CN103435715A - Preparation method and application of vanadium complexes of oligosaccharides and derivatives thereof - Google Patents
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Abstract
The invention discloses a preparation method and application of vanadium complexes of oligosaccharides and derivatives thereof. The preparation method comprises the following steps: hydrolyzing polysaccharides to obtain oligosaccharides; performing complex reaction on the oligosaccharides or derivatives thereof and VO<2+> to form complexes; and removing the excessive unreacted inorganic ions to obtain the vanadium complexes of the oligosaccharides. The vanadium complexes are used for inhibiting proliferation of BEL-7402 cancer cells and inhibiting activity of the enzyme PTP1B. The invention has the following advantages: 1, the oligosaccharides and derivatives thereof can be absorbed more easily, and have better biological activity, e.g. multiple pharmacological actions such as tumor resistance, resistance to various cardiovascular diseases, virus resistance, oxidation resistance, blood sugar reduction, immunity enhancement and the like; and 2, the oligosaccharides and derivatives thereof have better reaction activity, can react with ions to form complexes more easily due to serving as ligands, and can give full play to physiological activity of the minor element vanadium and the polysaccharide derivatives, so that the actions of the both are mutually coordinated and enhanced, thus improving availability of the vanadium in living organisms.
Description
Technical field
The invention belongs to the synthetic field of carbohydrate chemistry, adopt specifically oligosaccharides and Vanadyl by the chemical bond complexing, form the preparation method of title complex and the application of inhibition tumour and hypoglycemic activity in organism.
Background technology
People find the research of the biological activity of oligosaccharides and application thereof in recent years, and the oligosaccharides source is abundant, structure is unique, have the growth of promotion, antitumor, reducing blood-fat blood sugar, Green Tea Extract oxidation, immunomodulatory isoreactivity.Vanadium is a kind of essential trace element of life entity, have para-insulin, anticancer, promote bone growth, promote biological to grow, the effects such as anti-inflammatory, spermicide.As far back as 19th century, the inorganic salt of vanadium just are used to treat the diseases such as anaemia, malnutrition, pulmonary tuberculosis.1985, the para-insulin effect and the hypoglycemic activity that studies confirm that vanadium of Heylig etc.Consider inorganic vanadium fat-soluble little, bioavailability is low, toxicity than high, side effect is large, therefore the research of organic vanadium title complex is arisen at the historic moment.Along with the further investigation of domestic and international researcher to the preparation of organic vanadium title complex, activity, the mechanism of action, synthetic, the sign of the novel organic vanadium title complex with antitumous effect, para-insulin effect and hypoglycemic activity, active testing more and more receive people's concern.Development research to novel organic vanadium compound is conducive to alleviate cancer and the diabetes threat day by day serious to human health.
In the research to the organic vanadium title complex, find, the selection of organic ligand seems most important, and selecting to have bioactive suitable organic molecule is one of effective way increased the vanadium complex activity as part.For the selection of organic ligand, the general requirement part water-soluble and fat-soluble good, toxicity is low, stability is better.Wherein study more organic carboxylic-acid, amino acid and derivatives class thereof, carbohydrate and the assorted part that contains the ligating atoms such as N, S of comprising.Oligosaccharides, brown alga oligose, chitin oligo saccharide, carrageenin and the agaropectin oligoses etc. of marine source of take are representative, and they can be obtained by corresponding Sargassum polysaccharides degraded, and the structure uniqueness, have multiple biological activity, and huge Research Prospects is arranged.The present invention be take oligosaccharides as part, exploitation, design synthesizing new oligosaccharides vanadium complex increases its bioavailability, develop its suppress tumour and hypoglycemic aspect application.
Summary of the invention
The present invention be take oligosaccharides as raw material, obtain the oligosaccharides vanadium complex with the vanadylic sulfate coordination, determine that by Infrared spectroscopy vanadium is combined with the form of chemical bond with part, by ultraviolet-visible spectrum, prove that the coordination mode of marine alga vanadium complex is the side-on coordination of triangular form.Technical problem to be solved is oligosaccharides and VO
2+reaction conditions and have neither part nor lot in the VO of reaction
2+and the removal method of other mineral ions.
