JPH07225225A - Adsorption carrier for chromatography - Google Patents

Abstract

PURPOSE:To provide an adsorption carrier for chromatography which is excellent in uneven discrimination capability, representation and durability with easy manufacture. CONSTITUTION:Cyclodextrin inductor prepared by combining the oxygen of hydroxyl group of cyclodextrin to hydrocarbon radical containing carboxyl group, directly or through carbonyl group, is fixed to an insoluble base material. This chemically modified cyclodextrin fixing absorption carrier has higher uneven discrimination capability than non-modified cyclodextrin fixing ababsorption carrier, and useful for an adsorption carrier for chromatography.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel adsorption carrier for chromatography, and more particularly to an adsorption carrier for chromatography having an asymmetric discrimination ability.

[0002]

2. Description of the Related Art Cyclodextrin (hereinafter referred to as "CD") is a cylindrical cyclic compound in which D-glucopyranoside is bonded to α-1,4-glucoside, and the outside of the cylinder of the cyclic compound has many hydroxyl groups. It is hydrophilic, but the inside of the cylinder is hydrophobic. Since the inside of the cylinder is hydrophobic, this CD is known as a host compound in which various organic compounds having a hydrophobic group such as a phenyl group and a naphthyl group are included. Also, CD is D-glucopyranoside 1
Since it has 5 optically active carbons per molecule, it is also known as a compound having an asymmetric discrimination ability.

In recent years, the importance of separation and purification of optically active compounds has increased, and there has been an increasing tendency to utilize the asymmetric discrimination ability of CD for this purpose. For example, US Pat.
According to JP-A-9,399, there is known a method for separating and purifying an optically active compound by using an adsorption carrier obtained by immobilizing CD on silica gel having an epoxy group or a vinyl group as an adsorption carrier for chromatography. Has been. Further, JP-A-2-228558 discloses a method using an adsorption carrier obtained by immobilizing CD on a synthetic polymer having a carbonylimidazole group, and JP-A-4-23.
No. 0852 discloses a method using an adsorption carrier obtained by immobilizing CD activated with chlorocarbonic acid ester on silica gel having an amino group.

However, in these methods, the immobilization amount of CD is low and thus the separation ability is insufficient. Further, silica gel is used as the support, or the CD and the support are immobilized by a carbonate bond or a carbamate bond. Because there are
It cannot be used under alkaline conditions, and there is a problem that separation conditions and elution / washing conditions are greatly restricted.
In order to solve these problems, JP-A-4-106101
JP-A-4-25503 and JP-A-4-25503 disclose that CD or a derivative thereof is reacted with a bifunctional cross-linking agent, or a vinyl group or an acryl group is introduced into CD to form a monomer, which is then polymerized. An adsorption carrier having a high CD immobilization amount is obtained. However, the adsorption carrier obtained by these methods has problems that the fluidity is poor and the durability is poor because of low mechanical strength, the production is complicated and impractical, and that CD is produced by polymerization. Since its ability to discriminate asymmetry is decreased, it could not be used as an adsorption carrier for chromatography.

On the other hand, for the purpose of further improving the asymmetric discrimination ability of CD, in JP-A-64-53152, a chemically modified CD in which an amino acid is introduced into CD is immobilized on a support. A method using an adsorption carrier is exemplified. However, this method is not practical because the immobilization amount is low and the asymmetric discrimination ability is not greatly improved, so that the separation ability is insufficient and it is complicated to obtain a CD-modified product. Also, Analytical Chemistry (Ana. Chem.), 1990, [62], p.
In 1610, the hydroxyl group of CD is -O-CO-NH-P.
An example is a method using an adsorption carrier in which chemically modified CD substituted with one represented by a structural formula such as h or —O—CO—CH ₃ is immobilized on silica gel. However, in this method, although it is easier to obtain an adsorption carrier than the former, the separation ability is insufficient for the same reason as in the former, and moreover,
Since silica gel is used as the support, the problem that it cannot be used under alkaline conditions remains.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an adsorption carrier for chromatography which is excellent in asymmetric discrimination ability, simple in production of the adsorption carrier, and excellent in reproducibility and durability.

[0007]

The present invention has been made in order to achieve the above object, and a hydrocarbon group having a carboxyl group is bonded to oxygen of a hydroxyl group of CD directly or via a carbonyl group. The CD derivative (hereinafter, abbreviated as “CD derivative having a carboxyl group”),
The present invention relates to an adsorption carrier for chromatography, which is immobilized on a water-insoluble support. Hereinafter, the adsorption carrier for chromatography of the present invention will be described in detail.

