The method of obtaining innovating derivatives of chitosan oligosaccharide

 

(57) Abstract:

The invention relates to a method for producing derivatives of chitosan oligosaccharide and can be used in medical and food industries, as components of various compositions. The method of obtaining innovating derivatives of chitosan oligosaccharide, enzymatic depolymerization in the presence of papain and acetic acid, with subsequent spray drying of the product. The resulting product is then subjected alternately double dissolution in water and spray-dried, after which the obtained product is dissolved in water together with substances having an acid group selected from nicotinic acid, lactic acid, glycine hydrochloride, L-carnitine hydrochloride, glutamic acid, gamma-amino-beta-phenylalkanoic acid hydrochloride, adenosine phosphate, cocarboxylase, aspartame, gemfibrozil, aminocaproic acid hydrochloride, simplemodal acid, succinic acid, ascorbic acid, vitamin b3, methionine or alexamenos acid with subsequent drying of the resulting product. The invention allows to obtain oligosaccharides with not fully connected groups, octobriana relates to a method for obtaining derivatives of chitosan oligosaccharide and can be used in medical, cosmetic and food industries as components of various compositions.

The chitosans are polymers of biological origin. From a chemical point of view, the chitosan is deacetylating usually more than 70% of chitin (poly-2-acetamido-2 deoxy-D-glucose).

The chitosans as usual polysaccharides easy enough oligomerized different methods, in particular enzymatic oligomerization.

Known methods of oligomerization using enzymes, primarily of papain in the presence of hydrochloric, acetic, ascorbic acid [Korean Patent 142373, dated 31 March 1998]. Since oligosaccharides play the role of anion-exchange materials obtained in this case, the products are chlorides, acetates, ascorbates of chitosan oligosaccharide formed from the acid environment used to create the required pH for the enzymatic depolymerization of chitosan.

The resulting oligosaccharides amino fully bound used in the enzymatic treatment with acids, so they cannot directly be used for ion binding substances having acidic groups.

The invention consists in the floor is in and acetic acid, with subsequent spray drying of the product.

The difference of the invention is that the resulting product is subjected alternately double dissolution in water and spray-dried, after which the obtained product is dissolved in water together with substances having an acid group selected from nicotinic acid, lactic acid, glycine hydrochloride, L-carnitine hydrochloride, glutamic acid, gamma-amino-beta-phenylalkanoic acid hydrochloride, adenosine phosphate, cocarboxylase, aspartame, gemfibrozil, aminocaproic acid hydrochloride, niflumova acid, succinic acid, ascorbic acid, vitamin b3, methionine or alexamenos acid with subsequent drying of the resulting product.

The proposed method for obtaining derivatives of chitosan oligosaccharide is not known.

The following examples explain the present invention.

Example 1

Oligosaccharide chitosan n=2-20, obtained by enzymatic depolymerization in the presence of papain (5% chitosan 1.5% acetic acid, containing papain to 0.5% by weight of chitosan, temperature 50 C, 5 h), and dried in the spray dryer, with the content innovatsennoi acetic acid in the amount of 14 wt.% dissolve in water to 5/h, inlet temperature of hot air - 160-S, the temperature of the outlet air - 60-70C), resulting in the content of acetic acid is reduced to 9.2 wt.%. The resulting product is again dissolved in water and again passed through a spray drying the above conditions, resulting in the amount of acetic acid is reduced to 5.9 wt.%, which corresponds 16,82% of the amino groups, connected with acetic acid.

100 kg of the obtained chitosan oligosaccharide is dissolved in water to 5% solution and then add 56,16 kg of nicotinic acid, which corresponds to 75% of the salt linkage with the amine groups of chitosan oligosaccharide, and the long-term is stirred until complete choosing a poorly soluble oligosaccharide nicotinic acid. The resulting solution was passed through a spray drying the above conditions.

The resulting product contains, wt%:

Oligosaccharide chitosan 61,0

Monovacancy nicotinic acid 36,45

Monovacancy acetic acid 2,55

The number inovating of the product was determined by potentiometric titration.

Example 2

100 kg of the obtained chitosan oligosaccharide in the conditions of example 1, containing 5.9 wt.% the UKS is the outcome linking the amino groups of chitosan oligosaccharide, and long is stirred until complete choosing the oligosaccharide nicotinic acid. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 80,62

Monovacancy nicotinic acid 16,04

Monovacancy acetic acid 3,34

Example 3

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 10% solution and add 13.7 kg of lactic acid, which corresponds to 25% salt linking the amino groups of chitosan oligosaccharide. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 84,24

Monovacancy lactic acid of 12.26

Monovacancy acetic acid 3,5

Example 4

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 10% solution and add 27,15 kg of the hydrochloride of glycine, which corresponds to 40% salt linking of amino groups of chitosan oligosaccharide. The resulting solution was passed through RAID chitosan 75,2

Monovacancy hydrochloride glycine 21,7

Monovacancy acetic acid 3,1

Example 5

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 10% solution and add a 12.03 kg of the hydrochloride of L-carnitine (3-carboxy-hydroxy-N,N,N-trimethyl-1-Protamine hydroxide), which corresponds to 10% salt linking of amino groups of chitosan oligosaccharide. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 85,52