The following scheme of the concrete employing of the present invention:
The preparation method of oligosaccharides vanadium complex, at first by polysaccharide (take Sargassum polysaccharides as example), being hydrolyzed obtains oligosaccharides, then by the oligosaccharides or derivatives thereof as sulphating, carboxymethylation oligosaccharides etc. and VO
2+carry out complex reaction under certain condition, form title complex, remove the unnecessary mineral ion that has neither part nor lot in reaction, obtain the oligosaccharides vanadium complex.
Oligosaccharides comprises the oligochitosan that obtains from polysaccharide hydrolysis such as chitosan, carrageenin, algal polysaccharide, agarose, sodium alginate, synanthrin, brown alga oligose, agar oligosaccharides, Nutriflora P etc.Concrete scheme is as follows:
A kind of preparation method of oligosaccharides vanadium complex, at first be hydrolyzed polysaccharide to obtain oligosaccharides, then by oligosaccharides or derivatives thereof and VO
2+carry out complex reaction, forming title complex, removing the unnecessary mineral ion that has neither part nor lot in reaction, obtaining the oligosaccharides vanadium complex.
The described polysaccharide method that obtains oligosaccharides that is hydrolyzed is: sodium alginate is dissolved in distilled water, drips sulfuric acid and regulate H
+ultimate density is 0.22mol/L, under 90 ℃ of water-baths, degrades; Regulate degradation solution pH to 7, filtered while hot with NaOH solution; The concentrated solution alcohol precipitation, the crude product after vacuum-drying is dissolved in a small amount of water, removes by filter insolubles; Strongly acidic cation-exchange and the desalination of weak base type resin anion(R.A) for liquid glucose, alcohol precipitation after elutriant is concentrated, vacuum-drying obtains the brown alga oligose I, and molecular-weight average is 4.1kd.
The described polysaccharide method that obtains oligosaccharides that is hydrolyzed is: sodium alginate is added to distilled water, stir under 100 ℃ of water-baths, add H
2o
2reaction; Regulate degradation solution pH to 7, filtered while hot with NaOH solution; The concentrated solution alcohol precipitation, the crude product after vacuum-drying is dissolved in a small amount of water, removes by filter insolubles; Strongly acidic cation-exchange and the desalination of weak base type anionite-exchange resin for liquid glucose, alcohol precipitation after elutriant is concentrated; Vacuum-drying obtains the brown alga oligose II, and molecular-weight average is 1.6kd.
In the described polysaccharide method that obtains oligosaccharides that is hydrolyzed, be: get agarose and add distilled water, stir and make it be dissolved into the transparent colloid shape fully under 100 ℃ of water-baths, add concentrated hydrochloric acid, making concentration of hydrochloric acid is 0.2mol/L, 50 ℃ of stirring reactions 5 hours, adjust pH to 7 with NaOH solution; Suction filtration, concentrated, the concentrated solution alcohol precipitation, the crude product after vacuum-drying is dissolved in a small amount of water, removes by filter insolubles; With strongly acidic cation-exchange and the desalination of weak base type anionite-exchange resin, alcohol precipitation after elutriant is concentrated, vacuum-drying obtains agaropectin oligose, and molecular-weight average is 1.1kd.
The described polysaccharide method that obtains oligosaccharides that is hydrolyzed is: agaropectin oligose is added to the distilled water stirring and dissolving, add the alkalization of NaOH solution; Then divide three times and add Mono Chloro Acetic Acid, reaction 4h remain that pH value of solution is greater than 9 under 60 ℃; Drip acetic acid adjust pH to 7.0, vacuum concentration, concentrated solution precipitates with dehydrated alcohol, and precipitation is by 70% washing with alcohol repeatedly; Product is dissolved in a small amount of water through dialysis tubing dialysis 24h desalination, adds acetone precipitation, suction filtration, and with absolute ethanol washing repeatedly, vacuum-drying obtains the carboxymethyl agaropectin oligose.
