JP2002159848A - Method for producing organic-inorganic composite and metal oxide using saccharide derivertive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technology for producing a nano-scale metal oxide (an inorganic structure) and a raw material therefor, an organic-inorganic composite, by using an organic low molecular gel as a template. SOLUTION: After the gel of a glycopyranoside is formed in a mixture solution obtained from the glycopyranoside to which a benzylidene is bonded at 4- and 6-positions and to which an aminophenyl group or a pyridyl group is bonded at 1-position, and a sol-gel reaction solution containing the precursor of the metal oxide, the organic-inorganic composite stuck with the metal oxide on the surface of the glycopyranoside is obtained by proceeding the polymerization of the metal oxide retaining a gel formed system, and furthermore a metal oxide (for example, silica) structure is obtained by removing the glicopyranoside from this organic-inorganic composite. The metal oxide structure of a hollow spherical, a Lotus root or a cylindrical shape is obtained depending on the type of saccharides constituting the glycopyranoside.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a metal oxide having a novel structure which can be used as a catalyst or its support, an adsorbent, and other various functional materials, and an organic-inorganic composite which is a raw material thereof. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Inorganic porous materials typified by silica are frequently used as catalysts, supporting materials or adsorbing materials, chromatographic materials, etc., due to the selectivity of molecules due to their surface area and pore size. Improvements are being attempted. For the preparation of these porous materials, a method using a template is used.For the preparation of microporous materials such as zeolites, organic low molecular weight compounds, surfactants and block copolymers for mesoporous materials, and macroporous materials for There is an example using each emulsion. Also,
Among porous materials, a fibrous or hollow inorganic material is synthesized using a molecular association of tartaric acid, carbon fiber, and carbon nanotube as a template. On the other hand, in research on so-called biomineralization that uses the functions of biological materials, attempts have been made to create various forms of inorganic materials using biological materials as templates, and cylindrical organic-inorganic materials using self-assembled lipid tubes have been tried. Complexes and the like have also been obtained. However, heretofore, there have been almost no examples of preparing an organic-inorganic composite material or an inorganic material using an organic low-molecular gel as a template. Materials that reflect various gel structures and reflect the gel structure are expected to be applied to various applications as materials with anisotropy based on unique shapes, but there are very few technologies that embody such materials. .

It is well known that sols such as metal alkoxides are polymerized and crosslinked by a catalyst to form a metal oxide polymer and gel. The present inventors have, first,
By deriving such a sol-gel reaction on a low-molecular-weight gel, an organic-inorganic composite using the low-molecular-weight gel as a template and a technique for producing a metal oxide from the composite have been devised (Japanese Patent Application No. Hei 10-284,197). 11-108922, Japanese Patent Application 2000-
068044, Japanese Patent Application 2000-150869). That is, a cholesterol derivative which is an organic low molecule having an ionic site as a gel-forming agent (gelling agent) (Japanese Patent Application No. Hei 11
-108922) or a cyclohexane derivative (Japanese Patent Application No. 2000-068044) or a cholesterol derivative which is a low organic molecule having a hydrogen bonding site (Japanese Patent Application No. 2000-68092).
-150869), a metal oxide (more precisely, a precursor of the metal oxide) is attached to the low-molecular organic gel formed in an organic solvent by electrostatic attraction or hydrogen bonding to promote polymerization. Then, an organic-inorganic composite having a metal oxide attached to the surface of a low-molecular organic compound is prepared, and an inorganic structure (metal oxide) is prepared by removing the low-molecular organic compound from the composite.

[0004] The methods disclosed in these patent applications are useful techniques for preparing nanometer-sized organic-inorganic composite materials and inorganic materials (metal oxides) using low-molecular organic gels as templates. The structure obtained is limited to a cylindrical shape or a shape based on a cylindrical shape. For example, a hollow spherical structure has not been obtained yet. Also,
The fact that the synthesis of a cholesterol derivative or the like used as a gelling agent requires relatively skill is not a disadvantage.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a new technique which can produce a nano-scale metal oxide (inorganic structure) and a raw material thereof using an organic low molecular weight gel as a template. Is to do.

