CN1216077C - K-carrageenan oligosaccharide monomer and its preparation method - Google Patents
K-carrageenan oligosaccharide monomer and its preparation method Download PDFInfo
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- CN1216077C CN1216077C CN031389686A CN03138968A CN1216077C CN 1216077 C CN1216077 C CN 1216077C CN 031389686 A CN031389686 A CN 031389686A CN 03138968 A CN03138968 A CN 03138968A CN 1216077 C CN1216077 C CN 1216077C
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Abstract
The present invention relates to a K-carrageenan oligosaccharide monomer which is characterized in that K-carrageenan oligosaccharides of which the polymerization Dp is from 7 to 25 have the following molecular formula: C<18+12n>H<28+17n>O<21+12n>S<2+n>Na<2+n>, wherein n is from 2 to 11; the molecular weight are orderly 1506, 1914, 2322, 2730, 3138, 3546, 3954, 4362, 4770 and 5178. During preparation, K-carrageenan is degraded by acid, neutralized by alkali, concentrated, precipitated by alcohol, and washed, uses an ammonium bicarbonate solution as a mobile phase and uses a superdex 30 column for separation. In the present invention, the K-carrageenan oligosaccharides of which the polymerization degrees are from 7 to 25 can be obtained by one-time separation, and ion-exchange chromatography does not need using for further separation, which greatly simplifies technological operation and enhances the preparation efficiency of the oligosaccharides. The K-carrageenan oligosaccharide monomer uses the ammonium bicarbonate as the mobile phase; because the ammonium bicarbonate is easy to volatilize, the problem of difficult salt removal during the preparation of an oligosaccharide monomer sample is solved. The obtained K-carrageenan oligosaccharide monomer can be used for preparing oligosaccharide standard reagents and used as an oligosaccharide intermediate to further prepare saccharide medicines.
Description
Technical field
The present invention relates to a kind of K-carrageenan oligosaccharide, specifically relating to a kind of polymerization degree is K-carrageenan oligosaccharide monomer of 7-25 and preparation method thereof.
Background technology
Carrageenin is the cell wall polysaccharides of some red algae, be the Polygalactan sulfuric ester that is made of semi-lactosi and galactose derivate, wherein the K-carrageenin is by 1,4-sulfate-β-D-semi-lactosi and 1 that 3-connects, 3 of 4-connection, the polymkeric substance that 6-inner ether-α-the D-semi-lactosi alternately is formed by connecting.Carrageenin is widely used in fields such as medicine, food, agricultural and daily-use chemical industry owing to be a kind of natural polyanion sulfated polysaccharide.In the last few years, many important biomolecules of carrageenan oligosaccharide and derivative thereof were learned functions and physiologically active is familiar with by people gradually, all demonstrated good prospects for application at aspects such as antibiotic, antiviral, antitumor, anticoagulation and antiulcer agents.Disclosing a kind of as Japanese Patent JP3-170406A is the antiseptic-germicide of effective constituent with K-carrageenin acid hydrolysis products.But at present in the degraded technology of preparing and patent about carrageenan oligosaccharide, what obtain is the mixture of oligosaccharides, being unfavorable for further carrying out oligosaccharide structure is the further investigation of structure activity relationship with activity, be unfavorable for studying the relation and the mechanism of action thereof of K-carrageenan oligosaccharide and derivative and disease development from molecular level, thereby instruct the research and development of new drug, the therefore relevant monomeric preparation of K-carrageenan oligosaccharide is very necessary.If but adopt the method for chemosynthesis to prepare K-carrageenan oligosaccharide monomer; particularly the above oligosaccharide monomer of the polymerization degree (Dp)＞10 synthesizes; because of relating to a series of problems such as the mode of connection of the protection of active group, sugared unit and steric configuration, its technical difficulty and synthetic cost all are unacceptable.
Summary of the invention
The purpose of this invention is to provide a kind of K-carrageenan oligosaccharide monomer and preparation method thereof, can satisfy the demand of prior art with the oligosaccharide monomer of its preparation.
A kind of K-carrageenan oligosaccharide monomer is characterized in that the K-carrageenan oligosaccharide of polymerization degree Dp=7-25, and their molecular formula is respectively C
18+12nH
28+17nO
21+12nS
2+nNa
2+n, n=2-11 in the formula, structural formula is as follows:
In the formula: n=2-11
The monomeric preparation method of a kind of K-carrageenan oligosaccharide comprises the acid degradation of K-carrageenin, neutralizes with alkali, concentrate, alcohol precipitation, washing is again through column chromatography for separation, press elution peak and merge collection, concentrate, drying is characterized in that column chromatography for separation adopts the differential detector to detect, with the ammonium bicarbonate soln is moving phase, separates with the Superdex30 post.
