactant. Since the pores are filled with the template surfactant, the dimerizable group-containing silane compound does not enter the pores, but only reacts with the silanol groups at the entrance of the pores and is introduced. It is.
[0095]
A mesoporous silica having a one-dimensional pore structure is suspended in a solvent (for example, n-hexane, toluene, etc.), then a dimerizable group-containing silane compound is added, and the temperature is from about room temperature to about 80 ° C. for about 10 minutes to about 6 hours. By reacting, the dimerizable functional group can be introduced at the entrance of the pores of the mesoporous silica.
[0096]
The amount of the dimerizable group-containing silane compound used is such an amount that it can confine a functional substance encapsulated (filled) in the pores of mesoporous silica having a one-dimensional pore structure by dimerization after introduction. Although there is no particular limitation as long as it is present, it is usually about 2 to 20 parts by weight with respect to 100 parts by weight of mesoporous silica filled with the template surfactant.
[0097]
In addition to the above-mentioned method, various crosslinkable functional groups such as ester groups and amino groups can be used instead of the dimerizable functional group in the pore opening of the one-dimensional pore structure mesoporous inorganic material. If a bond that can be easily cleaved, such as an ester bond, an amide bond, or an acetal bond, is formed by the above method, it can be cleaved by an appropriate method to incorporate or remove chemical substances or release functional substances. Control can be performed.
[0098]
(iii) Surfactant removal
Next, after the dimerizable functional group is introduced into the mesoporous silica, the surfactant remaining in the pores is removed by solvent extraction or baking.
[0099]
When using a heat-sensitive organic functional group such as a coumarin group, removing the remaining surfactant by baking treatment will eliminate the introduced dimerizable functional group, so remove the surfactant with a solvent. It is preferable.
[0100]
The method of solvent extraction is not particularly limited, but it is preferable to remove the used surfactant with an alcohol (for example, aliphatic alcohols such as methanol and ethanol) that can be dissolved well. When alcohol is used, it is preferably removed as a mixed solution with hydrochloric acid. When hydrochloric acid is used, the concentration of hydrochloric acid in the mixed solution is not particularly limited, but is preferably about 0.5 to 5M.
[0101]
In the case of firing, the temperature is not particularly limited, but is preferably about 500 to 600 ° C.
[0102]
The present invention also includes a mesoporous silica having a one-dimensional pore structure thus obtained and having an organic functional group capable of dimerization at the entrance of the pore. In such mesoporous silica, the “organic functional group capable of dimerization” has not been dimerized yet, and the entrances of the pores are open. Moreover, the organic functional group is introduced at the entrance of the pore, and the organic functional group is not substantially introduced into the pore. The organic functional group that can be dimerized is introduced at a position that can block the entrance of the pore when the functional group is dimerized.
[0103]
( iv ) Filling with functional substances and dimerization of dimerizable functional groups
The dimerizable functional group-introduced mesoporous silica synthesized in this way can be blocked by closing the pore entrance by dimerizing the functional group.
[0104]
Dimerization can be performed by light irradiation such as ultraviolet irradiation with a wavelength corresponding to the type of functional group. The irradiation time can be appropriately set according to the amount of the functional group to be dimerized, and can be set, for example, while confirming the absorption peak of the dimerizable group.
[0105]
When a group capable of reversibly dimerizing with light, such as a coumarin derivative, is introduced as a dimerization compound, the dimerization is performed with ultraviolet rays having a wavelength of 310 nm or more (when a coumarin derivative is used as the dimerization compound). In general, it can be performed by irradiating light in a range of about 310 nm to 340 nm. The lamp used at this time is not particularly limited as long as it can irradiate ultraviolet rays having a wavelength of 310 nm or more, but a high-pressure mercury lamp is preferable. When a high-pressure mercury lamp is used, lamps with a wavelength of 310 nm or less can be excluded if the heat-resistant hard glass jacket is used. On the other hand, when a coumarin derivative is used as the dimerization compound, the dimerized functional group can be cleaved by irradiating with ultraviolet rays in the vicinity of 250 nm (for example, around 240 to 260 nm) and can be made into a single monomer. Ultraviolet irradiation with such a wavelength can be performed using a quartz glass container with a low-pressure mercury lamp. Such a reversible change can be confirmed by examining the presence or absence of absorption of a photodimerizable group (in the case of a coumarin derivative, absorption at 310 to 330 nm) in the ultraviolet spectrum.
