CN103626888A - Glucomannan succinate preparation method - Google Patents
Glucomannan succinate preparation method Download PDFInfo
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- CN103626888A CN103626888A CN201310669469.XA CN201310669469A CN103626888A CN 103626888 A CN103626888 A CN 103626888A CN 201310669469 A CN201310669469 A CN 201310669469A CN 103626888 A CN103626888 A CN 103626888A
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Abstract
The invention discloses a glucomannan succinate preparation method. The method adopts the natural materials of konjac polysaccharide, rhizoma bletillae polysaccharide and aloe polysaccharide or hydrolysates of the konjac polysaccharide, the rhizoma bletillae polysaccharide and the aloe polysaccharide, and uses an amide solvent as a medium, succinic anhydride as an acyl donor and N,N-diisopropylethylamine as a catalyst, the materials are reacted at the temperature of 80-110 DEG C for 2-6 hours, and ethyl alcohol or acetone, amount of which is 2-3 times that of the mixture, is added to precipitate, filtering and drying are performed to obtain the glucomannan succinate with the molar substitution degree of 0.1-1.0. According to the preparation method provided by the invention, the glucomannan succinate with controllable succinyl group substitution degree and good uniformity is directly obtained through one-step reaction, and the preparation method has the advantages of simplicity and convenience in operation, easy control, applicability to industrial production and the like. The glucomannan succinate has remarkably enhanced water solubility and an anti-oxidation effect, and can be applied to the fields of foods, cosmetics and drugs.
Description
Technical field
The present invention relates to a kind of glucomannan succinate and preparation method thereof, glucomannan succinate that a kind of succinyl substitution value is controlled, homogeneity is good and preparation method thereof is provided especially, belong to protective foods, makeup and medicine field.
Technical background
Glucomannan is a kind of common natural stickiness polysaccharide, and its main chain is that D-MANNOSE and D-Glucose form, and generally by β 1-4 position glycosidic link, connects, and often has part branched structure and ethanoyl to modify.Such polysaccharide distributes comparatively extensive, and such polysaccharide of finding in plant is at present widely used in fields such as food, makeup, medicines as konjac polysaccharide, Aloe polysaccharide, bletilla polysaccharide etc.In addition, natural polysaccharide is carried out chemical modification, obtains required physico-chemical property is a kind of important method, can further expand the range of application of polysaccharide.Common polysaccharide-modified mainly comprise hydrolysis, esterification etc., wherein one of widely used reaction is esterification, referring to work < < polysaccharide esterification > > (Yin Xueqiong such as Heinzes, Lin Qiangyi. Beijing: Chemical Industry Press, 2009).For example, adopt homogeneous phase nonaqueous phase solvent methyl-sulphoxide, at 4, N, under the catalysis of N-dimethyl aminopyridine, Propiram reacts 24h with succinyl oxide at 40 ℃, and the DS value of product is 1, and reaction is preferentially carried out at 6.Takahara etc. (Acta Biomaterialia, 2010,6:3138-3145) amylose starch has been carried out to succsinic acid acylation modification, the substitution value of product is in 0.6～2.1 scope.Jiang Yunpeng etc. (Carbohydrate Polymers, 2005,6:399-406) carrageenan has been carried out to succinylation, described raw material reacts 6h with succinyl oxide at 80 ℃, and the DS value of product is 2.7.Davarpanah etc. (Applied Surface Science, 2009,255:4171-4176) chitosan has been carried out to succinylation, at 50 ℃ of reaction 20h.Because the physico-chemical property of different classes of polysaccharide is different, esterification condition that need to be to target polysaccharide, comprises that catalyzer, temperature of reaction and time etc. are studied and is just expected to obtain target product.At present, the succinate study on the modification of glucomannan be there is not yet to report.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of glucomannan succinate.
The present invention, in early-stage Study, by controlling acid hydrolysis, can obtain the homogeneous glucomannan (number of patent application 201010166718.X) of desired molecule gauge lattice.For further reducing such polysaccharide stickiness, improve that it is water-soluble to expand its range of application; through exploratory development; after finding bletilla polysaccharide succinylation, its solution viscosity has remarkable reduction, thereby by the reaction factor of bletilla polysaccharide succinate is investigated, has completed the present invention.The present invention adopts following technical scheme:
A kind of preparation method of glucomannan succinate, described preparation method is as follows: choose glucomannan raw material, add amide solvent to dissolve, add again succinyl oxide and catalyst n, N-diisopropylethylamine, 80-110 ℃ of reaction 2-20 hour, add ethanol or the acetone of 2-3 times of volume to make precipitation, filter, gained precipitation is dry, obtains.
