Method for preparing immobilized β-cyclodextrin

FIELD: chemical technology.

SUBSTANCE: invention describes a method for preparing immobilized β-cyclodextrin. Method involves pretreatment of organic and inorganic sorbents - polyvinyl alcohol and sorbitol based on silica with glutaraldehyde for incorporation of aldehyde group molecules into sorbents, washing out with water and dimethylsulfoxide on glass porous filter, drying on glass porous filter followed by addition of prepared sorbents to dimethylsulfoxide solution containing dissolved β-cyclodextrin in the ratio sorbent : β-cyclodextrin : dimethylsulfoxide = 1.0:(0.4- 2.0);10, respectively, stirring the prepared suspension at temperature 25-70°C for 30-180 min, washing out and drying. Method provides preparing an insoluble sorbent with immobilized β-cyclodextrin used for removing cholesterol or its derivatives.

EFFECT: improved preparing method.

5 ex

 

The invention relates to food industry, in particular to the field of diet food.

To combat atherosclerosis world Health Organization recommends that proper nutrition and eating foods with low cholesterol content. Reducing the number entered in the body of cholesterol, it is possible to recover its normal content in the blood. One of the options for reducing the cholesterol is removed from the product. But it is important to keep other nutrients contained in the products.

Cyclodextrins - natural cyclic oligosaccharides - occupy an important place among the substances that can act as the owner of the complex type "host-guest". The use of CSD is not limited to only one sector of the food industry, covering such industries as pharmaceuticals and cosmetics, fine organic synthesis and petroleum, agricultural and processes protect the environment.

Cyclodextrins can form inclusion complexes with cholesterol [Nishijo J., Moriyama, S., Shiota, S., Chem. Pharm. Bull. (Tokio), 51, 1253-1257, 2003, Yong-Hoon Choi, Chul-Hak Yang, Hyun-Won Kirn, Seunho Jung, Journal of Inclusion Phenomena and Macrocyclic Chemistry, 39, 71-76, 2001]. Know the use of β-cyclodextrin (β-CD) removal of cholesterol from milk [D.K. Lee, J. Ahn, H.S. Kwak, J. Dairy Science, 82, 2327-2330, 1999, Aziz C. Award, Denise M. Smith (1995) US atent 5484624, 31 March], whipped cream [S.Y. Shim, J. Ahn, H.S. Kwak, J. Dairy Science, 86, 2767-2772, 2003], Cheddar cheese [H.S. Kwak, C.S. Jung, S.Y. Shim, J. Ahn, J.Agric. Food Chem., 50, 7293-7298, 2002], egg yolk [Kwak H.S., Ahn JJ, Lee DK (1998) US Patent 6110517, 29 July, Cully J, Vollbrecht HR (1992) US Patent 5292546, 4 March]. The most efficient use of β-cyclodextrin in insoluble forms, as it can be easily removed, regenerated and reused.

There are several sorbents with immobilized β-CD. This sorbent obtained by radical polymerization in water using 2-hydroxyethyl methacrylate [L. Janus, Crini G., El-Rezzi V., Morsellet M., Cambiaghi A., Tjrri G., Naggi, A., C. Vecchi, Reactive&Functional Polymers., 42, 173-180, 1999], sorbent, obtained by the reaction of monotoring derived β-CD with polyvinylidene [Seo T., T. Kajihara, T. Iijima, Macromol. Chem., 188, 2071-2075, 1987] or polyetheramines [Suh J., Lee S.H., Zoh K.D., J. Am. Chem. Soc., 114, 7916-7921, 1992]. The sorbent obtained inorganic base on glass beads (diameter 1 mm) under different conditions of silanization and immobilization β-CD. This has resulted in: glass beads (diameter 1 mm) with 20 mmol of 3-isocyanatopropyltrimethoxysilane and 30 mmol β-CD. The resulting sorbent was used for the removal of cholesterol from milk [H.S. Kwak, S.H. Kim, J.H. Kim, H.J. Choi, J. Kang, Arch. Pharm. Res., 27, 873-877, 2004]. The degree of removal of cholesterol was 40.2 per cent when mixing time of 6 hours. Removal of cholesterol from milk used so the e sorbent, obtained by polycondensation β-CD with epichlorohydrin [S.H. Kim, Ann J., H.S. Kwak, Arch. Pharm. Res., 27, 1183-1188, 2004].

From a number of patents, including patents US Patent 5484624 and RU Patent 2039469 known deletion derivatives of cholesterol from the yolk using β-cyclodextrin.

