CN102863555B - A kind of Chitosan sulfate schiff base and synthetic method thereof - Google Patents
A kind of Chitosan sulfate schiff base and synthetic method thereof Download PDFInfo
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- CN102863555B CN102863555B CN201210362053.9A CN201210362053A CN102863555B CN 102863555 B CN102863555 B CN 102863555B CN 201210362053 A CN201210362053 A CN 201210362053A CN 102863555 B CN102863555 B CN 102863555B
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Abstract
The present invention relates to household chemicals field and pharmaceutical industries, specifically a kind of Chitosan sulfate schiff base and synthetic method thereof.Chitosan sulfate schiff base is by chitosan sulfate esterification, and after sulphating, amino and rancinamycin IV react gained, as the formula (1),
Description
Technical field
The present invention relates to household chemicals field and pharmaceutical industries, specifically a kind of Chitosan sulfate schiff base and synthetic method thereof.
Background technology
Chitosan (Chitosan) be a kind of be extensively present in occurring in nature renewable, have no side effect, biocompatibility and the good native amino polysaccharide of degradation property, himself and derivative thereof have physiology, the pharmacological function character of many uniquenesses, are widely used in the multiple industry fields such as medicine, food, agricultural, daily use chemicals, environmental protection.The structures and characteristics that chitosan itself is special, has sterilization, bacteriostatic activity, and nontoxic, free of contamination characteristic, can as the object modified to developing secondary lead compound.Sulfated chitosan except having multiple better biological activity, also has extraordinary water-soluble compared with chitosan, but seldom has product sulfated chitosan being carried out to modification further.So, chitosan is further modified, there is very large DEVELOPMENT PROSPECT.
Rancinamycin IV is a kind of active compound containing phenolic hydroxyl group mainly extracted from plant, has good antibacterial, anti-oxidant isoreactivity.Can widespread use in food, medicine, the industry of change shape product.But because molecular weight is low, make rancinamycin IV poor stability.Existing bibliographical information, by small molecule active compound access macromolecular compound, can improve its stability, play synergism, expand its range of application.
Simultaneously chitosan also has certain oxidation-resistance as polyol itself, and sulfated chitosan compared with chitosan except there is better oxidation-resistance, also there is this feature of good aqueous solubility.For the oxidation-resistance of Tri-methyl Quaternary Ammonium Salt of Chitosan, access has the active group of good oxidation resistance, is expected to obtain more highly active chitosan derivatives.
Summary of the invention
The object of the invention is to provide a kind of Chitosan sulfate schiff base and synthetic method thereof and application.
For achieving the above object, the technical solution used in the present invention is:
A kind of Chitosan sulfate schiff base, Chitosan sulfate schiff base is by chitosan sulfate esterification, and after sulphating, amino and rancinamycin IV react gained, as the formula (1),
The synthetic method of Chitosan sulfate schiff base, first chitosan carries out sulphating, on sulphating after product amino with rancinamycin IV excessive concentration be in 20%-100% ethanolic soln with 20-60 DEG C of conditions under react 1-8h, namely obtain Chitosan sulfate schiff base after purifying; The molar weight of described rancinamycin IV is 1-3 times of sulfated chitosan.
In building-up process; first chitosan 2 bit amino is protected through Tetra hydro Phthalic anhydride; with excessive esterifying agent by 3 of chitosan with 6 whole sulphatings of hydroxyl; secondly sulphating after product is carried out removing 2 bit amino protections; finally the sulphating after product and rancinamycin IV that remove 2 bit amino protections are reacted, obtain Chitosan sulfate schiff base.
Described chitosan molecule amount is between 1-70 ten thousand, and deacetylation is 80-100%.
The advantage that the present invention has is: gained compound Chitosan sulfate schiff base of the present invention is compared with chitosan, and its oxidation-resistance is greatly improved.Because rancinamycin IV is exactly just have good oxidation-resistance, and when being accessed sulfated chitosan, does not destroy active function groups-phenolic hydroxyl group that it mainly plays oxidation-resistance, so can put forward the oxidation-resistance doing chitosan.More than enhance chitosan biological activity, and water compatible, play synergism, expand its Application Areas, can in household chemicals field widespread uses such as food, change shape product.
Simultaneously simple in synthesis technique step of the present invention, cost is lower, required equipment and raw material are easy to get.
Accompanying drawing explanation
The synthetic route chart that Fig. 1 provides for the embodiment of the present invention.
The infrared spectrogram of the chitosan that Fig. 2 provides for the embodiment of the present invention.
Fig. 3 provides sulfated chitosan infrared spectrogram for the embodiment of the present invention.
Fig. 4 provides the infrared spectrogram of sulfated chitosan rancinamycin IV schiff bases for the embodiment of the present invention.
