CN102321196B - O-salicylic acid esterified oligo-chitosan salicylaldehyde Schiff base bacteriostatic agent and preparation method thereof - Google Patents
O-salicylic acid esterified oligo-chitosan salicylaldehyde Schiff base bacteriostatic agent and preparation method thereof Download PDFInfo
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- CN102321196B CN102321196B CN 201110306402 CN201110306402A CN102321196B CN 102321196 B CN102321196 B CN 102321196B CN 201110306402 CN201110306402 CN 201110306402 CN 201110306402 A CN201110306402 A CN 201110306402A CN 102321196 B CN102321196 B CN 102321196B
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Abstract
The invention discloses a natural bacteriostatic agent of O-salicylic acid esterified oligo-chitosan salicylaldehyde Schiff base and a preparation method thereof. The preparation method comprises the following steps: firstly modifying C2-NH2 on a molecular structure of oligo-chitosan with strong bacteriostasis by salicylaldehyde so as to synthesize oligo-chitosan salicylaldehyde Schiff base; then performing condensation of C6-OH on the oligo-chitosan salicylaldehyde Schiff base by a DDC method to form O-salicylic acid esterified oligo-chitosan salicylaldehyde Schiff base. The preparation method has simple operations, and safe operation environment, and the obtained oligo-chitosan derivative has significantly improved antibacterial properties. The O-salicylic acid esterified oligo-chitosansalicylaldehyde Schiff base of the invention can be used as a bacteriostatic agent which has inhibition effect on escherichia coli, aureus staphylococcus, and saccharomyces cerevisiae.
Description
Technical field
The invention belongs to a kind of natural bacteriostatic agent-O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde and preparation method thereof.
Background technology
Along with living standards of the people improve, healthy and green concept is more and more accepted by masses.Exploitation is efficient, the natural anticorrosion antiseptic-germicide of safety, wide spectrum, stable performance more and more receives investigator's concern.The market requirement to the natural anticorrosion antiseptic-germicide is also inevitable growing.
Result of study both domestic and external shows, the anti-microbial activity of chitosan and molecular weight have certain dependency, and the chitosan oligomer that molecular weight obviously improves in 5000 following solvabilities shows stronger anti-microbial activity.But compare with existing chemosynthesis antiseptic-germicide, anti-microbial activity is still lower and Mycophyta be there is no suppress active.Compare with numerous natural extracts with anti-microbial activity, chitosan oligomer possesses numerous potential advantages of exploitation: 1) chitosan has biodegradable, biocompatibility, biological nontoxic; 2) C on its molecular structure
2-NH
2And C
6-OH is all desirable sites of structural modification, can further improve anti-microbial activity by chemical modification.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of natural bacteriostatic agent O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde.In recent years along with going deep into that various compounds are studied, the anti-microbial property of phenolic acid compound and antivirus action are gradually by cognitive and utilization.The present invention is intended to antibacterial stronger chitosan oligomer molecular structure C
2-NH
2And C
6The upper introducing of-OH has the phenolic hydroxyl group group of stronger bacteriostatic activity, thereby prepares a kind of novel natural bacteriostatic agent with many anti-microbial activities center.
For achieving the above object, the present invention takes following technical scheme:
A kind of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde is the C on 3000～5000 chitosan molecular structure at molecular weight
2-NH
2Be modified into the formation Schiff's base with salicylic aldehyde, wherein, the Schiff's base substitution value is greater than 95mol%; And the C in described chitosan molecular structure
6-OH and Whitfield's ointment esterification, its gamma value are 60mol%-75mol%.
With described O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde of the present invention as fungistat.
O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde of the present invention is as fungistat, and this fungistat is inhibited to intestinal bacteria, gold-coloured staphylococci and saccharomyces cerevisiae.
