CN101875704A - Water-soluble chitosan schiff base derivative and preparation method and application thereof - Google Patents
Water-soluble chitosan schiff base derivative and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses water-soluble chitosan schiff base derivative and the preparation method and the application thereof. The water-soluble chitosan schiff base derivative is prepared by making chitosan and reducing sugar react with schiff base, wherein the chitosan has the average molecular weight of 5,000-1,000,000D. The water-soluble chitosan schiff base derivative has the structural formula of (I), wherein the R is the structural formula formed by the reducing sugar, the x, the y and the z represent the degree of polymerization, the x/(x+y)=0.3-0.99, and the z/(x+y)=0.1-0.99. The water-soluble chitosan schiff base derivative can be well dissolved in the solution, has the DPPH free radical scavenging capacity and a certain antibacterial activity and can be used as the antioxidants and the antibacterial agent.
Description
(1) technical field
The present invention relates to a kind of water-soluble chitosan schiff base derivative and its production and application.
(2) background technology
Chitosan is a kind of natural biopolymer polysaccharide of chitin after deacetylated, and the source is abundant, is only second to xylogen.It contains a large amount of free amine groups, and this characteristic makes it to become the few positively charged biopolymer of occurring in nature figure place, has also given its unique biological activity.The chitosan nontoxicity has excellent biological compatibility, biocidal property, degradability, promotion wound healing ability or the like.Has very big value in industries such as health care, agricultural, chemical industry.It is water-soluble that but the intensive intramolecular hydrogen bond causes molecular weight to be difficult to greater than 5000 chitosan, can only be dissolved in the olefin(e) acid solution, and this has limited the application of chitosan greatly.
Yet have amino and hydroxyl in the chitosan molecule, can carry out chemically modified to privileged site,, just can weaken the hydrogen bond action in the chitosan molecule greatly by in repeating unit, introducing group, increase its solvability, thereby widen its range of application and give its new function.The method that obtains water-soluble chitosan of modifying preferably that industry is generally acknowledged has following several: acidylate, and carboxymethylation, sulfonation, quaternary ammoniated, etherificate or the like.
Water-soluble chitosan is a kind of very important derivative in the chitosan derivatives, except giving the chitosan good solubility, and can also be as a kind of important intermediate.Water-soluble chitosan directly uses as auxiliary material in food, chemical industry and pharmaceutical industries as a kind of biomaterial that has very much using value at present:
(1) cm-chitosan: have characteristics such as biocidal property and moisture retention preferably, be mainly used in medicine and the cosmetic field.
(2) Quaterisation chitosan: the derivative of modification rate more than 0.45 all has good water-solubility, also has the ability of good biocidal property and chelated mineral, is mainly used in environment protection and the daily necessities.
(3) sulfated chitosan: low-molecular-weight sulfated chitosan has Blood clotting, now has been applied to pharmaceutical industries, but sulfated chitosan does not have the ability of removing the DPPH free radical.
(4) acylation chitosan: the chitosan of acetylize about 50% has good water-solubility; it is fewer that the Application Areas of this type of material is developed now; mainly as the agromelioration agent or as the thickening material in the field of food; but compare with raw materials of chitosan, the ability of its anti-DPPH free radical is more weak.
Yet the method for existing chemically modified raw materials of chitosan has all more or less used deleterious organic reagent, catalyzer or the like during the course, has brought hidden danger for the safe handling of chitosan derivatives.So original intention of the present invention is to find the reaction scheme of a safety, green, possesses simultaneously and can produce the water-soluble chitosan ability low-cost, on a large scale.Simultaneously, we consider one of principal element of influencing human body health be in body and environment the increase of harmful free radical begin, so research and develop the chitosan derivatives of safety non-toxic, have important practical significance for delaying senility, enhancement human health with abilities such as anti-oxidant activities.
(3) summary of the invention
First technical problem that the present invention will solve is to provide a kind of novel water-solubility chitosan derivative, this water-solubility chitosan derivative has good solubility in solution, also have the DPPH radical scavenging activity when keeping certain bacteriostatic activity.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of water-soluble chitosan schiff base derivative, be by chitosan and reducing sugar through the west not alkali reaction make; The molecular-weight average of described chitosan is 5000D～1000000D; The structure of described chitosan schiff base derivative is suc as formula shown in (I):
In the formula (I), R is the structural formula that reducing sugar forms; X, y, z represent the polymerization degree, i.e. corresponding construction unit number in the molecular chain, wherein x/ (x+y)=0.3～0.99; Z/ (x+y)=0.1～0.99.