[0006]

SUMMARY OF THE INVENTION The present inventors have previously found that a sugar-based derivative (glycopyranoside) functions as a gelling agent for water and various organic solvents (Japanese Patent Application No. Hei 10-26139). 11-049950). The inventor has
As a result of further studies, they have found that nanoscale structures of various shapes can be obtained by performing a sol-gel reaction on a gel obtained from this derivative using the gel as a template, and derived the present invention.

Thus, the present invention provides: (1) a. Glycopyranoside having a structure in which the hydroxyl groups at the 4- and 6-positions of the monosaccharide are benzylidene and the hydroxyl group at the 1-position is dehydrogenated to bond an aminophenyl group or a pyridyl group; b. A sol-gel reaction solution comprising a metal oxide precursor, a catalyst for producing a metal oxide polymer by a sol-gel reaction from the metal oxide precursor and water, and c. If necessary, a step of preparing a homogeneous mixed solution containing an organic solvent capable of dissolving the glycopyranoside and the sol-gel reaction solution; (2) a. After heating the homogeneous mixture, cool or
Or b. Cooling the homogeneous mixture to form a gel of glycopyranoside; and (3) maintaining the gel-formed system and promoting polymerization of the metal oxide. And a method for producing an organic-inorganic composite in which a metal oxide is attached to the surface of glycopyranoside (claim 1).

The present invention further provides a method for producing a metal oxide, which comprises removing a low-molecular organic compound (glycopyranoside) from the organic-inorganic composite obtained by the above method (claim 2). ). In a preferred example of the method for producing a metal oxide according to the present invention, glycopyranoside is removed by calcination (claim 3). The method for producing a metal oxide of the present invention is particularly suitable for obtaining silica as a metal oxide (claim 4).

According to a preferred embodiment of the method for producing a metal oxide of the present invention, p-aminophenyl-4,6-benzylidene-α-D-galactopyranoside; p-aminophenyl-4,6 is used as glycopyranoside. -Benzylidene-
By using β-D-galactopyranoside; or p-aminophenyl-4,6-benzylidene-β-D-mannopyranoside, hollow and spherical silica can be obtained (Claim 5). In another preferred embodiment, the glycopyranoside is p-aminophenyl-4,6-
By using benzylidene-β-D-glucopyranoside, it is possible to obtain lotus root silica having a plurality of cylindrical holes extending therein (claim 6). Further, p-aminophenyl-4,6-benzylidene-α-D-glucopyranoside; or p-aminophenyl-4,6-benzylidene-α-D-galactopyranoside is used as the glycopyranoside, and cylindrical silica is used. (Claim 7).

According to another aspect of the present invention, an outside diameter of 300 mm as obtained by the above method (claim 5) is provided.
It provides silica having a hollow spherical shape with a thickness of -800 nm and a thickness of 20-150 nm (claim 8), and further has an outer diameter of 1 as obtained by the above method (claim 6).
Provided is silica having a lotus root shape in which a plurality of cylindrical holes having a diameter of 50 to 200 nm and an inner diameter of 5 to 10 nm extend therein (Claim 9).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each element constituting a metal oxide (inorganic structure) and an organic-inorganic composite as a raw material thereof according to the present invention, a production method (preparation method), and characteristics of those structures The features of the present invention will be described in detail along the line.

[0012]Gelling agent: sugar derivative  In the present invention, it is used as a gelling agent (gel forming agent).
Sugar derivatives are those in which the hydroxyl groups at the 4- and 6-positions of the monosaccharide are benzylic.
Amino-phenyl group or pyridyl at the 1-position
It is a glycopyranoside in which the group is a glycosidic bond. FIG.
Include glycopyra suitable for use in the present invention.
The chemical structure of the noside is shown. 1 is shown in FIG.
Glycopyranoside with an aminophenyl group attached at the position
There is a glycoside in which a pyridyl group is bonded to position 1 of a monosaccharide.
Lanosides can also be used as gelling agents
You. Generally, an aminophenyl group is a p-aminophenyl group
And the pyridyl group is bonded as a 4-pyridyl group
Is done.

The pyranoside having such a structure can gel various organic solvents such as water and alcohol and, according to the present invention, use the gel as a template to form a sol-gel of a metal oxide (a precursor of a metal oxide). The reaction can proceed to produce a metal oxide. This is because, in the present invention, a hydrogen bond is formed between a nitrogen atom of an aminophenyl group or a pyridyl group of glycopyranoside and a precursor of a metal oxide, and the precursor is adsorbed on a gel and polymerization proceeds. To be understood.