A kind of preparation method of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde, the method comprises the steps:
(1) with molecular weight be the mixed solution that 3000～5000 chitosan oligomer is placed in 2 volume %～4 volume % acetums and methyl alcohol, wherein, acetum and methyl alcohol are equal-volume, and the mass concentration of chitosan oligomer in the mixed solution of acetum and methyl alcohol is 4%～8%, swelling 1h-2h;
(2) salicylic aldehyde is dissolved in methyl alcohol, in this methyl alcohol and step (1), methyl alcohol used is isopyknic, join again after dissolving in the oligopolymerization chitosan sugar soln that step (1) that swelling completes obtains, at room temperature stir lower reaction 20～24h, wherein, salicylic aldehyde and chitosan oligomer consumption mol ratio (n
(-CHO/-NH2)) be 6～8: 1;
(3) the preparation liquid that obtains in step (2) is regulated pH and be neutral rear the filtration, trapped substance after immersion, washing, filtration and drying, is got substitution value greater than the chitosan oligomer schiff base of salicylaldehyde of 95mol%;
(4) the chitosan oligomer schiff base of salicylaldehyde that step (3) is synthetic is dissolved in methylene dichloride, and the concentration of dissolving is 1.0wt%～5.0wt%; After adding again the DMAP and the 3A molecular sieve as dewatering agent as catalyzer, add the Whitfield's ointment as ornamental equivalent, add DCC (N after stirring reaction 10min-15min under the ice-water bath condition, N '-dicyclohexyl carbimide), esterification 40～52h under condition of ice bath, various ratio of components are: the mass ratio of chitosan oligomer schiff base of salicylaldehyde, Whitfield's ointment and DCC is 1: 4～5: 4～5; The mass ratio of chitosan oligomer schiff base of salicylaldehyde and DMAP is 5～10: 1, and the 3A molecular sieve accounts for 4～6% of total reaction volume;
(5) after esterification, filter, collection filtrate is used successively with methylene dichloride and distilled water and is washed respectively, adds anhydrous Na after washing again
2SO
4Siccative, after filtration, the collecting precipitation thing is dry, removes methylene dichloride through distillation and obtains yellow O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde.
In the preparation method of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde of the present invention, in described step (3) to trapped substance through soaking, washing, filtering detailed process for being use washing with acetone, filter 23～4 time, use afterwards NaHCO
3Solution soaks under room temperature, stirs, and filters; Extremely neutral with washed with de-ionized water again; Soak with methyl alcohol more at last.
In the preparation method of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde of the present invention, in described step (3), in drying process, be to carry out vacuum-drying under 40 ℃ of conditions.
In the preparation method of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde of the present invention, in described step (5), collection filtrate in step (5) is used successively with methylene dichloride and distilled water and is distinguished in washing process, the consumption of each methylene dichloride used or distilled water respectively with collect the same volume of filtrate, and wash respectively 2～5 times.
In the preparation method of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde of the present invention, in described step (5), to remove in the methylene dichloride process in distillation, the temperature of distillation is 90 ℃.
In the preparation method of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde of the present invention, in described step (5), the gamma value that obtains yellow O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde is 60～75mol%.
Advantage of the present invention is:
The O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde that this preparation method obtains is owing to having introduced the stronger phenolic hydroxyl group of a plurality of biocidal properties, not only bacterium has been shown better inhibition (before being modification as the minimal inhibitory concentration to intestinal bacteria, gold-coloured staphylococci and saccharomyces cerevisiae 60～70% of chitosan oligomer) at antibiosis, the mould in fungi has also been shown stronger restraining effect.
The O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde natural bacteriostatic agent preparation method who provides in the present invention, simple to operate, operation environment safety, gained oligopolymerization chitosan derivative has obtained obvious improvement aspect anti-microbial property.
Description of drawings
Fig. 1 is the synthetic chitosan oligomer schiff base of salicylaldehyde of chitosan oligomer derivatize process of the present invention and the apparent proterties figure of O-Whitfield's ointment esterification chitosan oligomer Vanillin Schiff's base.Wherein, Fig. 1-a is the apparent proterties figure of chitosan oligomer; Fig. 1-b is the apparent proterties figure of chitosan oligomer schiff base of salicylaldehyde; Fig. 1-c is the apparent proterties figure of O-salicylate oligopolymerization chitosan sugar vanillin Schiff's base.