[0106]
In this way, by utilizing the dimerization and monomerization reaction of a coumarin derivative or the like capable of performing dimerization reversibly, the functional substance encapsulated in the pores of mesoporous silica can be released to the outside of the pores. On-off control of sustained release becomes possible. That is, the functional substance is released from the pores by irradiating light having a wavelength at which the bond of the dimerized organic functional group is cleaved, and the functional substance is irradiated by irradiating light having a wavelength at which the organic functional group is dimerized. Can be stopped, thereby allowing the functional substance to be released in the desired amount in the desired location. Further, such on-off control can be repeatedly performed by changing the conditions of the external stimulus.
[0107]
In a mesoporous inorganic material into which a functional group derived from a coumarin derivative has been introduced, a state in which pores are opened and closed by bonding and cleavage of the functional groups and the compounds in the pores are released and stored is shown in FIG.
[0108]
If the group dimerized by light cannot be cleaved, it may be cleaved according to the mode of bonding to mesoporous silica. For example, in the case of an ester bond, amide bond, etc., these may be hydrolyzed using an acid or the like. It is possible to cleave the bond and release the functional substance out of the pores. Thus, even in the case of irreversible bonding, on-off control can be performed to release the functional substance confined in the pores at a desired location or time.
[0109]
The substance to be filled in the pores of the mesoporous silica is not particularly limited as long as it is a functional substance that can enter the pores, and a substance can be appropriately selected according to the application. For example, steroid compounds such as cholestan, cholesterol, progesterone, testosterone, estradiol, vitamin compounds such as vitamin A and vitamin D, hormone compounds such as adrenaline and noradrenaline, pharmacologically active compounds such as penicillin and ibuprofen, phosphate esters, etc. Pesticide compounds, physiologically active compounds such as alkaloids and prostaglandins, amino acids containing oligopeptides, monosaccharides, saccharides containing polysaccharides, fatty acids containing fats, and nucleic acids containing oligonucleotides can be used.
[0110]
The method of filling the functional substance into the pores can be appropriately selected according to the type of the functional substance. For example, the present invention in a state where the functional group is not dimerized (off state). Mesoporous silica can be immersed in a liquid containing a functional substance, the functional substance can be introduced into the pores, and then dimerization of the functional groups can be performed to block the entrance of the pores.
[0111]
As a method for filling, a specific example in which a coumarin derivative is used as a dimerizable group functional group and cholestane, which is a kind of steroid, is used as a functional substance is shown below.
[0112]
The coumarin derivative organic group-modified mesoporous silica is immersed in an n-hexane solution of cholestane (the concentration of cholestane and the amount of the solution are not particularly limited) (about 24 hours). Thereafter, the mesoporous silica is filtered off and washed well with n-hexane. The mesoporous silica containing cholestane is passed through a heat-resistant hard glass jacket and irradiated with ultraviolet rays with a high-pressure mercury lamp so as to remove light with a wavelength of 310 nm or less. The irradiation time can be appropriately set according to the amount of mesoporous silica. The absorption of the photodimerizable group may be measured in the ultraviolet spectrum, and irradiation may be performed until there is no decrease in the photodimerizable group.
[0113]
In addition, by using a quartz glass container with a low-pressure mercury lamp, irradiation with ultraviolet rays around 250 nm can cleave the dimerized functional group and release (slow release) the functional substance. In this case, the irradiation time can be appropriately set according to the amount of the functional substance (cholestane) desired to be released slowly. In this case, the absorption of the photodimerizable group is measured in the ultraviolet spectrum, Irradiation may be stopped when the increase in absorption stops.
[0114]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these Examples.