The CD used in the present invention includes:
For example, a hydroxyl group such as α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, or their α-, β-, γ-, δ-cyclodextrin hydroxyalkylated products and glycosylated products. In addition to those modified with a substituent having
Even a methylated cyclodextrin or an acylated cyclodextrin may be a CD having at least one hydroxyl group, and may be a mixture thereof or a polymer thereof. Since these CDs have different asymmetric discrimination ability depending on the type of optical isomers to be separated, it is preferable to appropriately select and use them, for example, β-cyclohexyl for separation of phenylpropionic acid anti-inflammatory drugs such as ibuprofen It is preferable to use α-cyclodextrin for separating aromatic amino acids such as dextrin and phenylalanine.

To obtain these CDs, known methods (Tetra-hedron, 1
983, [39], p. 1417) or commercially available α-, β-, or γ-cyclodextrin (manufactured by Mercian), hydroxyethyl-β-cyclodextrin (manufactured by Aldrich), and the like. Specifically, for example, when obtaining hydroxypropyl-β-cyclodextrin, it can be obtained by heating β-cyclodextrin and chloropropyl alcohol in the presence of alkali. Further, when obtaining methyl-β-cyclodextrin, it is obtained by heating β-cyclodextrin and sodium hydride in dimethyl sulfoxide and further reacting with methyl iodide.

Further, the CD derivative having a carboxyl group used in the present invention is one in which a hydrocarbon group having a carboxyl group as a substituent is bonded to oxygen of a hydroxyl group of CD directly or through a carbonyl group. The hydrocarbon group having a carboxyl group is represented by -R-COOH (R represents a linear or branched saturated or unsaturated, alicyclic or aromatic divalent hydrocarbon group).
For example, _{R, -CH 2 -, - CH 2} CH 2 -, - CH
_{2 CH 2 CH 2 -, -} CH 2 CH (CH 3) -, - (C
_{H 2) 4 -, - CH} 2 CH (CH 2 CH 3) -, - (C
H ₂ ) ₅ −, − (CH ₂ ) ₆ −, CH ₂ CH ₂ CH (C
_{H 2 CH 3) CH 2 -} , - (CH 2) 8 -, - CH (C
_{H 3) - (CH 2)} 6 -, - (CH 2) 10 -, - (CH
₂ ) ₁₁ −, − (CH ₂ ) ₁₂ −, − (CH ₂ ) ₁₄ −, −
_{(CH 2) 16 -, -} (CH 2) 14 CH (CH 3) -, -
_{(CH 2) 17 -, -} (CH 2) 18 -, - (CH 2)
_{19 -, - CH (CH 2} CH 2 CH 3) -CH 2 -CH
_{(CH 3) - (CH 2} ) 3 -, - CH = CH -, - CH
_{2 CH = CH -, - CH} = CH-CH 2 -, CH = CH
-CH = CH -, - (CH 2) 4 CH = CH-, CH 2
CH = C (CH ₃₎ - include divalent hydrocarbon radical of a linear or branched, saturated or unsaturated 1 to 19 carbon atoms such as, -CH ₂ -cycC ₆ H ₁₀ -1,2- yl , -CH
_{2 -cycC 6} H ₁₀ -1,3- yl, -CH ₂ -Cyc
C ₆ H _10-1,4-yl, -CH ₂ CH ₂ -cycC ₆
H _{10-1,2-yl, -CH 2 CH 2 -cycC 6 H} 10
_{1,3-yl, -CH 2 CH 2 -cycC 6 H} 10 -
1,4-yl, -CH ₂ -cycC ₇ H ₁₂ -1,3- yl, CH ₂ cycC ₇ H ₁₂ -1,4- yl, -CH ₂ -
Phenylene-1,2-yl, -CH ₂ - phenylene -
1,3-yl, -CH ₂ - phenylene-1,4-yl,
Examples thereof include alicyclic or aromatic divalent hydrocarbon groups having 6 to 19 carbon atoms such as phenylene-1,2-yl, phenylene-1,3-yl, and phenylene-1,4-yl.