Further, reducing sugar of the present invention is preferred one of following: fructose, maltose, semi-lactosi, lactose, rhamnosyl, pectinose, seminose.The preferred reducing sugar of the present invention is fructose, lactose or seminose.
Second technical problem that the present invention will solve is to provide a kind of preparation method of safe, green, simple, with low cost, water-soluble chitosan schiff base derivative that can large-scale industrial production.
For solving second technical problem, the present invention adopts following technical scheme:
A kind of preparation method of water-soluble chitosan schiff base derivative, comprising the steps: to get raw materials of chitosan, to be dissolved in mass percent be in 0.5～20.0% the acid solution, adding reducing sugar is that 20～120 ℃, pressure are abundant stirring reaction under 1～5 atmospheric condition in temperature, reaction finishes the after product dialysis and removes impurity, concentrates after lyophilize or vacuum-drying promptly obtain described chitosan schiff base derivative; The molecular-weight average of described chitosan is 5000～1000000, and the deacetylation of chitosan is 30～99%.
Further, described chitosan is 1: 0.5～100.0 in the molar ratio of the amino mole number that wherein contains and described reducing sugar, be preferably 1: 1～and 3.
Further, the acid in the described acid solution is formic acid, acetate, propionic acid, butyric acid, hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid, preferred acetate.
Further, preferable reaction temperature is 40～80 ℃; Preferred reaction pressure is 1 normal atmosphere.
The present invention is ultraviolet spectrophotometer assaying reaction degree under the 420nm wavelength, and the reaction times is generally at 48～96 hours.
The 3rd technical problem that the present invention will solve is to provide two kinds of application of described chitosan schiff base derivative, and promptly described water-soluble chitosan schiff base derivative is as the application of fungistat and antioxidant.
Compared with prior art, beneficial effect of the present invention is embodied in following method:
A) water-soluble chitosan schiff base derivative of the present invention is a kind of important chitosan derivatives, in the solution of pH 1～13, has good solubility, also has the DPPH radical scavenging activity when having kept certain bacteriostatic activity, can be used as food preservative, fungistat, also can be used as the additive with anti-oxidant activity of makeup and skin care product and natural dyestuff.
B) safe, green, simple, with low cost can large-scale industrial production
(4) embodiment
With specific embodiment technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto:
Embodiment 1:
Get the 3g deacetylation and be 0.96 raw materials of chitosan (molecular weight 100000D) and be dissolved in 2% (weight percent, in the acetum down together), fully the dissolving back adds the 3.3g seminose, in a normal atmosphere, 60 ℃ of abundant stirring reactions 48 hours, (reaction solution of different time is answered in negate to measure its level of response under the 420nm wavelength, by 4 times of dilutions behind the filter membrane of 0.45 μ m, place the absorption value under the glass cuvette survey 420nm wavelength).Reaction finishes the after product dialysis and removes impurity, is concentrated into original volume 1/3 postlyophilization or vacuum-drying and promptly obtains required chitosan schiff base derivative.
Determine that with the mode of acid base titration or colloidal titration its modification rate is 35%, determines its structure with H NMR and IR.
1H NMR (D
2O) δ=1.96 (NHCOC
H 3); δ=2.84 (H2); δ=4.5,3.46-3.77 (chitosan skeleton H1, H3, H4, H5, the H on H6 and the grafted seminose).IR:3430cm
-1And 2930cm
-1(NH, the stretching vibration of-OH and-CH-), 1635cm
-1(west is alkali C=N not), 1384cm
-1(acid amides III band), 1156cm
-1(C-O-C between the chitosan repeating unit), 1073 and 1033cm
-1(the C-O stretching vibration on the chitosan skeleton).The derivative antibacterial circle diameter is listed in the table 1.
Embodiment 2:
Get the 1g deacetylation and be 0.90 raw materials of chitosan (molecular weight 100000D) and be dissolved in 1.2% (weight percent, in the acetum down together), fully the dissolving back adds 1.1g fructose, in a normal atmosphere, 70 ℃ of abundant stirring reactions 96 hours, (reaction solution of different time is answered in negate to measure its level of response under the 420nm wavelength, by 4 times of dilutions behind the filter membrane of 0.45 μ m, place the absorption value under the glass cuvette survey 420nm wavelength).Reaction finishes the after product dialysis and removes impurity, is concentrated into original volume 1/3 postlyophilization or vacuum-drying and promptly obtains required chitosan schiff base derivative.
Determine that with the mode of acid base titration or colloidal titration its modification rate is 48%, determines its structure with H NMR and IR.