Monovacancy hydrochloride of L-carnitine of 10.93

Monovacancy acetic acid 3,55

Example 6

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 5% solution and add 8,95 kg glutamic acid, which corresponds to 10% salt linking of amino groups of chitosan oligosaccharide, and the long-term is stirred until complete choosing the oligosaccharide poorly soluble glutamic acid. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:this acetic acid 3,64

Example 7

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 10% solution and add to 17.9 kg of aspartame (N-L-alpha-aspartame-L-phenylalanine 1-methyl ester), which corresponds to 10% salt linking of amino groups of chitosan oligosaccharide. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 81,19

Monovacancy aspartame 15,45

Monovacancy acetic acid 3,36

Example 8

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 10% solution and add 65,24 kg of phenibut (gamma-amino-beta-phenylalkanoic acid hydrochloride), which corresponds to 50% salt linking of amino groups of chitosan oligosaccharide. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 57,65

Monovacancy phenibut 39,96

Monovacancy acetic acid 2,39

Example 9

100 kg obtained in the conditions of example 1 alicenine phosphate (5-Danilova acid), which corresponds to 10% salt linking of amino groups of chitosan oligosaccharide, and the long-term is stirred until complete choosing the oligosaccharide poorly soluble adenosine phosphate. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 79,0

Monovacancy adenosine phosphate 17,72

Monovacancy acetic acid 3,28

Example 10

10 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 10% solution and add 0.52kg cocarboxylase (3-[(4-amino-2-methyl-5-pyrimidinyl)-methyl]-4-methyl-5(4,6,6-trihydroxy-3,5-dioxa-4,6-lifestages-1-yl) tiazoly chloride, P,P'-dioxide), which corresponds to 2% salt linking of amino groups of chitosan oligosaccharide. The resulting solution was subjected to freeze drying.

The resulting product contains, wt%:

Oligosaccharide chitosan 91,18

Monovacancy kokarboksilaza 5,04

Monovacancy acetic acid 3,78

Example 11

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid, dissolved in modestum 10% salt linking of amino groups of chitosan oligosaccharide, and long is stirred until complete choosing the oligosaccharide poorly soluble gemfibrozil. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 83,13

Monovacancy gemfibrozil 13,43

Monovacancy acetic acid 3,44

Example 12

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 10% solution and add to 20.4 kg hydrochloride aminocaproic acid, which corresponds to 20% salt linking of amino groups of chitosan oligosaccharide. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 79,48

Monovacancy hydrochloride aminocaproic acid 17,23

Monovacancy acetic acid 3,29

Example 13

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 5% solution and add 15,33 kg niflumova acid (2-[[3-(trifluoromethyl)phenyl]amino]-3-pyridineboronic acid), which is suitable for the optimum drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 83,03

Monovacancy niflumova acid 13,53

Monovacancy acetic acid 3,44

Example 14

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 10% solution and add 53,56 kg ascorbic acid (-lactone 2,3-degidro-L-Galanova acid), which corresponds to 50% salt linking of amino groups of chitosan oligosaccharide. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 62,09

Monovacancy ascorbic acid 35,34

Monovacancy acetic acid to 2.57

Example 15

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 10% solution and add 35,92 kg of succinic acid, which corresponds to 50% salt linking of amino groups of chitosan oligosaccharide. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 70,27

10 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 10% solution and add 1,33 kg of vitamin b3(D-(+)-3-(2,4-dihydroxy-3,3-dimethyl-Butylimino) propionic acid), which corresponds to 10% salt linking of amino groups of chitosan oligosaccharide. The resulting solution was subjected to freeze drying.

The resulting product contains, wt%:

Oligosaccharide chitosan 84,55

Monovacancy vitamin b311,95

Monovacancy acetic acid 3,5

Example 17

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid is dissolved in water to 10% solution and add 18,15 kg methionine, which corresponds to 20% salt linking of amino groups of chitosan oligosaccharide. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 81,02

Monovacancy methionine 15,63

Monovacancy acetic acid 3,35

Example 18

100 kg obtained in the conditions of example 1 of chitosan oligosaccharide containing 5.9 wt.% acetic acid, dissolve the SCP of chitosan oligosaccharide. The resulting solution was passed through a spray drying under the conditions of example 1.

The resulting product contains, wt%:

Oligosaccharide chitosan 79,72

Monovacancy accumula acid 17,13

Monovacancy acetic acid 3,15

The method of obtaining innovating derived oligosaccharide chitosan by enzymatic depolymerization in the presence of papain and acetic acid, with subsequent spray drying of the product, characterized in that the resulting product is then subjected alternately double dissolution in water and spray-dried, after which the obtained product is dissolved in water together with substances having an acid group selected from nicotinic acid, lactic acid, glycine hydrochloride, L-carnitine hydrochloride, glutamic acid, gamma-amino-beta-phenylalkanoic acid hydrochloride, adenosine phosphate, cocarboxylase, aspartame, gemfibrozil, aminocaproic acid hydrochloride, simplemodal acid, succinic acid, ascorbic acid, vitamin b3, methionine or alexamenos acid with subsequent drying of the resulting product.

 

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