The preparation method characteristic of glucomannan succinate of the present invention is, the konjac polysaccharide that described glucomannan raw material is natural origin, bletilla polysaccharide, Aloe polysaccharide or its degraded product.Wherein according to purposes needs, the preferred homogeneous polysaccharide of specified molecular weight.Described polysaccharide can derive from commercially available product, and its degraded product can adopt with reference to relevant open source information the method self-controls such as hydrolysis, enzymolysis.
The preparation method characteristic of glucomannan succinate of the present invention is, described amide solvent is selected N, dinethylformamide (DMF) or N, N-N,N-DIMETHYLACETAMIDE, the mass volume ratio of its consumption and glucomannan raw material is 1: 10-60, concrete consumption is determined according to the solubility property of polysaccharide raw material.Described glucomannan raw material and succinyl oxide are 1 by monosaccharide groups mol ratio: 0.5-10, concrete consumption is determined according to the required substitution value of product.The preferred 80-100 ℃ of described temperature of reaction, more preferably 90-100 ℃.Preferred 2-6 hour of described reaction times.Described glucomannan succinate product, is 0.1-1.0 by monosaccharide groups molar substitution, and its concrete substitution value product can as required, prepare by parameters such as the above-mentioned reaction feed ratio of optimal control, temperature of reaction and times.
Glucomannan succinate of the present invention, concrete substitution value product can be prepared as required.Product after modification is compared with prototype glucomannan, and its water-soluble and all significantly enhancing of antioxygenation, has potential using value at relevant food, makeup and medicine field.
The key content that the present invention is claimed is to complete on the preparation technology's project study to glucomannan succinate and a large amount of research work such as parameter optimization, quality control method research basis.Outstanding feature of the present invention be this preparation method by single step reaction can directly obtain succinyl substitution value controlled, all one's life good glucomannan succinate; there is easy and simple to handle, easy control, be suitable for the advantages such as suitability for industrialized production, be applicable to the preparation of natural origin glucomannan (as konjac polysaccharide, bletilla polysaccharide, Aloe polysaccharide etc.) succinate.This glucomannan succinate has the water-soluble of remarkable enhancing, and through Antioxidation in vitro test, unexpected discovery has significant anti-OH simultaneously
.and O
2 -the effects such as free radical, are particularly useful for the product preparation in food, makeup and medicine.
Accompanying drawing explanation
The BT70 of Fig. 1 for adopting the embodiment of the present invention 2 to obtain, the infrared spectra stacking diagram of BT-S1 and BT-S2.
The BT-S3's that Fig. 2 is 2 acquisitions of the employing embodiment of the present invention
1h-NMR schemes (400MHz, D2O).
Embodiment
Glucomannan succinate preparation method of the present invention, take bletilla polysaccharide as example be that involved method is the technique means that those skilled in the art can grasp and use by the represented method manufacture of following embodiment or discovery.But following examples must not be interpreted as the limiting to the claimed invention going up in all senses.
Embodiment 1
The preparation of bletilla polysaccharide succinate described in the present embodiment: the preparation of the raw materials such as bletilla polysaccharide 70 (BT70, Mw=70kDa) is carried out with reference to patent documentation (application number 201010166718.X).Take respectively dried BT70 raw material 10g, put in 50mL there-necked flask, add 15mLDMF, in 100 ℃ of stirring and dissolving.Under design temperature, add 3mLN, N-diisopropylethylamine, and be to add succinyl oxide, reaction certain hour, timing sampling at 1: 1 according to raw material monosaccharide groups and succinyl oxide mol ratio.Reaction solution adds the dehydrated alcohol of 2 times of amounts to separate out precipitation, and suction filtration is used absolute ethanol washing 3-4 time, and gained white powder is put in 60 ℃ of baking ovens dry, obtains reaction product.The mensuration of succinyl substitution value, with reference to (Acta Biomaterialia, 2010,6,3138) literature methods such as Takahara, adopts determination of acid-basetitration.Investigated respectively the reaction under 80,90,100 and 110 ℃ of four temperature of reaction, different product molar substitutions (DS) data of mensuration are in Table 1.