1H NMR (D
2O) δ=1.96 (NHCOC
H 3); δ=2.84 (H2); δ=4.5,3.46-3.77 (chitosan skeleton H1, H3, H4, H5, the H on H6 and the grafted fructose).IR:3430cm
-1And 2930cm
-1(NH, the stretching vibration of-OH and-CH-), 1635cm
-1(west is alkali C=N not), 1384cm
-1(acid amides III band), 1156cm
-1(C-O-C between the chitosan repeating unit), 1073 and 1033cm
-1(the C-O stretching vibration on the chitosan skeleton).The antibacterial circle diameter of derivative is listed in the table 1, and the concentration of partly removing of DPPH free radical is listed in the table 2, and solubleness is listed in the table 3.
Embodiment 3:
Get the 300g deacetylation and be 0.90 raw materials of chitosan (molecular weight 100000D) and be dissolved in 1.14% (weight percent, in the acetum down together), fully the dissolving back adds the 330g lactose, in a normal atmosphere, 70 ℃ of abundant stirring reactions 96 hours, (reaction solution of different time is answered in negate to measure its level of response under the 420nm wavelength, by 4 times of dilutions behind the filter membrane of 0.45 μ m, place the absorption value under the glass cuvette survey 420nm wavelength).Reaction finishes the after product dialysis and removes impurity, is concentrated into original volume 1/3 postlyophilization or vacuum-drying and promptly obtains required chitosan schiff base derivative.
Determine that with the mode of acid base titration or colloidal titration its modification rate is 56%, determines its structure with H NMR and IR.
1H NMR (D
2O) δ=1.96 (NHCOC
H 3); δ=2.84 (H2); δ=4.5,3.46-3.77 (chitosan skeleton H1, H3, H4, H5, the H on H6 and the grafted lactose).IR:3430cm
-1And 2930cm
-1(NH, the stretching vibration of-OH and-CH-), 1635cm
-1(west is alkali C=N not), 1384cm
-1(acid amides III band), 1156cm
-1(C-O-C between the chitosan repeating unit), 1073 and 1033cm
-1(the C-O stretching vibration on the chitosan skeleton).The antibacterial circle diameter of derivative is listed in the table 1, and the concentration of partly removing of DPPH free radical is listed in the table 2, and solubleness is listed in the table 3.
Embodiment 4:
Get the 100g deacetylation and be 0.90 raw materials of chitosan (molecular weight 100000D) and be dissolved in 1% (weight percent, in the acetum down together), fully the dissolving back adds 110g maltose, in a normal atmosphere, 60 ℃ of abundant stirring reactions 24 hours, (reaction solution of different time is answered in negate to measure its level of response under the 420nm wavelength, by 4 times of dilutions behind the filter membrane of 0.45 μ m, place the absorption value under the glass cuvette survey 420nm wavelength).Reaction finishes the after product dialysis and removes impurity, is concentrated into original volume 1/3 postlyophilization or vacuum-drying and promptly obtains required chitosan schiff base derivative.
Determine that with the mode of acid base titration or colloidal titration its modification rate is 23%, determines its structure with H NMR and IR.
1H NMR (D
2O) δ=1.96 (NHCOC
H 3); δ=2.84 (H2); δ=4.5,3.46-3.77 (chitosan skeleton H1, H3, H4, H5, the H on H6 and the grafted maltose).IR:3430cm
-1And 2930cm
-1(NH, the stretching vibration of-OH and-CH-), 1635cm
-1(west is alkali C=N not), 1384cm
-1(acid amides III band), 1156cm
-1(C-O-C between the chitosan repeating unit), 1073 and 1033cm
-1(the C-O stretching vibration on the chitosan skeleton).The derivative antibacterial circle diameter is listed in the table 1, and solubleness is listed in the table 3.
Implementation column 5:
The chitosan derivatives that we make embodiment 2 and embodiment 3 has carried out the external determination experiment of hexichol being removed ability for bitter taste acyl group free radical (DPPH).
Reagent: available from Shanghai lark prestige company, all the other reagent are homemade analytical pure to hexichol for bitter taste acyl group free radical (DPPH).