Here, the feature of the present invention is to change the type of monosaccharide constituting glycopyranoside used as a gelling agent (to convert the same saccharide to α- or β-isomer, as described later). ) Changes the shape of the organic-inorganic composite, and thus the inorganic structure (metal oxide) obtained by removing glycopyranoside from the composite. This depends on the difference in the bond angle between the sugar skeleton of the monosaccharide and the phenyl group bonded to the 4- and 6-positions by benzylidene and / or the aminophenyl group or the pyridyl group bonded to the 1-position. It is considered that a gel having various three-dimensional structures is formed, and an organic-inorganic composite and a metal oxide (inorganic structure) are formed using the gel as a template.

The glycopyranoside used in the present invention can be easily synthesized by devising a known reaction. FIG. 2 shows that p-aminophenyl-4,6-
The pyranoside used in the present invention is synthesized by using benzylidene-α-D-glucopyranoside (A in FIG. 2) and p-aminophenyl-4,6-benzylidene-β-D-mannopyranoside (B in FIG. 2) as examples. 1 shows a reaction scheme. Briefly, by reacting benzaldehyde with a monosaccharide nitrophenyl compound (commercially available reagent) at room temperature in the presence of a suitable Lewis acid catalyst (eg, zinc chloride), the 4- and 6-positions of the monosaccharide are benzylidene. To give nitrophenyl-4,6-benzylideneglycopyranoside.
However, when the monosaccharide constituting the pyranoside is mannose, benzylideneation can occur not only at the 4- and 6-positions but also at the 2- and 3-positions. Therefore, dimethoxytoluene is used with a catalyst such as pyridinium salt of toluenesulfonic acid. And react at slightly elevated temperature (FIG. 2B). By subjecting the obtained nitrophenylated glycopyranoside to catalytic reduction using a reducing catalyst such as Pd-C, the target aminophenyl-4,
6-benzylidene glycopyranoside is obtained.

[0016]Manufacturing method (preparation method)  According to the present invention, an organic-inorganic composite and a metal oxide (
First, the sugar derivative as described above is produced.
(Glycopyranoside) and sol-gel reaction solution
Thus, a uniform mixture containing them is prepared.

The sol-gel reaction solution includes at least a precursor of a metal oxide (inorganic material) (a starting material of the metal oxide: metal alkoxide, metal chloride) so that an initial sol in which the sol-gel reaction proceeds is formed. , A metal diketonate, etc .: described below), a catalyst (acid, alkali, amine, etc.) for generating a metal oxide by a sol-gel reaction from a precursor of the metal oxide, and water (hydrolysis of a metal oxide precursor) Required in small quantities). However, if this alone is not sufficient for the solubility of the sol-gel reaction system or a gel is not formed in water, an organic solvent that dissolves the glycopyranoside and the sol-gel reaction solution and generates a gel is added.

In the method of the present invention, a glycopyranoside gel is formed in the mixture thus obtained. Here, the term gel used in connection with the present invention generally refers to a state in which the solvent is completely bound and solidified. It also includes a state where they are bonded to each other and aggregated. This gel formation step is performed by heating the above-mentioned homogeneous mixed solution and then cooling it to room temperature to form a gel. When the gel formation temperature is lower than room temperature, the glycopyranoside and the sol-gel reaction solution are mixed at room temperature, and the system is cooled to form a gel. During this step, a gel of glycopyranoside is generally formed first, and the sol-gel reaction of the metal oxide partially proceeds.

In the present invention, the polymerization of the metal oxide is further advanced while maintaining the system in which the gel has been formed as described above under such a condition that the gel is not broken. That is, a system in which gel formation occurs at room temperature is maintained at room temperature, and a system in which gel is formed by cooling is maintained at the cooling temperature for an appropriate time (generally, several days or more).
Hydrolysis and polycondensation proceed by the sol-gel reaction of the metal oxide, and the degree of polymerization of the metal oxide increases, and the metal oxide which cannot be dissolved in the solution adheres and precipitates on the glycopyranoside gel surface.