Embodiment
The invention will be further described by way of example more below, provides implementation detail of the present invention, but be not intended to limit protection scope of the present invention.
Embodiment 1
Sulfated chitosan rancinamycin IV schiff bases is compound shown in (formula 1)
Synthetic route
The present embodiment is by above synthetic route synthesis target compound.
(1) synthetic compound (): under nitrogen protection, 5g chitosan and 10g phthalic acid is intoxicated reacts 8h in 120mL95%N, N-dimethylformamide solvent, temperature of reaction is 120 DEG C.After reaction terminates, by reaction solution impouring 1000mL mixture of ice and water, product is separated out.Products therefrom is through purifying after 72h with dehydrated alcohol soxhlet extraction, 60 DEG C of vacuum-dryings obtain compound (one) 8.5g.
(2) synthetic compound (two): 10mL chlorsulfonic acid is added dropwise in 60mL pyridine, react after 40 minutes in ice-water bath, reacting liquid temperature is increased to 100 DEG C.Get 5g compound () again to add to wherein, and react 3h under 100 DEG C of conditions, after reaction terminates, be cooled to room temperature.In reaction solution impouring 200mL water, after question response liquid and the abundant mixing of water, poured into by gained solution in 500mL dehydrated alcohol, compound (two) is separated out.Products therefrom is after washing twice with dehydrated alcohol, and 60 DEG C of vacuum-dryings obtain compound (two) 7.3g.
(3) synthetic compound (three): 5g compound (two) is dissolved in 100mL20% hydrazine hydrate solution that (commercially available water ammonia hydrazine solution is 85%; after diluting 4.25 times;); under the protection of nitrogen; 4h is reacted under 100 DEG C of conditions; after reaction terminates, in reaction solution impouring 400mL dehydrated alcohol, product is separated out.Products therefrom is through purifying after 72h with dehydrated alcohol soxhlet extraction, 60 DEG C of vacuum-dryings obtain compound (three) 2.4g.
(4) synthetic compound sulfated chitosan rancinamycin IV schiff bases: 2g compound (three) and 1.5g rancinamycin IV are scattered in 100mL10% ethanolic soln, 2h is reacted under 25 DEG C of conditions, after reaction terminates, in reaction solution impouring 500mL dehydrated alcohol, product is separated out.Products therefrom is through purifying after 72h with dehydrated alcohol soxhlet extraction, 60 DEG C of vacuum-dryings obtain product 2.6g.Products made thereby is buff powder, soluble in water.
Fig. 2 to be deacetylation be 90% chitosan: 3421.10cm-1 is the stretching vibration absorption peak of O-H and N-H, 2881.13cm-1 be the absorption peak of C-H stretching vibration, 1600.63cm-1 be the flexural vibration absorption peak of NH2, 1076.09cm-1 and 1153.22cm-1 is the absorption peak of C-O stretching vibration, 898.85cm-1 is stretching vibration absorption peak Fig. 3 of chitosan six-ring is the infrared spectrogram of sulfated chitosan: compared to Figure 1 1253cm-1 is sulfuric acid vibration and receives peak, 786cm-1 is C-O-S vibration absorption peak and 1608 amino vibration peak are retained.The charateristic avsorption band of Fig. 4 to be the infrared spectrogram of sulfated chitosan rancinamycin IV schiff bases: 1639.20cm-1 be schiff bases.1519.92cm
-1, 690.25cm
-1for the charateristic avsorption band of benzene.More than prove the formation of target compound.
Embodiment 2
Difference from Example 1 is:
Synthetic compound sulfated chitosan rancinamycin IV schiff bases: 2g compound (three) and 2g rancinamycin IV are scattered in 100mL30% ethanolic soln, react 3h under 30 DEG C of conditions, after waiting reaction to terminate, in reaction solution impouring 500mL dehydrated alcohol, product is separated out.Products therefrom is through purifying after 72h with dehydrated alcohol soxhlet extraction, 60 DEG C of vacuum-dryings obtain product 2.6g.
Embodiment 3
Difference from Example 1 is:
Synthetic compound sulfated chitosan rancinamycin IV schiff bases: 2g compound (three) and 2.5g rancinamycin IV are scattered in 100mL100% ethanolic soln, 3h is reacted under 25 DEG C of conditions, after reaction terminates, in reaction solution impouring 500mL dehydrated alcohol, product is separated out.Products therefrom is through purifying after 72h with dehydrated alcohol soxhlet extraction, 60 DEG C of vacuum-dryings obtain product 2.6g.