Method: take by weighing a certain amount of water-soluble chitosan schiff base derivative sample and put into test tube, the aqueous solution dissolving that adds certain volume respectively, join to such an extent that mother liquid medicine concentration is 2mg/mL, be made into this solution that drug level is 0.2,0.4,0.6,0.8,1.0,1.5, the solution of 2.0mg/mL.The sample solution 100 μ L and the 0.1mmol/L DPPH solution 100 μ L (sample real reaction concentration is 50 μ g/mL, 16.7 μ g/mL, 5.6 μ g/mL) in 96 orifice plates that add each concentration, every part establish 5 parallel.Sample adds back middling speed vibration 30s, measures its light absorption value (A under room temperature (25 ℃) and 517nm wavelength
p); Measure successively again after placing 20min under the room temperature; Measure the sample blank absorb light (A that does not add DPPH simultaneously
c: 100 μ L samples+100 μ L methyl alcohol) and add DPPH but do not add the light absorption value (A of sample
Max: 100 μ L DPPH+100 μ L methyl alcohol).With 100 μ g/mLV
CMeasure inhibiting rate (IR%) in contrast.
Partial results is listed in the table 2.From experimental result, chitosan schiff base derivative is a large amount of owing to containing-and OH has the ability of good removing DPPH free radical.
Principle: hexichol for bitter taste acyl group free radical (DPPH) be a kind of very stable be the free radical at center with nitrogen, its alcoholic solution is intense violet color, at the 517nm place one absorption peak is arranged.When having free-radical scavengers in the reactive system, it can match with the single electron of DPPH and the absorption peak at 517nm place is disappeared gradually, and the degree that this color shoals becomes stoichiometric relation with the sharing electron number.Therefore change the removing situation that degree can be used for detecting free radical according to disappear speed and peak value, thus the resistance of oxidation of evaluation test sample.Compare with other method have with DPPH screening free-radical scavengers easy, advantage fast.
Implementation column 6:
The water-soluble chitosan schiff base derivative that we make implementation column 1,2,3,4 has carried out the determination experiment of bacteriostasis.
Test organisms: intestinal bacteria (Escherichi a coli, E.coli), (Staphylococcusaureus S.aureus), is that Microbiological Lab provides by this to streptococcus aureus.
The activation of bacterial classification: will be tried bacterium and be inoculated in the 50mL liquid nutrient medium (LB substratum) 37 ℃ of 100r/min shaking table overnight incubation.With dilution plate counting process counting, making CFU is 10
7The bacteria suspension of individual/mL is standby.
Get 0.1mL CFU and be the bacteria suspension of 107/mL and coat on the LB culture dish, the Oxford cup of getting Φ 10mm is positioned on the culture dish, adds 0.6% acetic acid solution of the derivative of 0.2ml in the cup of Oxford, and 2 Oxford cups of every plate are cultivated 24h for 37 ℃.Cultivate and finish back survey antibacterial circle diameter.Data are listed in the table 1.
Comparative Examples 1: get xitix and compare, DPPH partly removes concentration and lists in the table 2.
Comparative Examples 2: get raw materials of chitosan and compare, DPPH partly removes concentration and lists in the table 2, and solubleness is listed in the table 3.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Intestinal bacteria antibacterial circle diameter (mm) | ??18.00±0.20 | ??17.50±0.50 | ??17.20±0.30 | ??18.00±0.20 |
| Staphylococcus aureus antibacterial circle diameter (mm) | ??17.00±0.15 | ??16.75±0.25 | ??16.90±0.20 | ??17.00±0.25 |
Table 2
| Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | |
| Concentration (mg/ml) | ??2.0 | ??1.0 | ??0.005 | ??2.0 |
| DPPH free radical scavenging activity (%) | ??52 | ??35 | ??50 | ??16 |
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 2 | |
| Solubleness (g/l) | ??7.2 | ??11.2 | ??20.3 | ??8.4 | ??0.0 |
| PH stability | ??＜7.5 | ??＜13.0 | ??＜13.0 | ??＜7.5 | ??＜4.0 |
Claims (10)
1. water-soluble chitosan schiff base derivative is characterized in that: described chitosan schiff base derivative be by chitosan and reducing sugar through the west not alkali reaction make; The molecular-weight average of described chitosan is 5000D～1000000D; The structure of described chitosan schiff base derivative is suc as formula shown in (I):
In the formula (I), R is the structural formula that reducing sugar forms; X, y, z represent the polymerization degree, x/ (x+y)=0.3～0.99 wherein, z/ (x+y)=0.1～0.99.
2. water-soluble chitosan schiff base derivative as claimed in claim 1 is characterized in that: described reducing sugar is selected from one of following: fructose, maltose, semi-lactosi, lactose, rhamnosyl, pectinose, seminose.