Described oligosaccharides or derivatives thereof and VO2+ in the method for carrying out complex reaction are: during the brown alga oligose I is dissolved in to distilled water, with NaOH solution, adjust pH to 12, remain pH value of solution>=12 in whole reaction process; Stir 30-50min under 30 ℃ of water-baths, add VOSO
45H
2o, reaction 4-8h becomes clear to solution; Reaction solution concentrates alcohol precipitation, precipitation; By 70% washing with alcohol repeatedly; Product is dissolved in a small amount of water through dialysis tubing dialysis 24h desalination, adds acetone precipitation, suction filtration, and with absolute ethanol washing repeatedly, 40 ℃ of vacuum-drying 24h obtain brown alga oligose I vanadium complex.
The invention also discloses a kind of application of oligosaccharides vanadium complex, for the inhibition to the BEL-7402 cancer cell multiplication.
The present invention further discloses a kind of application of oligosaccharides vanadium complex, for inhibitory enzyme PTP1B activity.
The present invention has following advantage:
1, oligosaccharides and derivative thereof more easily are absorbed itself, have better biological activity, as multiple pharmacological effect such as antitumor, anti-various cardiovascular diseasess, antiviral, anti-oxidant, hypoglycemic and strengthening immunity;
2, oligosaccharides and derivative thereof have better reactive behavior, the easier and ionic reaction formation title complex as part, can give full play to the physiologically active of trace element vanadium and polysaccharide derivates, make both effects mutually coordinate and strengthen, improve vanadium utilizability in vivo.
Embodiment
Embodiment 1:
The 10g sodium alginate is dissolved in 500mL distilled water, drips sulfuric acid and regulate H
+ultimate density is 0.22mol/L, and 24h degrades under 90 ℃ of water-baths.NaOH solution is regulated degradation solution pH to 7, filtered while hot.The concentrated solution alcohol precipitation, the crude product after vacuum-drying is dissolved in a small amount of water, removes by filter insolubles.Strongly acidic cation-exchange and the desalination of weak base type resin anion(R.A) for liquid glucose, alcohol precipitation after elutriant is concentrated, 40 ℃ of vacuum-drying 24h obtain the brown alga oligose I, and molecular-weight average is 4.1kd.
1g brown alga oligose I is dissolved in 20mL distilled water, and 40%NaOH solution is adjusted pH to 12, remains pH value of solution >=12 in whole reaction process.Stir 30min under 30 ℃ of water-baths, add 0.25g VOSO
45H
2o, reaction 4-8h becomes clear to solution.Reaction solution concentrates alcohol precipitation, precipitates by 70% washing with alcohol more than 2 times.Product is dissolved in a small amount of water through dialysis tubing dialysis 24h desalination, adds acetone precipitation, suction filtration, and with absolute ethanol washing, more than 2 times, 40 ℃ of vacuum-drying 24h obtain brown alga oligose I vanadium complex.
Embodiment 2, get the 10g sodium alginate and add in the three-necked flask that contains 200mL distilled water, under 100 ℃ of water-baths, stir 30min, add the H of 20mL30%
2o
2reaction 50min.NaOH solution is regulated degradation solution pH to 7, filtered while hot.The concentrated solution alcohol precipitation, the crude product after vacuum-drying is dissolved in a small amount of water, removes by filter insolubles.Strongly acidic cation-exchange and the desalination of weak base type anionite-exchange resin for liquid glucose, alcohol precipitation after elutriant is concentrated, 40 ℃ of vacuum-drying 24h obtain the brown alga oligose II, and molecular-weight average is 1.6kd.