The disadvantage of these methods is the need to remove from egg yolk or plasma residual amount of β-cyclodextrin, which remains in the product after removal of cholesterol (patent RU 2053690, US Patent 5449771).

The objective of this invention to provide a new insoluble immobilized β-CD-based organic and inorganic sorbents through their aldehyde groups to avoid this stage in the process of removal of cholesterol and its derivatives. Aldehyde groups were introduced using glutaraldehyde.

This object is achieved in that a method of obtaining immobilized β-cyclodextrin provides preprocessing of organic and inorganic sorbents polyvinyl alcohol and sorbents based on silica - glutaraldehyde for introduction in their molecules of aldehyde groups, their washing water and dimethylsulfoxide (DMSO) on a glass Frit, drying on a glass Frit, the introduction of these sorbents in a solution of dimethyl sulfoxide containing RAS is voennyi it β -cyclodextrin at a ratio of sorbent : β-cyclodextrin : DMSO 1:0,4-2,0-10; stirring the resulting suspension at a temperature of 25°C for 30-180 minutes, washing and drying.

As organic sorbent used polyvinyl alcohol (PVA) is a hydrophilic polymer which is the product of large synthesis. The polymer is chemically stable (in the terms used in the biotechnology industry), resistant biodegradable, non-toxic. Good reologicheskie properties allow its use in large reactors.

Inorganic sorbents based on silica is chemically inert materials that are inside the grains of large pores of uniform size. It is the beads with high mechanical strength. Macroporous silica has long been used in biotechnological processes.

Rinse with water and dimethylsulfoxide produce to remove residual glutaraldehyde. The process to produce a glass Frit, which provides the removal of glutaraldehyde without loss of sorbents when washing and drying.

The ratio of sorbent: β-cyclodextrin: DMSO is 1:0.4 to 2.0 to 10 wt., the number of added β-cyclodextrin may vary, but preferably, it amounted to not less than 0.4 wt., to direct the the course of the reaction towards the production of the product and not more than 2.0 wt., since further increase in the number make β-cyclodextrin does not affect the course of the reaction and does not increase the yield of the product.

The method is as follows.

Introduce aldehyde groups in the polyvinyl alcohol and the sorbents based on silica, including using glutaraldehyde. The obtained sorbents washed with water and dimethylsulfoxide and filtered on a glass Frit Dissolve β-cyclodextrin in dimethyl sulfoxide (DMSO) and added sorbent for the reaction. Obtained during the reaction of immobilized sorbent β-cyclodextrin washed on a glass Frit with water, with alcohol and dried in air. Unreacted in the reaction β-cyclodextrin in DMSO optionally re-use.

The method is illustrated by examples.

Example 1. 1 g of PVA was dissolved in 10 ml of distilled water to the obtained solution under stirring was added 1 ml of 25%solution of glutaraldehyde and 0.1 ml of concentrated hydrochloric acid. The mixture was stirred without stirring at a temperature of 50°C for 3 hours, then the resulting gel was subjected to mechanical crushing and selected fraction with a particle size of 0.1-0.5 mm In 10 ml of dimethyl sulfoxide was dissolved 1.6 g β-cyclodextrin. Aqueous suspension of PVA containing aldehyde groups on filytrovali on a glass Frit, and 1 g of the obtained wet sorbent was made in 10 ml of dimethyl sulfoxide, containing β-cyclodextrin, which is the proportion of sorbent : β-cyclodextrin : DMSO 1:1,6:10. The reaction mixture was stirred at 37°C for 1 hour. The resulting sorbent with immobilized it β-cyclodextrin was washed on the Frit with water, ethyl alcohol and dried in air. Concentration β-cyclodextrin on the sorbent was 0.5 mmol/g Contents β-cyclodextrin on the sorbent was determined by the method with phenolphthalein [H. Dubois, Gillers K.A., Hamilton AS, et. al. Colorometric method for determination of sugars and related substances / Anal. Chem, V.28 (3), 350-356, 1956].

Example 2. 1 g of PVA was dissolved in 10 ml of distilled water to the obtained solution under stirring was added 1 ml of 25%solution of glutaraldehyde and 0.1 ml of concentrated hydrochloric acid. The mixture was stirred without stirring at a temperature of 50°C for 3 hours, then the resulting gel was subjected to mechanical crushing and selected fraction with a particle size of 0.1-0.5 mm In 10 ml of dimethyl sulfoxide was dissolved 1.6 g β-cyclodextrin. Aqueous suspension of PVA containing aldehyde groups, was filtered on a glass Frit, and 1 g of the obtained wet sorbent was made in 10 ml of dimethyl sulfoxide containing β-cyclodextrin, which is the proportion of sorbent : β-cyclodextrin : DMSO 1:1,6:10. The reaction mixture paramashiva and at 45° C for 1 hour. The resulting sorbent with immobilized it β-cyclodextrin was washed on the Frit with water, ethyl alcohol and dried in air. Concentration β-cyclodextrin on the sorbent was 0.39 mmol/g Contents β-cyclodextrin on the sorbent was determined by the method with phenolphthalein [16].