Suitable examples of the CD derivative having a carboxyl group used in the present invention include compounds in which the hydrogen of the CD derivative is substituted with the following groups. _{-CH 2 COOH, - (CH 2} ) 2 COOH, - (CH
₂ ) ₃ COOH,-(CH ₂ ) ₄ COOH,-(CH
_{2) 5 COOH, -CH (CH} 3) COOH, -C
_{(O) CH 2 COOH, -C} (O) - (CH 2) 2 -C
OOH, -C (O) - ( CH 2) 3 -COOH, -C
_{(O) - (CH 2)} 4 -COOH, -C (O) - (CH
_{2) 5 -COOH, -C (O} ) -CH (CH 3) COO
H, -C (O) -CH = CH-COOH,

[Chemical 1]

For obtaining these, a known method (Starch, 1971, [23], P. 1).
67)) and the like. In particular,
For example, when obtaining carboxymethyl-β-cyclodextrin, it is obtained by heating β-cyclodextrin and chloroacetic acid in the presence of alkali. Further, when carboxypropionyl-β-cyclodextrin is obtained, it is obtained by reacting β-cyclodextrin with succinic anhydride or succinic acid chloride in a dimethylsulfoxide-pyridine mixed solution.

The amount of the carboxyl group per one CD molecule of the CD derivative having these carboxyl groups (hereinafter,
It is called "substitution degree". Is different depending on the type of optical isomer to be separated, but is not particularly limited as long as it is 1 or more, and the CD derivative having a carboxyl group used is a mixture of CDs having different degrees of substitution. (Average of substitution degree of mixture is called average substitution degree). The substitution degree or average substitution degree of these CD derivatives having a carboxyl group can be adjusted by changing the amount of carboxylic acid in the above reaction. For example, with respect to the carboxymethyl-β-cyclodextrin, 18 mol of chloroacetic acid per 1 mol of CD is reacted to obtain carboxymethyl-β-cyclodextrin having an average substitution degree of 6 to 10, and 7 mol of chloroacetic acid per 1 mol of CD. Reaction of the moles yields carboxymethyl-β-cyclodextrin with an average degree of substitution of 2-6.

The water-insoluble support in the present invention means
There is no particular limitation as long as it has a functional group capable of binding to a carboxyl group, or one that can be introduced, agarose, dextran, polysaccharides such as cellulose and so-called soft beads such as polyacrylamide, polystyrene, polymethacrylate, polyvinyl. Hard synthetic polymer beads such as alcohol and copolymers thereof, or inorganic hard beads such as alumina and titania, which have alkali resistance, are desirable. Also, if an adsorption carrier is not used under alkaline conditions, an alkali-unstable support such as silica gel can be used. The particle size and shape of the beads, the presence or absence of pores, and the pore size are not particularly limited, but usually 1 to 3000 μm, preferably 2 to 300 μm are suitable, and the shape of the beads is preferably porous spherical. These supports are preferably selected and used according to the intended use of the carrier, for example, for use as an adsorption carrier for high performance liquid chromatography,
Hard synthetic polymer beads such as polymethacrylate and inorganic hard beads such as silica gel are preferable.

The above-mentioned functional groups of the water-insoluble support which can be bonded to the carboxyl group include amino group, epoxy group, hydroxyl group, carboxyl group,
Examples thereof include an alkynyl group and an alkenyl group, but a support having an amino group or an epoxy group capable of immobilizing a large amount of a CD derivative having a carboxyl group on the support is particularly preferable. The introduction of these functional groups into the support can be easily carried out by a known method in the presence of a suitable solvent. Specifically, for example, an epoxy-modified support having an epoxy group introduced therein includes epihalohydrins such as epichlorohydrin, diglycidyl ethers such as 1,4-butanediol diglycidyl ether, and 1,7-octadiene. It can be rapidly obtained by reacting a diepoxide such as ene diepoxide with a support having a hydroxyl group under alkaline conditions.

The obtained epoxy-modified support is prepared by using aminoalkanes such as ammonia, hydrazine or methylamine, diaminoalkanes such as 1,3-propanediamine and hexamethylenediamine, polyasparagine and polyglutamine. An amino-modified support having an amino group can be obtained by reacting such basic polyamino acids as described above with polyvinylamine and polyamines such as polyethyleneimine. The amino-modified support can be similarly obtained by using an epoxy group-containing copolymer composed of glycidyl methacrylate and a vinyl monomer copolymerizable therewith instead of the above epoxy-modified support. Further, the amino-modified support is made a carboxy-modified support by reacting with an acid anhydride such as succinic anhydride, or a maleic anhydride copolymer composed of maleic anhydride and a vinyl monomer copolymerizable therewith. You can also The above amino-modified support can also be obtained by reacting a diamine such as ethylenediamine with the present copolymer.