Next, this is dried under appropriate conditions, the excess solvent is removed, and the glycopyranoside having a gel structure is left to obtain an organic-inorganic complex. Further, if the glycopyranoside is removed, a metal oxide (inorganic structure) is obtained. Becomes The removal of glycopyranoside can be carried out by elution using a solvent, but it is generally preferable to carry out calcination.

[0021]Metal oxide (inorganic structure)  Organic-inorganic composite and metal oxide according to the present invention
Metal oxides (inorganic materials) used to prepare
As precursors of glycopyranosi as described above
Adheres via hydrogen bonds in the gel consisting of
Sol-gel reaction proceeds on the surface to produce the desired metal oxide
There is no particular limitation as long as it can be performed.

For example, in addition to silica, alumina and borate, alkoxides and chlorides of transition metals such as titania, zirconia and hematite, diketone and the like can be mentioned. Specifically, silica is tetraethoxysilane, methyltriethoxysilane, tetrachlorosilane, alumina is aluminum tri-sec-butoxide, aluminum (III) 2,4-pentanedionate, borate is trimethoxyborane, and titania is titanium ethoxide. For zirconia, zirconium tetra-n-butoxide or the like is used.

[0023]Shape of metal oxide  As described above, according to the present invention, the glycoside serving as a gelling agent
By changing the type of sugar that makes up the pyranoside,
The shape of the metal oxide (inorganic structure)
it can. For example, α-galactose, β-galactose
Or glycopyranoside based on α-mannose
When using, the outer diameter is 300-800 nm and the thickness is
A hollow spherical silica with a diameter of 20-150 nm is obtained.
You. Such a nano-sized hollow spherical silicon
The mosquito structure has not been obtained before.

When glycopyranoside consisting of β-glucose is used as a gelling agent, the outer diameter is 150 μm.
A lotus root-shaped metal oxide (silica structure) having -200 nm and a plurality of cylindrical holes (microtubes) having an inner diameter of 5 to 10 nm is obtained.

Further, when a glycopyranoside based on α-glucose is used, a cylindrical (outer diameter of 20-
A silica structure (30 nm, inner diameter 5-10 nm) is obtained. Interestingly, when α-galactopyranoside is used as a gelling agent, a hollow spherical silica structure is generally obtained as described above, but when ethanol is added in addition to water as a solvent, As a result, a cylindrical silica structure (outer diameter of about 1400 nm) is obtained.

Thus, the metal oxide (inorganic structure) obtained by the present invention, in particular, a cylindrical or lotus root-like silica structure can be obtained by utilizing the width of a surface having an inner surface and an outer surface.
It is expected to be applied as a catalyst, a support for the catalyst, an adsorbent, a separating agent, and the like, and further, as an ion conductor by enclosing metal fine particles therein. Further, the metal oxide (inorganic structure) obtained by the present invention
Among them, in particular, nano-scale hollow spherical silica is applied as a functional thin film such as a super water repellent film or an anti-reflective film by controlling the fractal structure (concavo-convex structure) by being supported on an appropriate thin film. It can be expanded.