1g brown alga oligose II is dissolved in 20mL distilled water, and 40%NaOH solution is adjusted pH to 12, remains pH value of solution >=12 in whole reaction process.Stir 30min under 30 ℃ of water-baths, add 0.25g VOSO
45H
2o, reaction 4-8h becomes clear to solution.Reaction solution concentrates alcohol precipitation, precipitates by 70% washing with alcohol more than 2 times.Product is dissolved in a small amount of water through dialysis tubing dialysis 24h desalination, adds acetone precipitation, suction filtration, and with absolute ethanol washing, more than 2 times, 40 ℃ of vacuum-drying 24h obtain brown alga oligose II vanadium complex.
Embodiment 3:
Get the 9g agarose and add in the round-bottomed flask that contains 600mL distilled water, stir under 100 ℃ of water-baths and make it be dissolved into the transparent colloid shape fully, add the 10mL concentrated hydrochloric acid, making concentration of hydrochloric acid is 0.2mol/L, and 50 ℃ of stirring reactions 5 hours, adjust pH to 7 with NaOH solution.Suction filtration, concentrated, the concentrated solution alcohol precipitation, the crude product after vacuum-drying is dissolved in a small amount of water, removes by filter insolubles.With strongly acidic cation-exchange and the desalination of weak base type anionite-exchange resin, alcohol precipitation after elutriant is concentrated, 40 ℃ of vacuum-drying 24h obtain agaropectin oligose, and molecular-weight average is 1.1kd.
The 1g agaropectin oligose is dissolved in 20mL distilled water, and 40%NaOH solution is adjusted pH to 12, remains pH value of solution >=12 in whole reaction process.Stir 30min under 30 ℃ of water-baths, add 0.25g VOSO
45H
2o, reaction 4-8h becomes clear to solution.Reaction solution concentrates alcohol precipitation, precipitates by 70% washing with alcohol more than 2 times.Product is dissolved in a small amount of water through dialysis tubing dialysis 24h desalination, adds acetone precipitation, suction filtration, and with absolute ethanol washing, more than 2 times, 40 ℃ of vacuum-drying 24h obtain the agaropectin oligose vanadium complex.
Embodiment 4:
The 4g agaropectin oligose is poured in the three-necked flask with mechanical stirring device, added 100mL distilled water to dissolve, add the NaOH solution alkalization 1h of 60mL1mol/L.Then divide three times and add the 4.8g Mono Chloro Acetic Acid, reaction 4h remain that pH value of solution is greater than 9 under 60 ℃.Drip acetic acid adjust pH to 7.0, vacuum concentration, concentrated solution precipitates with dehydrated alcohol, precipitates by 70% washing with alcohol more than 2 times.Product is dissolved in a small amount of water through dialysis tubing dialysis 24h desalination, adds acetone precipitation, suction filtration, and with absolute ethanol washing, more than 2 times, 40 ℃ of vacuum-drying 24h obtain the carboxymethyl agaropectin oligose.
The preparation of carboxymethyl agaropectin oligose vanadium complex: 1g carboxymethyl agaropectin oligose is dissolved in 20mL distilled water, and 40%NaOH solution is adjusted pH to 12, remains pH value of solution >=12 in whole reaction process.Stir 30min under 30 ℃ of water-baths, add 0.25g VOSO
45H
2o, reaction 4-8h becomes clear to solution.Reaction solution concentrates alcohol precipitation, and precipitation by 70% washing with alcohol repeatedly.Product is dissolved in a small amount of water through dialysis tubing dialysis 24h desalination, adds acetone precipitation, suction filtration, and with absolute ethanol washing, more than 2 times, 40 ℃ of vacuum-drying 24h obtain carboxymethyl agaropectin oligose vanadium complex.