[0115]
Example 1
(1) Synthesis of hexagonal mesoporous silica (MCM-41) (with template surfactant)
22.86 g of sodium silicate (silicon: 0.20 mol; sodium: 0.184 mol) is completely dissolved in 100 g of water. Separately, 48.86 g of tetramethylammonium hydroxide (0.134 mol) and 38.72 g of hexadecyltrimethylammonium bromide (0.102 mol) were added to 100 g of water and heated to 35 ° C. to completely dissolve. Let The two uniform aqueous solutions are mixed and stirred well at room temperature for 2 hours.
[0116]
Next, a solution in which 13.28 g of sulfuric acid (0.13 mol) was dissolved in 51 g of water was slowly added to the above solution and stirred at room temperature for 2 hours to form a precipitate. The pH value of the solution portion of this mixed solution was about 10.5. The mixture was transferred to a polypropylene bottle and allowed to stand at 100 ° C. for 24 hours. After cooling to room temperature, concentrated sulfuric acid was added until the pH value reached about 10.5, then 11.83 g (0.15 mol) of potassium chloride was added, and the mixture was allowed to stand again at 100 ° C. for 24 hours. Thereafter, concentrated sulfuric acid was added twice to adjust the pH value to about 10.5. The produced precipitate was filtered off, washed thoroughly with distilled water, and dried at 105 ° C. for 24 hours. Thus, hexagonal mesoporous silica containing a template surfactant having a stable structure was synthesized.
[0117]
(2) Synthesis of 7-allyloxycoumarin
To an acetone solution (100 mL) of 3.24 g (20 mmol) of commercially available 7-hydroxycoumarin, 4.15 g (30 mmol) of anhydrous potassium carbonate was added (insoluble), and then 6.05 g (50 mmol) of allyl bromide was added. This mixed solution was allowed to react at 70 ° C. for 12 hours. After insoluble matters were filtered off, the reaction solution was distilled under reduced pressure to obtain 4.02 g of residue (crude yield: 99%). This solid was recrystallized from ethanol to obtain 3.85 g (yield: 95%) of the title compound. The analytical data of the obtained compound are shown.
¹H NMR (CDCl_Three, 400 MHz): 4.60 (d, 2H), 5.49 (dd, 1H), 6.0 to 6.08 (m, 1H), 6.24 (d, 1H), 6.85 (d, 1H), 6.86 (dd, 1H), 7.38 (d, 1H), 7.64 (d, 1H).
Infrared spectrum (KBr method) (major absorption): 3082, 1726, 1615, 1285, 1228, 1128, 1127, 998, 843 cm^-1.
[0118]
(3) Preparation of 3- (7-coumaroxy) propyltriethoxysilane
2.02 g (10 mmol) of 7-allyloxycoumarin and 1.80 g (11 mmol) of triethoxysilane were dissolved in 50 mL of toluene, and dry nitrogen was blown in for about 10 minutes. Thereafter, 0.5 mL of a catalyst solution (a solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex diluted with toluene to 2 mM) was added to the solution, and room temperature was added. For 20 hours. After distilling off the solvent (toluene) under reduced pressure, the obtained oily product was dried under reduced pressure to obtain a crude product (3.45 g; crude yield 95%). This crude product was used as such for the next synthesis ((4) of Example 1 below). The analytical data of the obtained compound are shown.
¹H NMR (CDCl_Three, 400 MHz): 0.75 (dd, 2H), 1.23 (t, 9H), 1.80 to 1.95 (m, 2H), 3.78 (q, 6H), 4.00 (t, 2H), 6.23 (d, 1H), 6.80-6.90 (m, 2H), 7.35 (d, 1H), 7.63 (d, 1H).
¹³C NMR (CDCl_Three99 MHz): 9.97, 18.39, 22.61, 58.12, 70.58, 101.22, 112.23, 112.73, 112.79, 128.56, 143.29, 155. 71, 161.05, 162.16.
Infrared spectrum (KBr method) (major absorption): 2970, 1736, 1616, 1124, 1078 cm^-1.