Application examples
Remove the mensuration of hydroxy radical qiao resistance of oxidation:
Measure the ability of the removal hydroxy radical qiao of synthesized gallic acid chitosan trimethylammonium quaternary amine and chitosan trimethylammonium quaternary amine respectively and contrast:
After product prepared by embodiment 1-3 and Tri-methyl Quaternary Ammonium Salt of Chitosan vacuum lyophilization to constant weight, prepare desired concn in table one respectively, get prepared solution 1mL, phosphoric acid buffer 1mL(and prepare phosphoric acid buffer: get 41.58gNa respectively
2hPO
412H
2o, 5.2887gNaH
2pO
42H
2o, adds water and is dissolved to 1000ml.), the sarranine 1ml of 360ug/m, 2mmol/LEDTA-Fe0.5ml, sample liquid 1.0ml, 3% hydrogen peroxide 1ml, mix in test tube, react 30min in 37 degree of water-baths after, working sample is in the absorbancy at 520nm place, and blank group 1ml distilled water substitutes test sample, control group 1.0ml distilled water and 1ml phosphoric acid buffer substitute sample and hydrogen peroxide (note: sample all surveys twice, averages).
Remove hydroxyl radicals (%) [(the blank 520nm of A sample 520nm-A)/(A contrasts the blank 520nm of 520nm-A)] × 100
Experimental result: synthesized by above-described embodiment, the removal hydroxyl radicals of sulfated chitosan rancinamycin IV schiff bases and chitosan is as shown in table 1, the removal hydroxyl radicals of synthesized sulfated chitosan rancinamycin IV schiff bases is obviously better than chitosan.
Table 1, the ability (%) of the removal hydroxy radical qiao of chitosan and sulfated chitosan rancinamycin IV schiff bases
Claims (3)
1. a Chitosan sulfate schiff base, is characterized in that: Chitosan sulfate schiff base is by chitosan sulfate esterification, and after sulphating, amino and rancinamycin IV react gained, shown in (1),
2. the synthetic method of a Chitosan sulfate schiff base according to claim 1, it is characterized in that: first chitosan carries out sulphating, after sulphating amino with rancinamycin IV excessive concentration be in 20%-100% ethanolic soln with 20-60 DEG C of conditions under react 1-8h, namely obtain Chitosan sulfate schiff base after purifying; The molar weight of described rancinamycin IV is 1-3 times of sulfated chitosan.
3., by the synthetic method of Chitosan sulfate schiff base according to claim 2, it is characterized in that: described chitosan molecule amount is between 1-70 ten thousand, and deacetylation is 80-100%.
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| CN104231112B (en) * | 2014-04-29 | 2016-03-23 | 深圳大学 | A kind of synthetic method of CARB OXYMETHYL-CHITOSAN sulfation product |
| CN104530259B (en) * | 2015-01-14 | 2017-01-11 | 皖西学院 | Chitosan type Schiff base, preparing method thereof and feather cleaning deodorant based on same |
| CN106832058B (en) * | 2017-03-07 | 2019-06-07 | 陕西科技大学 | A kind of O- succinic acid Chitosan Schiff-base and preparation method thereof |
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| CN1471921A (en) * | 2003-07-05 | 2004-02-04 | 中国科学院海洋研究所 | Use of chitin oligosaccharide sulphate and/or chitin sulfate for preparing medicine for diabetes |
| CN1740789A (en) * | 2004-08-25 | 2006-03-01 | 中国科学院海洋研究所 | The Study on Antioxidant Activities method of location sulfated chitosan |
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| JP2001187801A (en) * | 1999-12-28 | 2001-07-10 | Daishin Kagaku Kk | N-alkylchitosan derivative and its production method |
| JP2002226503A (en) * | 2001-01-30 | 2002-08-14 | Daishin Kagaku Kk | Method for producing n-alkylchitosan derivative, n- alkylchitosan derivative and polymer produced by using the derivative |
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| CN1471921A (en) * | 2003-07-05 | 2004-02-04 | 中国科学院海洋研究所 | Use of chitin oligosaccharide sulphate and/or chitin sulfate for preparing medicine for diabetes |
| CN1740789A (en) * | 2004-08-25 | 2006-03-01 | 中国科学院海洋研究所 | The Study on Antioxidant Activities method of location sulfated chitosan |
| CN102399304A (en) * | 2011-07-22 | 2012-04-04 | 中国科学院烟台海岸带研究所 | Chitosan quaternary amine salt gallate, synthetic method thereof and application thereof |
| CN102373193A (en) * | 2011-09-27 | 2012-03-14 | 华东理工大学 | Microbial cell immobilizing carrier and related application |
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| Magnetic Catechol-Chitosan with Bioinspired Adhesive Surface: Preparation and Immobilization of ω-Transaminase;Kefeng Ni, et al.;《PLoS one》;20120717;第7卷(第7期);第6页右栏第3段第3~9行 * |
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