3. the preparation method of a water-soluble chitosan schiff base derivative as claimed in claim 1, it is characterized in that described preparation method is: getting raw materials of chitosan, to be dissolved in mass percent be in 0.5～20.0% the acid solution, adding reducing sugar is that 20～120 ℃, pressure are abundant stirring reaction under 1～5 atmospheric condition in temperature, reaction finishes the after product dialysis and removes impurity, concentrates after lyophilize or vacuum-drying promptly obtain described chitosan schiff base derivative; The molecular-weight average of described chitosan is 5000D～1000000D, and the deacetylation of chitosan is 30～99%.
4. the preparation method of water-soluble chitosan schiff base derivative as claimed in claim 3 is characterized in that: described chitosan is 1: 0.5～100.0 in the molar ratio of the amino mole number that wherein contains and described reducing sugar.
5. the preparation method of water-soluble chitosan schiff base derivative as claimed in claim 3 is characterized in that: described chitosan is 1: 3～1 in the molar ratio of the amino mole number that wherein contains and described reducing sugar.
6. the preparation method of water-soluble chitosan schiff base derivative as claimed in claim 3, it is characterized in that: described acid is formic acid, acetate, propionic acid, butyric acid, hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid.
7. the preparation method of water-soluble chitosan schiff base derivative as claimed in claim 3 is characterized in that: described being reflected under 40～80 ℃ the temperature condition carried out.
8. the preparation method of water-soluble chitosan schiff base derivative as claimed in claim 3, it is characterized in that: described being reflected under the 1 atmospheric pressure condition carried out.
9. water-soluble chitosan schiff base derivative as claimed in claim 1 is as the application of fungistat.
10. water-soluble chitosan schiff base derivative as claimed in claim 1 is as the application of antioxidant.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839569A (en) * | 2012-08-02 | 2012-12-26 | 翔瑞（泉州）纳米科技有限公司 | Chitosan wet tissue paper and preparation method thereof |
| CN103156844A (en) * | 2011-12-15 | 2013-06-19 | 天津市国际生物医药联合研究院 | Application of Schiff base compound in inhibition of activity of NDM-1 |
| CN104138594A (en) * | 2013-05-06 | 2014-11-12 | 南开大学 | Uses of D-homocysteine-L-phenylalanine dipeptide derivatives in preparation of new Delhi metallo-beta-lactamase 1 inhibitors |
| CN106117391A (en) * | 2016-06-28 | 2016-11-16 | 田东县浙缘农业科技有限公司 | A kind of preparation method of chitosan aroma type Schiff |
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| US5747475A (en) * | 1995-04-04 | 1998-05-05 | Wound Healing Of Oklahoma | Chitosan-derived biomaterials |
| CN1468869A (en) * | 2003-06-02 | 2004-01-21 | 中国海洋大学 | N-lactose acyl chitosan |
| US6756363B1 (en) * | 2000-11-17 | 2004-06-29 | Wound Healing Of Oklahoma, Inc. | Solutions and films of glycated chitosan |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5747475A (en) * | 1995-04-04 | 1998-05-05 | Wound Healing Of Oklahoma | Chitosan-derived biomaterials |
| US6756363B1 (en) * | 2000-11-17 | 2004-06-29 | Wound Healing Of Oklahoma, Inc. | Solutions and films of glycated chitosan |
| CN1468869A (en) * | 2003-06-02 | 2004-01-21 | 中国海洋大学 | N-lactose acyl chitosan |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103156844A (en) * | 2011-12-15 | 2013-06-19 | 天津市国际生物医药联合研究院 | Application of Schiff base compound in inhibition of activity of NDM-1 |
| CN103156844B (en) * | 2011-12-15 | 2016-11-16 | 天津市国际生物医药联合研究院 | The application in the medicine of preparation suppression NDM-1 activity of the Schiff base compounds |
| CN102839569A (en) * | 2012-08-02 | 2012-12-26 | 翔瑞（泉州）纳米科技有限公司 | Chitosan wet tissue paper and preparation method thereof |
| CN102839569B (en) * | 2012-08-02 | 2016-03-02 | 戴李宗 | A kind of chitosan wet tissue paper and preparation method thereof |
| CN104138594A (en) * | 2013-05-06 | 2014-11-12 | 南开大学 | Uses of D-homocysteine-L-phenylalanine dipeptide derivatives in preparation of new Delhi metallo-beta-lactamase 1 inhibitors |
| CN104138594B (en) * | 2013-05-06 | 2020-08-14 | 南开大学 | Application of D-homocysteine-L-phenylalanine dipeptide derivative in preparation of new Delhi metallo-beta-lactamase 1 inhibitor |
| CN106117391A (en) * | 2016-06-28 | 2016-11-16 | 田东县浙缘农业科技有限公司 | A kind of preparation method of chitosan aroma type Schiff |
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Open date: 20101103 |