[0119]
(Four) Synthesis of organic group-introduced mesoporous silica derived from coumarin derivatives
2 g of the mesoporous silica prepared in the above (1) is suspended in 20 mL of n-hexane, and then 0.2 g of 3- (7-coumaryloxy) propyltriethoxysilane prepared in the above (3) is added, and 30 g at room temperature. Grafting was performed with stirring for a minute to introduce a coumarin group-derived functional group. The solvent was distilled off under reduced pressure at 80 ° C. for 2 hours, followed by vacuum drying at 150 ° C. for 12 hours. Removal of the template (surfactant) remaining in the organic group-containing mesoporous silica derived from the obtained coumarin derivative was performed by refluxing at 80 ° C. for 4 hours using 100 mL of ethanol containing 1M hydrochloric acid. Thereafter, the supernatant was removed, and the solid was again refluxed with the same ethanol solution. After a total of three reflux treatments, the solid was filtered off, washed thoroughly with ethanol, and dried at 80 ° C. for 12 hours. The complete removal of the template surfactant was confirmed by gas chromatography, thermogravimetry and elemental analysis. The mesoporous silica obtained by the above operation is designated as Sample 2A.
[0120]
(Five) On-off control of sustained release of cholestane using organic group-introduced mesoporous silica derived from coumarin derivatives
In 20 mL of n-hexane solution in which 1 g of cholestane was dissolved, 1 g of mesoporous silica into which an organic group derived from a coumarin derivative was introduced was suspended at room temperature for 24 hours. Mesoporous silica was filtered off, washed 5 times with n-hexane, and dried at 60 ° C. for 12 hours. The amount of cholestane remaining in mesoporous silica was calculated from the amount of cholestane in n-hexane used for washing. As a result, it was found that 33.0% by weight of cholestane was encapsulated in mesoporous silica.
[0121]
The solids of the cholestane-encapsulated mesoporous silica were irradiated with ultraviolet rays excluding those having a wavelength of 310 nm or less through a heat-resistant hard glass jacket for 3 hours using a high-pressure mercury lamp. The mesoporous silica was suspended again in 20 mL of n-hexane and sufficiently stirred at room temperature for 24 hours. Thereafter, the solid was filtered off and washed with a sufficient amount of n-hexane. All filtrates were collected and the amount of eluted cholestan was quantified by gas chromatography. The detected amount of cholestane was 5%, and 28% still remained.
[0122]
The mesoporous silica solid itself is irradiated with ultraviolet light having a wavelength of 240 to 260 nm for about 5 minutes using a quartz glass container with a low-pressure mercury lamp, and then the mesoporous silica is suspended in 20 mL of n-hexane again at room temperature. Stir well for 48 hours. Thereafter, the solid was filtered off and washed with a sufficient amount of n-hexane. As a result of collecting all the filtrates and quantifying the amount of eluted cholestane by gas chromatography, 6% of the contained cholestane, that is, 22% of cholestane was eluted.
[0123]
A conceptual diagram of on-off control of sustained release of cholestane using organic group-introduced mesoporous silica derived from a coumarin derivative is shown in FIG.
[0124]
Example 2
In the introduction of the functional group derived from the coumarin derivative in Example 1, mesoporous silica was synthesized by performing the same operation as in Example 1 except that grafting was performed for 24 hours (Sample 2B). In addition, using the obtained mesoporous silica, on-off control of sustained release of cholestane was examined by the same method as in Example 1. As a result, the cholestane stored in the pores was 5%, and the cholestane released thereafter was 2%.
[0125]
Example 3
In the introduction of the functional group derived from the coumarin derivative in Example 1, the mesoporous layer was subjected to the same operation as in Example 1 except that the surfactant was removed by solvent extraction before introducing the functional group, and then grafting was performed. Silica was synthesized (Sample 2C). Further, on / off control of sustained release of cholestane was investigated by the same method as in Example 1 using the obtained mesoporous silica. As a result, 13% of cholestanes were stored in the pores, and 2% were released thereafter.