The restraining effect of oligosaccharides vanadium complex to the BEL-7402 cancer cell multiplication
Adopt sulphonyl rhodamine B (sulforhodamine B, SRB) protein staining method
[131]to human liver cancer cell, BEL-7402 is screened.The well-grown human liver cancer cell BEL-7402 of tryptic digestion, then, with 10% bovine serum 1640 suspension 200 μ L, adjusting cell count is 2 * 10
5mL
-1, adding to 96 orifice plates, the 0.1mL/ hole, become different gradient solutions (16 μ g/mL, 63 μ g/mL, 250 μ g/mL, 1000 μ g/mL, 4000 μ g/mL) to add respectively in cell hole diluted chemical compound, and each extent of dilution is established 4 holes, and 37 ℃, 5%CO
2effect 72h.After the sudden and violent leakage of sample, cell is fixed with 12% trichoroacetic acid(TCA), and dyes with the sulphonyl rhodamine B, then by microplate reader, surveys the OD value at 515nm place.Inhibiting rate (Inhibition ratio) calculation formula is as follows:
Ir＝[(A
2-A
1)/A
2]×100％
In formula: A
1for adding the OD value after sample solution, A
2for the OD value of control group, Ir is inhibiting rate.Test-results is in Table 1.
Table 1
By data in table, can find out, four kinds of oligosaccharides vanadium complexes that the present invention obtains all show restraining effect preferably to the BEL-7402 cancer cell multiplication.
The restraining effect of oligosaccharides vanadium complex to enzyme PTP1B
PTP 1B (PTP1B) is the member of classics in Protein-tyrosine-phosphatase (PTPs) family, is a kind of non-receptor type tyrosine phosphatase.PTP1B is the negative regulatory factor in the insulin signaling conductive process, by dephosphorylation, is hydrolyzed the insulin receptor of phosphorylation and the transmission that the tyrosine on acceptor suppresses insulin signaling thereof.Therefore insulin signaling weakening in transmittance process can cause glycometabolic disorder in body cell, to the restraining effect of PTP1B, is conducive to the conduction of insulin signaling, is conducive to glycometabolicly normally carry out, and the treatment of diabetes is had to important meaning.
Reaction system comprises the MoPs damping fluid of pH7.4, and final concentration is 2 * 10
-5the PTP1B of mol/L, final concentration is 1 * 10
-2the p-NPP of mol/L, the alga oligosaccharide vanadium complex that primary dcreening operation concentration is 80 μ g/mL (the alga oligosaccharide vanadium complex is used DMSO to dissolve and cryopreservation).Reaction system mixes and is placed on 37 ℃ of lower water-bath half an hour, adds the NaOH solution termination reaction of 1mol/L, is placed in the light absorption value of measuring 405nm place on microplate reader to observe enzyme variation and the alga oligosaccharide vanadium complex inhibition situation to it of living.
In formula, V
samplemean to be added with the enzyme original speed of alga oligosaccharide vanadium complex, V
dMSOexpression is without the enzyme original speed of alga oligosaccharide vanadium complex, and the primary dcreening operation of each compound arranges 3 multiple holes, and %Inhibition is inhibiting rate.Test-results is in Table 2.
Table 2
Show that by above data the oligosaccharides vanadium complex all has certain restraining effect to PTP1B.Wherein carboxymethyl agaropectin oligose vanadium complex is the best inhibitor of PTP1B, and the potential using value that suppresses blood sugar increasing is arranged.
Claims (8)
1. the preparation method of an oligosaccharides and derivative vanadium complex thereof is characterized in that: at first polysaccharide is hydrolyzed and obtains oligosaccharides, then by oligosaccharides or derivatives thereof and VO
2+carry out complex reaction, forming title complex, removing the unnecessary mineral ion that has neither part nor lot in reaction, obtaining the oligosaccharides vanadium complex.
2. preparation method according to claim 1, is characterized in that the described polysaccharide method that obtains oligosaccharides that is hydrolyzed is: sodium alginate is dissolved in distilled water, drips sulfuric acid and regulate H
+ultimate density is 0.22mol/L, under 90 ℃ of water-baths, degrades; Regulate degradation solution pH to 7, filtered while hot with NaOH solution; The concentrated solution alcohol precipitation, the crude product after vacuum-drying is dissolved in a small amount of water, removes by filter insolubles; Strongly acidic cation-exchange and the desalination of weak base type resin anion(R.A) for liquid glucose, alcohol precipitation after elutriant is concentrated, vacuum-drying obtains the brown alga oligose I, and molecular-weight average is 4.1kd.