The impact of table 1 temperature of reaction on BT70 succinyl-ester substitution value
Conclusion: reaction all can be carried out in selected temperature range, and wherein 90-100 ℃ of speed of reaction is more suitable; Reaction times is more excellent with 6h.Higher temperature (being greater than 120 ℃), longer reaction times (being greater than 20h) may cause product that certain degraded occurs.
Embodiment 2
The preparation of bletilla polysaccharide succinate described in the present embodiment: take respectively dried BT70 raw material 1.0g, adopt 100 ℃ of temperature of reaction, except the molar feed ratio of BT70 and succinyl oxide changes into 1: 0.5,1: 1,1: 3,1: 5,1: 10, all the other operations are carried out with reference to embodiment 1.Investigation BT70 is with the molar feed ratio of succinyl oxide on the impact of reacting, and measurement result is in Table 2.
The impact of table 2 reaction raw materials mol ratio on BT70 succinyl-ester substitution value
The structured testing of reaction product: (1) results of IR shows, BT70 and succinate reaction product BT70-S1 (DS0.38), BT70-S2 (DS0.85) etc. are at 1750cm
-1near corresponding carbonyl charateristic avsorption band obviously strengthens, referring to accompanying drawing 1; (2) proton nmr spectra analytical results shows, BT70-S3 (DS0.69) product occur succinyl-CH
2cH
2-(2.6～2.7ppm) replaces signal, referring to accompanying drawing 2.Result shows that this reaction product structure is correct.
Conclusion: reaction raw materials mol ratio has considerable influence to product substitution value, can, by selecting suitable feed ratio (1: 0.5～1: 10), obtain the reaction product of required substitution value (the highest by 0.9).Higher feed ratio (being greater than 1: 20), can not obviously increase product substitution value.The work such as Heinze < < polysaccharide esterification > > (Yin Xueqiong; Lin Qiangyi. Beijing: Chemical Industry Press; 2009; 45 pages) bibliographical information; the substituted in reaction of Propiram succinylation modification preferentially occurs in 6; under this reaction conditions, succinyl the position of substitution is inferred similarly, mainly occurs in 6 hydroxyls that steric hindrance is less.
Embodiment 3
The preparation of glucomannan succinate described in the present embodiment: take respectively dried BT40 (1.0g), BT70 (1.0g), BT180 (0.5g), konjac polysaccharide (0.2g) and Aloe polysaccharide (0.5g) raw material, the molar feed ratio of polysaccharide and succinyl oxide is 1: 10, adopt 100 ℃ of temperature of reaction, reaction times 6h, all the other operations are carried out with reference to embodiment 1.Investigated respectively the preparation of different glucomannan succinyl oxides, measurement result is in Table 3.
The substitution value of the different glucomannan succinyl-of table 3 ester
Conclusion: adopt described reaction method, all can obtain the corresponding succinyl-ester products of different glucomannan.
Embodiment 4
The Antioxidation in vitro of BT70 succinate test described in the present embodiment: adopt part reaction product in embodiment 2, with reference to " the anti-oxidant activity research of bletilla polysaccharide succinate " (University Of Suzhou's journal medicines such as Wang Hucheng, 2012,32,597) literature method, has investigated respectively BT70 succinate to OH
., O
2 -with hexichol for bitter taste hydrazides (DPPH
.) antioxygenation, and adopt 2010 editions official methods to measure its solution solvent viscosity ratio (η r, 1% aqueous solution) parameter, the results are shown in Table 4.
External free radical scavenging effect and the solution solvent viscosity ratio parameter thereof of table 4BT70 succinyl-ester
Result shows: the BT70 succinyl-ester after modification has significant In Vitro Anti OH
.and O
2 -activity, its antioxygenation and substitution value increase to direct ratio; BT70 and succinyl-ester thereof are to DPPH
.also have certain restraining effect, clearance rate in 30～48.6% scopes, but to DS without obviously relevant.BT70 succinyl-ester solution solvent viscosity ratio also reduces along with the increase of DS, and its water-soluble significantly strengthens.The bletilla polysaccharide succinate of result proof modification has significant In Vitro Anti OH
.and O
2 -effect, its water-soluble also significantly enhancing, has novel physico-chemical property and potential using value simultaneously.