By immobilizing a CD derivative having a carboxyl group on a support having these functional groups, the adsorption carrier for chromatography of the present invention can be obtained.

When the CD derivative having a carboxyl group of the present invention is immobilized on a support, the functional group portion of the support is bonded to the carboxyl group portion of the CD derivative having a carboxyl group. The length between the support itself and the CD derivative having a carboxyl group is not particularly limited, but the number of atoms is 0 to 100, preferably the number of atoms is 0.
10 is desirable. The present invention is characterized in that a CD derivative in which a hydrocarbon group having a carboxyl group is bonded to oxygen of a hydroxyl group of CD directly or via a carbonyl group is immobilized on a water-insoluble support. Since it is an adsorption carrier for chromatography, the method for binding the CD derivative having a carboxyl group introduced thereto and the support is not particularly limited, but it is necessary depending on the functional group of the CD derivative having a carboxyl group and the support. In that case, it can be carried out in an appropriate solvent using an appropriate catalyst, a reaction agent or the like. For example, as a catalyst, an acid such as hydrochloric acid, sodium carbonate, or sodium hydrogencarbonate, or an alkali is mainly used, and for example, as a reactant, N-hydroxysuccinimide, dicyclohexylcarbodiimide,
A condensing agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide or N, N′-carbonyldiimidazole and a bisoxazoline compound such as 1,4-tetramethylenebisoxazoline are used. As the solvent, an organic solvent such as 1,4-dioxane, N, N-dimethylformamide, dimethylsulfoxide or pyridine, water or its phosphoric acid or carbonate buffer solution, etc. are used.

According to the present invention, it is possible to obtain an adsorption carrier for chromatography, which is characterized in that the CD derivative having a carboxyl group is immobilized on a water-insoluble support. The adsorption carrier for use can be used as a simple adsorption carrier for liquid chromatography as an adsorption carrier for high-performance liquid chromatography, and by packing it in a column, not only optical isomers but also various isomers including positional isomers and geometric isomers Can be separated.

[0020]

The present invention will be described in more detail with reference to examples. However, it goes without saying that these are examples of the adsorption carrier for chromatography of the present invention, and the present invention is not limited to these.

Example 1 Production of adsorption carrier immobilized with carboxymethyl-α-cyclodextrin (average degree of substitution = 7.0) Epoxy group in epoxy group-containing gel-like copolymer obtained from glycidyl methacrylate and glycerin dimethacrylate Is subjected to ring opening modification with 1,3-propanediamine,
Dry under vacuum for 5 hours. Thus, an amino-modified support having a group capable of binding to CD having a carboxyl group and its derivative (amino group; 4 per 1 g of dry support)
mmol) was prepared. α-cyclodextrin 10
g was dissolved in 110 ml of 13% aqueous sodium hydroxide solution, 28 g of 50% aqueous sodium chloroacetate solution was added, and the mixture was stirred at 80 ° C. for 1 hour, and the reaction solution was cooled with ice to 1N.
It was neutralized with hydrochloric acid. After 200 ml of acetone was added to this reaction solution, the resulting precipitate was collected by filtration, and the residue was washed with acetone to obtain 9.0 g of white solid carboxymethyl-α-cyclodextrin. The average degree of substitution of the compound thus obtained was confirmed to be 7.0 by 1H-NMR at 60 MHz.

10 g of carboxymethyl-α-cyclodextrin obtained by the above method was dissolved in 240 ml of 0.05M sodium chloride aqueous solution, and 10 g of the amino-modified support obtained by the above-mentioned method was added and stirred well. did. 1-Ethyl 3- (3
After adding 16 g of -dimethylaminopropyl) carbodiimide and stirring at room temperature for 12 hours, the adsorption carrier was collected by filtration and washed with water and acetone in this order. From the increase in weight before and after the reaction, it was confirmed that 180 μmol of α-cyclodextrin was immobilized on 1 g of the dry adsorption carrier in the thus obtained adsorption carrier.