The organic-inorganic structure produced according to the present invention and used as a raw material of the metal oxide (inorganic structure) is also changed to the above-described metal oxide (inorganic structure) depending on the glycopyranoside used as the gelling agent. It will be apparent that it has a corresponding variety of shapes. These organic-inorganic composites are useful as precursors for the above-described metal oxides (inorganic structures), but themselves are expected to have various uses. For example, an organic-inorganic composite is formed after an organic functional molecule is previously included in a gel. Accordingly, application to, for example, a battery material by forming a complex with a gel electrolyte solution and a nonlinear optical material by forming a complex with a gel containing a dye molecule is expected. Further, application development as an inclusion material such as a catalyst, a bactericide, and an aromatic using the inclusion effect of the cylindrical and spherical structures is possible.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The characteristics of the present invention will be described below.
Examples will be described below, but the present invention is not limited to these examples.
Not. In the chemical structural formula shown in the drawings,
Carbon and hydrogen atoms have been omitted according to conventional notation.
Sometimes.Example 1: Synthesis of glycopyranoside (gelling agent)  Compound 1a (p-aminophenyl-4,6-benzylide
-Α-D-glucopyranoside): shown in FIG.
Compound 1a is synthesized as follows according to the reaction scheme
did. p-Nitrophenyl-α-D-glucopyranoside
(1.0 g, 3.32 mmol) and benzaldehyde (4.0 ml, 39.6
mmol) and zinc chloride (0.96 mg, 7.08 mmol) in the presence of a catalyst.
At room temperature under a nitrogen atmosphere. 20 hours later, reaction
The solution was added in 50 ml of water. Decant the aqueous solution
The remaining oil was crystallized by adding 50 ml of petroleum ether.
Was. The obtained crystals were collected by filtration. Recrystallize with methanol
Was. This p-nitrophenyl-4,6-benzylidene
-Α-D-glucopyranoside in methanol (50 ml) and T
Dissolve in a mixed solvent of HF (10ml) and use Pd-C catalyst
Then, catalytic reduction with hydrogen was performed. Pd-C by filtration
After removing the catalyst and evaporating the solvent under reduced pressure, the silica column
The compound was purified by chromatography. Yield 25%:
mp 216.7-217.0 ° C;¹1 H NMR (300 MHz, DMS
O-d6) δ = 3.66-4.11 (m, 6H), 4.74 (d, J = 6.7 Hz,
 2H), 5.21-5.24 (m, 3H), 5.30 (d, J = 5.2 Hz, 1H), 5.6
0 (s, 1H), 6.51 (d, J = 8.8 Hz, 2H), 6.79 (d, J = 8.8 Hz,
 2H), 7.36-7.47 (m, 5H); IR (KBr) 3312 cm^-1,
 2909, 1647, 1510, 1456, 1396, 1363, 1217,1089, 10
45, 999, 806, 763. The other compounds 1b, 2a and 2b are prepared in the same manner.
Was synthesized. For those, only the analysis data is shown.
You.

Compound 1b (p-aminophenyl-4,6
Synthesis of -benzylidene-β-D-glucopyranoside):
Yield 31%: mp 245.6-246.0 ° C; ¹ H NMR (300 MH
z, DMSO-d6) δ = 3.26-3.54 (m, 4H), 3.70 (t,
J = 3.7 Hz, 1H), 4.17-4.22 (m, 1H), 4.71 (s, 2H), 4.82
(d, J = 4.7 Hz, 1H), 5.39 (d, J = 4.8 Hz, 1H), 5.52 (d,
J = 5.3 Hz, 1H), 6.49 (d, J = 8.6 Hz, 2H), 6.76 (d, J = 8.6
Hz, 2H), 7.36-7.45 (m, 5H); IR (KBr) 3368 cm
⁻¹ , 3298, 2870, 1624, 1510, 1383, 1228, 1086, 101
3, 920,826, 771.

Compound 2a (p-aminophenyl-4,6
Synthesis of -benzylidene-α-D-galactopyranoside): 39% yield: mp 224.0-224.6 ° C .; ¹ H NMR (300
MHz, DMSO-d6) δ = 3.78-4.68 (m, 6H), 4.71
(s, 2H), 4.87 (t, J = 6.0 Hz, 1H), 4.92 (t, J = 6.7 Hz, 1
H), 5.28 (t, J = 3.4 Hz, 1H), 5.56 (s, 1H), 6.50 (d, J =
8.8 Hz, 2H), 6.79 (t, J = 8.8 Hz, 2H), 7.36-7.48 (m, 5
H); IR (KBr) 3310 cm ⁻¹ , 2909, 1635, 1509, 14
56, 1368, 1217, 1089, 1047, 999, 806.

Compound 2b (p-aminophenyl-4,6
-Benzylidene-β-D-galactopyranoside): 76% yield: mp 206.1-206.9 ° C .; ¹ H NMR (300
MHz, DMSO-d6) δ = 3.56-3.64 (m, 3H), 4.04
-4.11 (m, 3H), 4.72 (d, J = 7.2 Hz, 1H), 4.95 (s, 2H),
5.00 (s, 1H), 5.21 (s, 1H), 5.57 (s, 1H), 6.52 (d, J =
8.7 Hz, 2H), 6.80 (d, J = 8.7 Hz, 2H), 7.36-7.48 (m, 5
H); IR3440 cm ⁻¹ , 2934, 1610, 1593, 1516, 1495,
1344, 1246, 1095, 997, 920, 850, 752.