[0126]
Example 4
In Example 1, when synthesizing mesoporous silica, an organic substituent-containing silane compound such as 3- (7-coumaroxy) propyltriethoxysilane was coexisted, and the preparation of mesoporous silica and the functionality derived from the coumarin derivative were conducted by one-pot synthesis. Except for introducing the group, the same operation as in Example 1 was performed to prepare mesoporous silica (Sample 2D). Further, on / off control of sustained release of cholestane was investigated by the same method as in Example 1 using the obtained mesoporous silica. As a result, no cholestane was stored in the pores.
[0127]
FIG. 3 shows the results of examining the UV absorption after 200-minute light irradiation (wavelength> 310 nm) for the mesoporous inorganic materials Sample 2A to 2D prepared in Examples 1 to 4.
[0128]
In Sample 2A, it was found that absorption at 324 nm of coumarin almost disappeared, and almost all (> 98%) of coumarin was dimerized. In the case of Sample 2B and Sample 2C, a decrease in absorption at 324 nm was observed, and it was found that each part (25% for Sample 2B and 63% for Sample 2C) was dimerized. On the other hand, Sample 2D hardly confirmed dimerization by light (<1%).
[0129]
Comparative Example 1: Cholestan sustained release using mesoporous silica having no dimerizable functional group
The surfactant was removed from the mesoporous silica obtained in (1) of Example 1 using ethanol containing hydrochloric acid in the same manner as described in (4) of Example 1. This mesoporous silica was suspended in 20 mL of n-hexane solution in which 1 g of cholestane was dissolved at room temperature for 24 hours. Mesoporous silica was filtered off, washed 5 times with n-hexane, and dried at 60 ° C. for 12 hours.
[0130]
After cholestan was encapsulated in this manner, the mesoporous silica was suspended again in 20 mL of n-hexane and sufficiently stirred at room temperature for 24 hours. Thereafter, the solid was filtered off and washed with a sufficient amount of fresh n-hexane. As a result of collecting all the filtrates and quantifying the amount of eluted cholestane by gas chromatography, most of the cholestane used first was eluted in n-hexane, and the remaining amount of cholestane in mesoporous silica was 2% or less. .
[0131]
Comparative Example 2: Slow release of cholestane using organic group-introduced mesoporous silica derived from a coumarin derivative that was not irradiated with light
The mesoporous silica into which the organic group derived from the coumarin derivative obtained in (4) of Example 1 was introduced was suspended in a 20 mL n-hexane solution in which 1 g of cholestane was dissolved at room temperature for 24 hours. Mesoporous silica was filtered off, washed 5 times with n-hexane, and dried at 60 ° C. for 12 hours.
[0132]
Thereafter, the mesoporous silica was directly suspended in 20 mL of n-hexane without performing ultraviolet irradiation, and sufficiently stirred at room temperature for 24 hours. Thereafter, the solid was filtered off and washed with a sufficient amount of fresh n-hexane. All filtrates were collected, and the amount of cholestane eluted was quantified by gas chromatography. Most of the cholestane used first was eluted in n-hexane, and the residual amount in mesoporous silica was 2% or less.
[0133]
Example 5: On-off control of sustained release of pyrene using a coumarin derivative organic group-introduced mesoporous silica
The sustained release on / off control using the mesoporous silica of the present invention was performed in the same manner as in Example 1 except that 1 g of pyrene was used instead of cholestane as the substance to be encapsulated. The amount of pyrene encapsulated after washing with n-hexane after ultraviolet irradiation with a high-pressure mercury lamp was 1.05% as a ratio (weight) to mesoporous silica. Pyrene irradiated with a low-pressure mercury lamp and encapsulated after washing with n-hexane was 0.28% as a ratio (weight) to mesoporous silica.