Example 2 Preparation of carboxymethyl-β-cyclodextrin (average degree of substitution = 3.6) immobilized adsorption carrier In the immobilization method of Example 1, carboxymethyl-α was used.
Instead of 10 g of cyclodextrin, commercially available carboxymethyl-β-cyclodextrin (average degree of substitution =
The same operation as in the immobilization method of Example 1 was performed except that 10 g of 3.6 g, manufactured by CYCLOLAB) was used. The weight of the adsorption carrier thus obtained before and after the reaction was 150 μmol of β-cyclodextrin per 1 g of the dry adsorption carrier.
It was confirmed that it was fixed.

Example 3 Production of adsorption carrier immobilized with carboxymethyl-β-cyclodextrin (average degree of substitution = 10.0) 20 g of β-cyclodextrin was dissolved in 280 ml of 10% sodium hydroxide aqueous solution, and 50% chloroacetic acid was further added. After adding 60 g of an aqueous sodium solution and stirring at 80 ° C. for 1 hour, the reaction solution was neutralized with 1N hydrochloric acid while cooling with ice. After adding 1800 ml of methanol to this reaction liquid, the generated precipitate was collected by filtration and washed with methanol. Further, this precipitate was recrystallized from water-methanol to obtain 11.0 g of carboxymethyl-β-cyclodextrin as a white solid.
The average degree of substitution of the compound thus obtained was confirmed to be 10.0 by 1H-NMR at 60 MHz.
In the immobilization method of Example 1, carboxymethyl-α
-The same operation as in the immobilization method of Example 1 was performed except that 10 g of carboxymethyl-β-cyclodextrin (average degree of substitution = 10.0) obtained by the above method was used instead of 10 g of cyclodextrin. It was The weight of the adsorption carrier thus obtained before and after the reaction was 130 μmol of β-cyclodextrin per 1 g of the dry adsorption carrier.
It was confirmed that it was fixed.

Example 4 Carboxymethyl- (hydroxypropyl-β-cyclodextrin) (average degree of substitution =
10.0) Production of immobilized adsorption carrier In the carboxymethylation method of Example 1, instead of 10 g of α-cyclodextrin, commercially available hydroxypropyl-β-cyclodextrin (average substitution degree = 1.6,
The same operation as in the carboxymethylation method of Example 1 was performed except that 8 g of Aldrich) was used. The average degree of substitution of the compound thus obtained was confirmed to be 10.0 by 1H-NMR at 60 MHz. In the immobilization method of Example 1, 10 g of carboxymethyl- (hydroxypropyl-β-cyclodextrin) (average degree of substitution = 10.0) obtained by the above method instead of 10 g of carboxymethyl-α-cyclodextrin. The same operation as in the immobilization method of Example 1 was performed except that was used. The adsorbent carrier thus obtained, from the weight increase before and after the reaction,
It was confirmed that 130 μmol of hydroxypropyl-β-cyclodextrin was immobilized per 1 g of the dry adsorption carrier.

Example 5 Carboxypropionyl-β-
Cyclodextrin (average degree of substitution = 6.3) Production of immobilized adsorption carrier In the immobilization method of Example 1, carboxymethyl-α was used.
-The same operation as in the immobilization method of Example 1 was performed except that 10 g of commercially available carboxypropionyl-β-cyclodextrin (average degree of substitution = 6.3, manufactured by CYCLOLAB) was used instead of 10 g of cyclodextrin. The adsorbent carrier thus obtained contained 150 μm of β-cyclodextrin per 1 g of the dry adsorbent carrier due to the weight increase before and after the reaction.
It was confirmed that ol was immobilized.

Example 6 Preparation of carboxymethyl- (β-cyclodextrin-epichlorohydrin copolymer) (average degree of substitution = 1.9) immobilized adsorption carrier In the immobilization method of Example 1, carboxymethyl-α was used.
Instead of 10 g of cyclodextrin, commercially available carboxymethyl- (β-cyclodextrin-epichlorohydrin copolymer) (average degree of substitution = 1.9, CYCLO
The same operation as in the immobilization method of Example 1 was performed except that 10 g of LAB) was used. From the weight increase before and after the reaction, it was confirmed that 200 μmol of β-cyclodextrin was immobilized on 1 g of the dry carrier in the thus obtained adsorption carrier.