Compound 3a (p-aminophenyl-4,6
Synthesis of -benzylidene-α-D-mannopyranoside):
According to the reaction scheme shown in FIG. 2B, compound 3a was synthesized as follows. p-Nitrophenyl-α-D-mannopyranoside (500 mg, 1.66 mmol) was added to anhydrous DMF (10 ml).
And pyridinium p-toluenesulfonate (32 mg, 0.13 mmol) and α, α-dimethoxytoluene (303 mg, 1.49 mmol) were added and reacted at 80 ° C. under a nitrogen atmosphere. Two hours later, the solvent was removed by distillation under reduced pressure, and the compound was obtained by silica column chromatography. This p-nitrophenyl-4,6-benzylidene-
α-D-Mannopyranoside was dissolved in methanol (50 ml), and catalytic reduction with hydrogen was performed using a Pd-C catalyst. After the Pd-C catalyst was removed by filtration and the solvent was distilled off under reduced pressure, the compound was purified by silica column chromatography. Yield 58%: mp 198.9-199.4 ° C; ¹ H NM
R (300 MHz, DMSO-d6) δ = 3.69-4.10 (m, &
H), 4.78 (s, 2H), 5.12 (d, J = 5.2 Hz, 1H), 5.21 (s, 1H
H), 5.32 (d, J = 4.0 Hz, 1H), 5.63 (s, 1H), 6.52 (d, J =
8.6 Hz, 2H), 6.72 (d, J = 8.6 Hz, 2H), 7.37-7.47 (m, 5
H); IR (KBr) 3395 cm ⁻¹ , 3314, 2912, 1626, 151
0, 1375, 1226, 1097, 1035, 926, 831, 749.

[0033]Example 2: Gelation experiment  Pyranosides 1a, 1b, 2a, 2 synthesized in Example 1
Gels for various organic solvents using b and 3a as gelling agents
The chemistry was examined. The gelation experiment was performed as follows. Gelation
The concentration of the agent was 3.0 (wt / v)%. That is, the gelling agent
(0.3mg) and solvent (0.1ml) into a screw sample bottle
The mixture was heated and dissolved until the solid content was dissolved. Got
Cool the solution to room temperature and leave for 1 hour to observe gel formation.
I thought. Table 1 shows the results. Exists as a gel
In this case, it is described as “G”. If the solution remains
"S", "R" when precipitates appear, and "R" when insoluble
Indicated as "I".

[0034]

[Table 1]

[0035]Example 3: Organic-inorganic composite and metal oxidation
Preparation of goods  Glucopyranosides 1a, 1b, 2 synthesized in Example 1
a, 2b, 3a each 5.0 × 10⁻⁶~ 5.0 × 10⁻⁵mol following
The composition was dissolved in a sol-gel reaction solution. ： Water (5-1
0mg) / TEOS (tetraethoxysilane) (8-20mg)
/ Benzylamine (5-10 mg). In addition, the gelling agent
The following solution was used when no gel was formed. : Eta
Knol (8 mg) / TEOS (tetraethoxysilane) (8
-20mg) / water (5-10mg) / benzylamine (5-10m
g). The resulting mixture is sealed in a glass tube and heated (80
After cooling to room temperature, gel formation was confirmed.
After that, it is left at room temperature for 7 to 10 days,
The response progressed. Next, the reaction solution is filtered to remove the polymer.
And then under nitrogen at 200 ° C for 2 hours and at 500 ° C
Heat at 500 ° C for 4 hours under air stream for 2 hours
And a metal oxide (silica) was obtained.

FIGS. 3 to 5 show SEM (scanning electron microscope) and TEM (transmission electron microscope) photographs of the obtained silica.
Shown in The silica structure obtained from compounds 1a and 1b showed a cylindrical structure. The outer diameter of the silica obtained using the compound 1a was 20 to 30 nm from the SEM photograph, and the length was 350 to 700 nm. From the TEM photograph, the inner diameter of the tube was 5-10 nm (FIG. 3). The outer diameter of the silica obtained using compound 1b was 150-200 nm, and the inner diameter of the tube was 50-100 nm. In addition, the inner tube consisted of a bundle of 5-10 nm microtubes (FIG. 4).