[0134]
Except for using 1 g of pyrene instead of cholestane as the substance to be encapsulated, when performed in the same manner as Comparative Examples 1 and 2, the amount of pyrene encapsulated after washing with n-hexane was 0.00%. The
As is apparent from the results of Examples 1 and 2 and the comparative example, when photodimerization is performed by ultraviolet irradiation, the encapsulated functional substances (cholestane and pyrene) are gradually released even by washing with a solvent of these functional substances. However, by dimerizing the organic group into a monomer by irradiation with a short wavelength ultraviolet ray, the encapsulated functional substances (cholestane and pyrene) can be gradually released out of the pores, that is, on-off of the sustained release of the inclusion by light. Control was possible. Since coumarin can be dimerized reversibly by light, it is expected that this on-off function can be performed repeatedly.
[0135]
【The invention's effect】
According to the present invention, the opening and closing function of the pores is controlled by introducing a functional group that is bonded or cleaved by an external stimulus into the pore opening of the mesoporous inorganic material having a structure in which one-dimensional pores are regularly arranged. Given to the material. This makes it possible for the mesoporous inorganic material of the present invention to enclose, release, or control specific substances. Specifically, the pores of the mesoporous inorganic material can be opened and closed by changing the conditions of the external stimulus, and by such an opening and closing function, harmful chemical substances can be removed, desired chemical substances can be taken in, or It is possible to release and control the functional substance filled in the pores.
[0136]
The mesoporous inorganic material of the present invention has a function of including a functional chemical substance in a solid material and releasing it from the inside to the outside (sustained release), and is used in various fields (for example, pharmaceuticals, agricultural chemicals, cosmetics). In various catalysts, fertilizers, fragrances, etc.), it can be used as a technique capable of supplying a necessary amount at a required time according to a given environment.
[0137]
For example, in conjunction with an external odor sensor, when an odor is observed, the encapsulated aromatic compound is gradually released to the outside to keep the air in the space comfortable or to respond to the arrival of pests, etc. The usage method of spraying can be considered. In addition, it can be used as a drug delivery system in which mesoporous silica encapsulating a drug is injected into the body by injection or the like, and then the ultraviolet ray is irradiated only to the affected area so that the drug acts only on the affected area. On the other hand, when the concentration of the chemical substance existing in the environment becomes high, there is a usage method in which the dimerized functional group is opened and the chemical substance is absorbed into the pores and removed from the system. I can expect.
[0138]
Thus, the mesoporous inorganic material of the present invention provides an excellent technical means applicable to various fields.
[Brief description of the drawings]
FIG. 1 is a drawing showing a state in which a compound in a pore is released and stored using a mesoporous inorganic material into which a functional group derived from a coumarin derivative is introduced.
FIG. 2 is a conceptual diagram of on-off control of sustained release of cholestane using organic group-introduced mesoporous silica (MCM-41) derived from a coumarin derivative.
FIG. 3 is a drawing showing the results of examining the UV absorption of the mesoporous inorganic materials prepared in Examples 1 to 4.

Claims (21)

A mesoporous silicon-containing oxide having a structure in which one-dimensional pores are regularly arranged,
A mesoporous silicon-containing oxide having a functional group dimerized by light irradiation at the pore opening. The mesoporous silicon-containing oxide according to claim 1, wherein the mesoporous silicon-containing oxide is mesoporous silica. The mesoporous silicon-containing oxide according to claim 1 or 2, wherein the functional group dimerized by light irradiation is an organic functional group derived from a coumarin derivative or a chalcone. The mesoporous silicon-containing oxide according to any one of claims 1 to 3, wherein the functional group dimerized by light irradiation is an organic functional group derived from a coumarin derivative dimerized by ultraviolet rays. A functional substance is filled in the pores,
The pore diameter is 1 to 30 nm,
The functional substance is a substance that can enter the pores of the pore size, and steroid compound, vitamin compound, hormone compound, penicillin, ibuprofen, phosphate ester, alkaloid, prostaglandin, amino acid, saccharide, The mesoporous silicon-containing oxide according to any one of claims 1 to 4, which is at least one selected from the group consisting of fatty acids and nucleic acids. The mesoporous silicon-containing oxide according to claim 5, wherein the functional substance is cholestane or pyrene. A mesoporous silicon-containing oxide having a structure in which one-dimensional pores are regularly arranged,