Comparative Example Production of β-Cyclodextrin-Immobilized Adsorption Carrier The epoxy group in the epoxy group-containing gel-like copolymer obtained from glycidyl methacrylate and glycerin dimethacrylate was ring-opened modified with water, and then vacuum-treated for 5 hours. Dried. To 10 g of this support, 85 ml of 1,4-dioxane
Was further added, and 15 g of N, N′-carbonyldiimidazole was further added under a nitrogen atmosphere, and the mixture was stirred at 50 ° C. for 3 hours, and then the support was filtered and washed with 1,4-dioxane. The thus obtained N-carbonylimidazole-immobilized support (N
-Carbonylimidazole group; 1.8 mmol per 1 g of dry support), about 10 g of β-cyclodextrin and 150 ml of N, N-dimethylformamide were added, and the mixture was stirred at 60 ° C for 15 hours, and then the adsorption carrier was collected by filtration. And washed with alcohol. From the weight increase before and after the reaction, it was confirmed that 100 μmol of β-cyclodextrin was immobilized on 1 g of the dry adsorption carrier in the thus obtained adsorption carrier.

Application Example The adsorption carriers obtained in Examples 2, 3, 5, 6 and Comparative Example were each filled in a stainless steel chromatographic tube having an inner diameter of 4.6 mm and a length of 150 mm by a slurry method, and the high performance liquid chromatograph was applied. Methionine β-naphthylamide (Met-NA), dansyl valine (Dns-Va)
1) and 2-phenoxypropionic acid (2-PPA) were analyzed, and the results shown in Table 1 were obtained. In the table, k'represents a capacity ratio expressed by (retention capacity of first eluted component-column void volume) / (column void volume), and α is capacity ratio of second eluted component. Shows the separation factor obtained by dividing by. Further, with respect to the adsorption carrier obtained in Example 2, various carboxylic acids were analyzed by the same method as described above. The results are shown in Table 2. K ′ and α in the table are the same as those in Table 1.

The analytical conditions are as follows unless otherwise specified. Eluent: 2% acetic acid-triethylamine buffer (pH 4)
/ Acetonitrile (9/1) +0.1 M sodium chloride Flow rate; 0.2 ml / min Column temperature; 15 ° C. Detector; UV spectrophotometer Detection wavelength; 254 nm Furthermore, the adsorption carrier obtained in Example 2 was as described above. Methionine β-naphthylamide was analyzed in a similar manner under alkaline eluent. The chromatogram is shown in FIG. Except for the eluent, the analysis conditions are the same as described above. The eluent is shown below. Eluent; 2% acetic acid-triethylamine (pH 9.5) /
Acetonitrile (9/1) + 0.1M sodium chloride

[0031]

[Table 1]

[0032]

[Table 2]

From these results, the adsorption carrier for chromatography obtained according to the present invention has a higher chiral discrimination ability than the adsorption carrier for chromatography obtained by the conventional method, and the conventional adsorption carrier for chromatography. Separation in an alkaline eluent, which is not possible with the adsorbent carrier, was made possible.

[0034]

As is apparent from the application examples, the adsorption carrier for chromatography of the present invention allows a conventional CD to be reacted by immobilizing a CD derivative having a carboxyl group on a water-insoluble support. It has a higher asymmetric discrimination ability than the adsorption carrier for chromatography. Moreover, the durability and reproducibility are excellent, and the manufacturing method is easy. Further, the adsorption carrier for chromatography of the present invention may be any one having a support having an alkali resistance when it is intended for separation, elution and washing under alkaline conditions. Therefore, the adsorption carrier for chromatography according to the present invention has a possibility of separating various optical isomers, and is a powerful means for measuring application to a wide range of industrial separation / purification facilities in addition to simple analysis and preparative means. It is clear that

[Brief description of drawings]

1 is a chromatogram using the carrier of Example 2. FIG.

Claims (4)

[Claims] 1. The oxygen of the hydroxyl group of cyclodextrin,
An adsorption carrier for chromatography, characterized in that a cyclodextrin derivative in which a hydrocarbon group having a carboxyl group is bonded directly or via a carbonyl group is immobilized on a water-insoluble support. 2. The adsorption carrier for chromatography according to claim 1, which is immobilized on a support by using a carboxyl group as a substituent of a hydrocarbon group. 3. The adsorption carrier for chromatography according to claim 1, which is immobilized on a support by using a carboxyl group as a substituent of a hydrocarbon group, and the support has an amino group or an epoxy group. 4. The hydrocarbon group is a linear or branched saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms or an alicyclic or aromatic hydrocarbon group having 7 to 20 carbon atoms, and the hydrocarbon is The adsorption carrier for chromatography according to claim 1, which is immobilized on a support by using a carboxyl group as a substituent of the group, and the support has an amino group or an epoxy group.