In the case of compound 2a, different silica structures were obtained depending on the solvent used in the gelation and sol-gel polymerization processes. The silica structure obtained from the system using ethanol had a cylindrical shape with a diameter of about 1400 nm. On the other hand, the silica structure obtained in an aqueous system is hollow and spherical,
Its outer diameter was 300-700 nm and its thickness was 20-100 nm.
The silica obtained using 3a, which is a gelling agent derived from mannose, has a hollow spherical shape, an outer diameter of 400-800 nm, and an inner diameter of 400-800 nm.
The structure was 150-650 nm (FIG. 5). When 2b was used as the gelling agent, hollow and spherical silica was obtained.

[Brief description of the drawings]

FIG. 1 shows a chemical structural formula of a sugar derivative (glycopyranoside) used as a gelling agent in the present invention.

FIG. 2 shows a reaction scheme for synthesizing glycopyranoside used as a gelling agent in the present invention.

FIG. 3 is a scanning electron micrograph (a) and a transmission electron micrograph (b) showing the crystal structure of a metal oxide (silica) obtained using the glycopyranoside of 1a in FIG. 1 as a gelling agent.

FIGS. 4A and 4B are a scanning electron micrograph (a) and a transmission electron micrograph (b) showing the crystal structure of a metal oxide (silica) obtained by using the glycopyranoside of 1b in FIG. 1 as a gelling agent.

5 is a scanning electron micrograph (a) and a transmission electron micrograph (b) showing the crystal structure of a metal oxide (silica) obtained using the glycopyranoside of 3a in FIG. 1 as a gelling agent.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C01G 1/02 C01G 1/02 C07H 15/203 C07H 15/203 17/02 17/02 17/02 (72) Inventor Jin Jinhe, Fukuoka Pref., Japan AA25 BB07 BB16 HH17 HH30 JJ42 LL06 MM01

Claims (9)

[Claims] (1) a. Glycopyranosides in which the hydroxyl groups at the 4- and 6-positions of the monosaccharide are benzylidene and the aminophenyl or pyridyl group is glycosylated at the 1-position; b. A sol-gel reaction solution comprising a metal oxide precursor, a catalyst for producing a metal oxide polymer by a sol-gel reaction from the metal oxide precursor and water, and c. If necessary, a step of preparing a homogeneous mixed solution containing an organic solvent capable of dissolving the glycopyranoside and the sol-gel reaction solution; (2) a. After heating the homogeneous mixture, cool or
Or b. Cooling the homogeneous mixture to form a gel of glycopyranoside; and (3) maintaining the gel-formed system and promoting polymerization of the metal oxide. And a method for producing an organic-inorganic composite in which a metal oxide is attached to the surface of glycopyranoside. 2. A method for producing a metal oxide, comprising removing glycopyranoside from the organic-inorganic composite obtained by the method according to claim 1. 3. The method for producing a metal oxide according to claim 2, wherein glycopyranoside is removed by calcination. 4. The method for producing a metal oxide according to claim 2, wherein the metal oxide is silica. 5. Glycopyranoside includes p-aminophenyl-4,6-benzylidene-α-D-galactopyranoside; p-aminophenyl-4,6-benzylidene-
5. The process for producing a metal oxide according to claim 4, wherein hollow spherical silica is obtained using β-D-galactopyranoside; or p-aminophenyl-4,6-benzylidene-β-D-mannopyranoside. Method. 6. Use of p-aminophenyl-4,6-benzylidene-β-D-glucopyranoside as glycopyranoside to obtain a lotus root-like silica having a plurality of cylindrical holes extending therein. A method for producing the metal oxide according to claim 4. 7. A method for forming a glycopyranoside using p-aminophenyl-4,6-benzylidene-α-D-glucopyranoside; or p-aminophenyl-4,6-benzylidene-α-D-galactopyranoside in a cylindrical form. The method for producing a metal oxide according to claim 4, wherein silica is obtained. 8. Silica having an outer diameter of 300 to 800 nm and a hollow spherical shape having a thickness of 20 to 150 nm. 9. A silica having a root shape in which a plurality of cylindrical holes having an outer diameter of 150 to 200 nm and an inner diameter of 5 to 10 nm extend therein.