3. preparation method according to claim 1, is characterized in that the described polysaccharide method that obtains oligosaccharides that is hydrolyzed is: sodium alginate is added to distilled water, stir under 100 ℃ of water-baths, add H
2o
2reaction; Regulate degradation solution pH to 7, filtered while hot with NaOH solution; The concentrated solution alcohol precipitation, the crude product after vacuum-drying is dissolved in a small amount of water, removes by filter insolubles; Strongly acidic cation-exchange and the desalination of weak base type anionite-exchange resin for liquid glucose, alcohol precipitation after elutriant is concentrated; Vacuum-drying obtains the brown alga oligose II, and molecular-weight average is 1.6kd.
4. preparation method according to claim 1, it is characterized in that the described polysaccharide method that obtains oligosaccharides that is hydrolyzed is: get agarose and add distilled water, stir and make it be dissolved into the transparent colloid shape fully under 100 ℃ of water-baths, add concentrated hydrochloric acid, making concentration of hydrochloric acid is 0.2mol/L, 50 ℃ of stirring reactions 5 hours, adjust pH to 7 with NaOH solution; Suction filtration, concentrated, the concentrated solution alcohol precipitation, the crude product after vacuum-drying is dissolved in a small amount of water, removes by filter insolubles; With strongly acidic cation-exchange and the desalination of weak base type anionite-exchange resin, alcohol precipitation after elutriant is concentrated, vacuum-drying obtains agaropectin oligose, and molecular-weight average is 1.1kd.
5. preparation method according to claim 1, is characterized in that the described polysaccharide method that obtains oligosaccharides that is hydrolyzed is: agaropectin oligose is added to the distilled water stirring and dissolving, add the alkalization of NaOH solution; Then divide three times and add Mono Chloro Acetic Acid, reaction 4h remain that pH value of solution is greater than 9 under 60 ℃; Drip acetic acid adjust pH to 7.0, vacuum concentration, concentrated solution precipitates with dehydrated alcohol, and precipitation is by 70% washing with alcohol repeatedly; Product is dissolved in a small amount of water through dialysis tubing dialysis 24h desalination, adds acetone precipitation, suction filtration, and with absolute ethanol washing repeatedly, vacuum-drying obtains the carboxymethyl agaropectin oligose.
6. preparation method according to claim 1, is characterized in that described oligosaccharides or derivatives thereof and VO
2+in the method for carrying out complex reaction, be: during the brown alga oligose I is dissolved in to distilled water, with NaOH solution, adjust pH to 12, remain pH value of solution>=12 in whole reaction process; Stir 30-50min under 30 ℃ of water-baths, add VOSO
45H
2o, reaction 4-8h becomes clear to solution; Reaction solution concentrates alcohol precipitation, precipitation; By 70% washing with alcohol repeatedly; Product is dissolved in a small amount of water through dialysis tubing dialysis 24h desalination, adds acetone precipitation, suction filtration, and with absolute ethanol washing repeatedly, 40 ℃ of vacuum-drying 24h obtain brown alga oligose I vanadium complex.
7. the application of an oligosaccharides vanadium complex is characterized in that: for the inhibition to the BEL-7402 cancer cell multiplication.
8. the application of an oligosaccharides vanadium complex is characterized in that: for inhibitory enzyme PTP1B activity.
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| CN107118284A (en) * | 2017-06-02 | 2017-09-01 | 福建农林大学 | A kind of sulfated oligosaccharide zinc and preparation method thereof |
| CN107118284B (en) * | 2017-06-02 | 2019-05-03 | 福建农林大学 | A kind of sulfated oligosaccharide zinc and preparation method thereof |
| CN109734761A (en) * | 2019-02-28 | 2019-05-10 | 福建农林大学 | A kind of preparation method and applications of Enteromorpha fucose complex compound |
| CN111848827A (en) * | 2020-06-10 | 2020-10-30 | 青岛海大生物集团有限公司 | Novel chlorella polysaccharide bactericide and preparation method thereof |
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