The present invention adopts the Superdex30 post to separate, and once can obtain the polymerization degree is all odd number K-carrageenan oligosaccharides of 7-25, need not further to separate with ion exchange chromatography again, has simplified technological operation greatly and has improved the preparation efficiency of oligosaccharides.The present invention adopts bicarbonate of ammonia as moving phase, because of its easy volatilization, through concentrating repeatedly and can removing substantially, has overcome the difficulty of desalination in the oligosaccharide monomer specimen preparation greatly, has improved the quality of product.Simultaneously, the present invention has overcome the difficulty that existing synthetic technology is difficult to prepare a large amount of oligosaccharides, for the structure activity relationship of further carrying out oligosaccharides and derivative thereof and Study on mechanism and aspect the research and development of instructing new drug, all has important practical significance.The K-carrageenan oligosaccharide monomer that the present invention obtains also can be used for preparing the oligosaccharides standard reagent and further is prepared into the carbohydrate medicine as the oligosaccharides intermediate.
Description of drawings and embodiment
The present invention is described further below in conjunction with the drawings and specific embodiments.
Accompanying drawing 1 prepares the elution curve of K-carrageenan oligosaccharide for the present invention.
Accompanying drawing 2 prepares the infrared spectrogram of K-carrageenin 7-21 sugar for the present invention.
Accompanying drawing 3 prepares the ESI/MS mass spectrum of K-carrageenin nine sugar for the present invention.
Accompanying drawing 4 prepares the nucleus magnetic resonance figure of K-carrageenin nine sugar for the present invention
Embodiment
The acid of the K-carrageenin being used 0.05-1.0M is behind 60-100 ℃ of degraded 20-180min, neutralize with alkali, after rotation concentrates, with alcohol precipitation, washing, detect with the differential detector again, bicarbonate of ammonia with 0.05-0.5M is moving phase, separates with the Superdex30 post, presses elution peak and merges collection, concentrate, lyophilize promptly then.Totally 10 kinds of carrageenin monomer oligosaccharides, their molecular weight is followed successively by 1506,1914, and 2322,2730,3138,3546,3954,4362,4770 and 5178.
Wherein said acid is hydrochloric acid, sulfuric acid, nitric acid and oxalic acid; Alkali is sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus.
As can be seen from Figure 1, the polymerization degree is that all odd number K-carrageenan oligosaccharides of 7-25 have all obtained good separation.As can be seen from Figure 2, each oligosaccharides is at 1253cm
-1And 848cm
-1All there is strong absorption peak at the place, is respectively the characteristic absorbance of S=O stretching vibration and C-O-S in 4-sulfate-β-D-semi-lactosi, at 924cm
-1The absorption peak at place is α-D-3, the characteristic absorbance of 6 inner ether semi-lactosis, and what show that the present invention prepares is K-carrageenin series oligosaccharides.1891 is [M-Na among Fig. 3
+]
-The peak calculates that its molecular weight is 1914, conforms to the molecular weight of K-carrageenin nine sugar its fragmention to be carried out further analysis revealed it contains five G4S and four AnGal saccharide residues, is K-carrageenin nine sugar.The signal ownership of K-carrageenin nine each carbon of sugar is as table 1 among Fig. 4.
The nucleus magnetic resonance figure carbon signal ownership of table 1:K-carrageenin nine sugar.
| ?Residue | ?C1 | ?C2 | ?C3 | ?C4 | ?C5 | ?C6 |
| ?αG4S re?βG4S re?G4S int?α-G4S nre?AnGal ?adjacent?to?αre ?AnGal ?adjacent?to?βre ?AnGal | ?86.2 ?94.2 ?102.3 ?102.5 ?89.3 ? ?89.9 ? ?89.9 | ?69.2 ?69.0 ?68.9 ?- ?- ? ?- ? ?68.9 | ?76.5 ?78.3 ?75.5 ?73.3 ?- ? ?- ? ?78.8 | ?76.2 ?74.5 ?- ?77.9 ?- ? ?- ? ?78.3 | ?- ?- ?76.2 ?71.6 ?- ? ?- ? ?77.7 | ?60.9 ?61.0 ?- ?61.3 ?- ? ?- ? ?68.9 |
Claims (1)
1 one kinds of K-carrageenan oligosaccharide monomers is characterized in that the K-carrageenan oligosaccharide of polymerization degree Dp=7-25, and their molecular formula is respectively C
18+12nH
28+17nO
21+12nS
2+nNa
2+n, n=2-11 in the formula, structural formula is as follows:
In the formula: n=2-11.
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| CN031389686A CN1216077C (en) | 2003-08-04 | 2003-08-04 | K-carrageenan oligosaccharide monomer and its preparation method |
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| CN1216077C true CN1216077C (en) | 2005-08-24 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100518829C (en) * | 2005-04-30 | 2009-07-29 | 中国科学院海洋研究所 | Preparing process of kappa-carrageenan for medicine capsule |
| CN100413509C (en) * | 2006-07-21 | 2008-08-27 | 宁波大学 | Use of lambda-carrageenan oligose in preparing blood vessel proliferation inhibitor |
| CN100365008C (en) * | 2006-07-21 | 2008-01-30 | 宁波大学 | Process for preparing red alga oligose |
| CN102516323B (en) * | 2011-10-25 | 2014-05-07 | 中国海洋大学 | Low molecular weight carrageenan oligosaccharide and preparation method and application thereof |
| CN113735984B (en) * | 2021-08-17 | 2023-03-21 | 苏州苏大卫生与环境技术研究所有限公司 | Preparation process of carrageenan odd oligosaccharide |
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