Claims (9)
1. the preparation method of a glucomannan succinate, it is characterized in that described preparation method is as follows: choose glucomannan raw material, add amide solvent to dissolve, add again succinyl oxide and catalyst n, N-diisopropylethylamine, 80-110 ℃ of reaction 2-20 hour, add ethanol or the acetone of 2-3 times of volume to make precipitation, filter, gained precipitation is dry, obtains.
2. the preparation method of glucomannan succinate according to claim 1, is characterized in that konjac polysaccharide, bletilla polysaccharide, Aloe polysaccharide or its degraded product that described glucomannan raw material is natural origin.
3. the preparation method of glucomannan succinate according to claim 1, is characterized in that described amide solvent is DMF or N,N-dimethylacetamide, and the mass volume ratio of its consumption and glucomannan raw material is 1: 10-60.
4. the preparation method of glucomannan succinate according to claim 1, is characterized in that described glucomannan raw material and succinyl oxide are 1 by monosaccharide groups mol ratio: 0.5-10.
5. the preparation method of glucomannan succinate according to claim 1, is characterized in that the preferred 80-100 ℃ of described temperature of reaction, more preferably 90-100 ℃.
6. the preparation method of glucomannan succinate according to claim 1, is characterized in that preferred 2-6 hour of described reaction times.
7. the preparation method of glucomannan succinate according to claim 1, is characterized in that described glucomannan succinate is 0.1-1.0 by monosaccharide groups molar substitution.
8. glucomannan succinate according to claim 1, the application in preparing food, makeup and medicine.
9. glucomannan succinate according to claim 8, the application in preparing food, makeup and medicine, is characterised in that this glucomannan succinate has the water-soluble and antioxygenation of enhancing simultaneously.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087625A (en) * | 2014-07-08 | 2014-10-08 | 清华大学 | Preparation method of poly butylenes succinate |
| CN106279454A (en) * | 2015-06-02 | 2017-01-04 | 福建省泉州市味博食品有限公司 | The physical property method of modifying of a kind of soluble soybean polysaccharide and preparation |
| CN107007555A (en) * | 2017-06-06 | 2017-08-04 | 南京大学 | It is acylated the preparation and application of Glucomannan nano particle |
| CN108078939A (en) * | 2018-01-25 | 2018-05-29 | 庄明莲 | A kind of anti-cancer medicament carrier preparation and its application |
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| CN1280989A (en) * | 2000-08-18 | 2001-01-24 | 干信 | Process for preparing dodecanoyl Konjak-glucomannoligose-sodium sulfonate |
| CN102241788A (en) * | 2010-05-10 | 2011-11-16 | 辽宁诺康医药有限公司 | Preparation method for glucomannan acid hydrolyzed product |
| CN102863550A (en) * | 2012-10-25 | 2013-01-09 | 西南大学 | Preparation method of octylene succinic acid konjac glucomannan ester |
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| CN1280989A (en) * | 2000-08-18 | 2001-01-24 | 干信 | Process for preparing dodecanoyl Konjak-glucomannoligose-sodium sulfonate |
| CN102241788A (en) * | 2010-05-10 | 2011-11-16 | 辽宁诺康医药有限公司 | Preparation method for glucomannan acid hydrolyzed product |
| CN102863550A (en) * | 2012-10-25 | 2013-01-09 | 西南大学 | Preparation method of octylene succinic acid konjac glucomannan ester |
Non-Patent Citations (1)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087625A (en) * | 2014-07-08 | 2014-10-08 | 清华大学 | Preparation method of poly butylenes succinate |
| CN104087625B (en) * | 2014-07-08 | 2016-07-13 | 清华大学 | A kind of preparation method of poly butylene succinate |
| CN106279454A (en) * | 2015-06-02 | 2017-01-04 | 福建省泉州市味博食品有限公司 | The physical property method of modifying of a kind of soluble soybean polysaccharide and preparation |
| CN106279454B (en) * | 2015-06-02 | 2019-01-25 | 福建省泉州市味博食品有限公司 | A kind of physical property method of modifying of soluble soybean polysaccharide |
| CN107007555A (en) * | 2017-06-06 | 2017-08-04 | 南京大学 | It is acylated the preparation and application of Glucomannan nano particle |
| CN108078939A (en) * | 2018-01-25 | 2018-05-29 | 庄明莲 | A kind of anti-cancer medicament carrier preparation and its application |
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Application publication date: 20140312 |