Example 3. To 1 g of inorganic sorbent (aminirovanie silica ACI) was added 8 ml of a 12.5% solution of glutaraldehyde in 0.1 M phosphate buffer pH 7.0 and stirred at room temperature for 30 minutes Then the sorbent was washed on a glass Frit with water and dimethylsulfoxide. In 10 ml of dimethyl sulfoxide was dissolved 1 g β-cyclodextrin and made 1 g of inorganic sorbent, which is the proportion of sorbent : β-cyclodextrin : DMSO 1:1:10. The reaction mixture was stirred at 50°C for 2 hours. The resulting sorbent was washed on the Frit with water, ethyl alcohol and dried in air. Concentration β-cyclodextrin on the sorbent was 0.2 mmol/g Contents β-cyclodextrin on the sorbent was determined by the method with phenolphthalein [16].

Example 4. 1 g of PVA was dissolved in 10 ml of distilled water to the obtained solution under stirring was added 1 ml of 25%solution of glutaraldehyde and 0.1 ml of concentrated hydrochloric sour the s. The mixture was stirred without stirring at a temperature of 50°C for 3 hours, then the resulting gel was subjected to mechanical crushing and selected fraction with a particle size of 0.1-0.5 mm In 10 ml of dimethyl sulfoxide was dissolved 0.4 g β-cyclodextrin. Aqueous suspension of PVA containing aldehyde groups, was filtered on a glass Frit, and 1 g of the obtained wet sorbent was made in 10 ml of dimethyl sulfoxide containing β-cyclodextrin, which is the proportion of sorbent : β-cyclodextrin : DMSO 1:0,4:10. The reaction mixture was stirred at 45°C for 1 hour. The resulting sorbent with immobilized it β-cyclodextrin was washed on the Frit with water, ethyl alcohol and dried in air. Concentration β-cyclodextrin on the sorbent was 0.1 mmol/g Contents β-cyclodextrin on the sorbent was determined by the method with phenolphthalein [16].

Example 5. 1 g of PVA was dissolved in 10 ml of distilled water to the obtained solution under stirring was added 1 ml of 25%solution of glutaraldehyde and 0.1 ml of concentrated hydrochloric acid. The mixture was stirred without stirring at a temperature of 50°C for 3 hours, then the resulting gel was subjected to mechanical crushing and selected fraction with a particle size of 0.1-0.5 mm In 10 ml of solution dimethyls is epoxide was dissolved 2.0 g β -cyclodextrin. Aqueous suspension of PVA containing aldehyde groups, was filtered on a glass Frit, and 1 g of the obtained wet sorbent was made in 10 ml of dimethyl sulfoxide containing β-cyclodextrin, which is the proportion of sorbent : β-cyclodextrin : DMSO 1:2:10. The reaction mixture was stirred at 37°C for 1 hour. The resulting sorbent with immobilized it β-cyclodextrin was washed on the Frit with water, ethyl alcohol and dried in air. Concentration β-cyclodextrin on the sorbent was 0.5 mmol/g Contents β-cyclodextrin on the sorbent was determined by the method with phenolphthalein [16].

Using the proposed method allows to obtain a new insoluble immobilized β-cyclodextrin on the basis of organic and inorganic sorbents, which can be used to obtain diet food low in cholesterol and its derivatives. The proposed method based on this invention are expected to be used on dairy enterprises of the Russian Federation, as well as for the production of egg powder. Immobilization of cyclodextrin on the sorbent will avoid the stage of purification of the product from the residual amount of β-cyclodextrin and allow multiple use of cyclodextrin in the process.

The way to obtain immobilized β-cyclodextrin, including preprocessing of organic and inorganic sorbents - polyvinyl alcohol and sorbent again on silica with glutaraldehyde for the introduction of molecules of the aldehyde groups, rinse with water and dimethylsulfoxide over a glass Frit, drying on a glass Frit, making the obtained sorbents in a solution of dimethyl sulfoxide containing dissolved in it β-cyclodextrin at a ratio of sorbent : β-cyclodextrin : dimethyl sulfoxide 1:0,4-2,0:10, stirring the resulting suspension at a temperature of 25-70°C for 30-180 min, washing and drying.



 

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