A method for producing a mesoporous silicon-containing oxide having a functional group dimerized by light irradiation at the pore opening,
(1) A step of preparing a mesoporous silicon-containing oxide having a structure in which one-dimensional pores are regularly arranged using a surfactant as a template in an aqueous solution,
(2) A step of introducing a functional group to be dimerized by light irradiation into the pore opening of the mesoporous silicon-containing oxide before removing the surfactant contained in the mesoporous silicon-containing oxide obtained in the step (1). And (3) removing the surfactant,
Manufacturing method. The production method according to claim 7, wherein the mesoporous silicon-containing oxide is mesoporous silica. The production method according to claim 8, wherein the functional group dimerized by light irradiation is an organic functional group derived from a coumarin derivative or a chalcone . The manufacturing method in any one of Claims 7-9 whose functional group dimerized by light irradiation is an organic functional group derived from the coumarin derivative dimerized by an ultraviolet-ray. The method according to any one of claims 7 to 10, wherein an acid treatment is performed between the step (1) and the step (2). It has a structure in which one-dimensional pores are regularly arranged, has a functional group dimerized by light irradiation at the pore opening, is filled with a functional substance, and A method for producing a mesoporous silicon-containing oxide having a pore size of 1 to 30 nm,
(1) A step of preparing a mesoporous silicon-containing oxide having a structure in which one-dimensional pores are regularly arranged using a surfactant as a template in an aqueous solution,
(2) before removing the surfactant contained in the mesoporous silicon-containing oxide obtained in step (1), introducing a functional group to be dimerized by light irradiation into the pore opening of the mesoporous inorganic material;
(3) a step of removing the surfactant;
(4) including a step of filling a functional substance into pores of a mesoporous silicon-containing oxide, and (5) a step of bonding the functional group introduced in (2) by a reaction of dimerization by light irradiation,
A functional substance is a substance that can enter the pores of the above-mentioned pore diameter, and is a steroid compound, vitamin compound, hormone compound, penicillin, ibuprofen, phosphate ester, alkaloid, prostaglandin, amino acid, saccharide, fatty acid And at least one method selected from the group consisting of nucleic acids. The method according to claim 12, wherein the mesoporous silicon-containing oxide is mesoporous silica. The production method according to claim 12 or 13, wherein the functional group to be dimerized by light irradiation is an organic functional group derived from a coumarin derivative or a chalcone. The manufacturing method in any one of Claims 12-14 whose functional group dimerized by light irradiation is an organic functional group derived from the coumarin derivative dimerized by an ultraviolet-ray. The production method according to claim 12, wherein the functional substance is cholestane or pyrene. The method according to any one of claims 12 to 16, wherein an acid treatment is performed between the step (1) and the step (2). A method for controlling the release of a functional substance,
(1) It has a structure in which one-dimensional pores are regularly arranged, has a functional group reversibly dimerized by light irradiation in the pore opening, and is filled with a functional substance in the pore, And in the mesoporous silicon-containing oxide whose pore diameter is 1 to 30 nm,
Irradiating light having a wavelength at which the bond of the dimerized organic functional group is cleaved to release the functional substance out of the pores; and (2) irradiating light having a wavelength at which the organic functional group is dimerized. A step of stopping the release of the functional substance in (1),
A functional substance is a substance that can enter the pores of the above-mentioned pore diameter, and is a steroid compound, vitamin compound, hormone compound, penicillin, ibuprofen, phosphate ester, alkaloid, prostaglandin, amino acid, saccharide, fatty acid And at least one method selected from the group consisting of nucleic acids. The method according to claim 18, wherein the mesoporous silicon-containing oxide is mesoporous silica. The method according to claim 18 or 19, wherein the functional group that is reversibly dimerized by light irradiation is an organic functional group derived from a coumarin derivative that is dimerized by ultraviolet light. The method according to any one of claims 18 to 20, wherein the functional substance is cholestane or pyrene.

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