Fig. 2 is the IR collection of illustrative plates of chitosan oligomer and O-salicylate chitosan oligomer Schiff's base.Wherein, Fig. 2-d is the IR collection of illustrative plates of chitosan oligomer; Fig. 2-e is the IR collection of illustrative plates of O-salicylate chitosan oligomer Schiff's base.
Fig. 3 is the comparison diagram to the inhibitions of various microorganisms of the O-salicylate chitosan oligomer schiff base of salicylaldehyde aqueous solution of the oligopolymerization chitosan sugar aqueous solution of concentration 1wt% and concentration 1wt%.Wherein, the right side figure of Fig. 3-f be the oligopolymerization chitosan sugar aqueous solution of concentration 1wt% to colibacillary inhibition figure, the left side figure of Fig. 3-f is that the O-salicylate chitosan oligomer schiff base of salicylaldehyde aqueous solution of concentration 1wt% is to colibacillary inhibition figure; The right side figure of Fig. 3-g be the oligopolymerization chitosan sugar aqueous solution of concentration 1wt% to the inhibition figure of gold-coloured staphylococci, the left side figure of Fig. 3-g is that the O-salicylate chitosan oligomer schiff base of salicylaldehyde aqueous solution of concentration 1wt% is to the inhibition figure of gold-coloured staphylococci; The right side figure of Fig. 3-h be the oligopolymerization chitosan sugar aqueous solution of concentration 1wt% to the inhibition figure of saccharomyces cerevisiae, the left side figure of Fig. 3-h is that the O-salicylate chitosan oligomer schiff base of salicylaldehyde aqueous solution of concentration 1wt% is to the inhibition figure of saccharomyces cerevisiae; The right side figure of Fig. 3-s is the inhibition figure of the oligopolymerization chitosan sugar aqueous solution of concentration 1wt% unknown mould that the laboratory is separated, and the left side figure of Fig. 3-s is the inhibition figure of the O-salicylate chitosan oligomer schiff base of salicylaldehyde aqueous solution of concentration 1wt% unknown mould that the laboratory is separated.
Embodiment
Embodiment
Be in the acetum of 5000 the chitosan oligomer 2 volume % that are dissolved in 60ml, to be placed in the three-necked flask that agitator is housed with the 2.0g relative molecular weight; Add again 60ml methyl alcohol, mix rear swelling 1h.Add the aldehyde (CHO/-NH that is dissolved in 60ml methyl alcohol in reaction system
2Mol ratio is 8: 1), stirring reaction 24h under room temperature.
Take out reaction solution, the NaOH solution adjust pH that drips 10wt% is neutral, uses 180ml washing with acetone, filter 23 at every turn; Use afterwards 180ml 5wt%NaHCO
3Solution soaks, stirs 100min under room temperature, filter; Use again repeatedly extremely neutral with washed with de-ionized water.Use at last the methyl alcohol soaked overnight, after filtering under 40 ℃ of conditions vacuum-drying to constant weight, obtain the chitosan oligomer schiff base of salicylaldehyde, be 100mol% through its Schiff's base substitution value of ultimate analysis.
The chitosan oligomer Schiff's base 1.5g that gets preparation is scattered in the methylene dichloride of 40ml, be placed in the 250mL four-necked bottle that agitator and reflux are housed, add again the 6g Whitfield's ointment, (0.25gDMAP 4-dimethyl pyrimidine) and 3A molecular sieve 5g, adding 6gDCC after stirring reaction 10min under the ice-water bath condition, discharging after reaction 48h.
After slurry filtration, the filtrate of collecting is washed respectively 3 times in order to methylene dichloride and distilled water successively, remove oil layer with separating funnel after washing.The consumption of each methylene dichloride or distilled water is identical with the volume of collecting filtrate respectively.Add anhydrous Na after washing 3 times
2SO
4Siccative, filter with separating funnel and collect filtrate, revolve to steam with Rotary Evaporators and remove methylene dichloride, remove in the methylene dichloride process in distillation, the temperature of distillation is 90 ℃, removing the O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde that obtains pink decorating film after methylene dichloride, is 73mol% through measuring its gamma value.
Wherein the measuring method of gamma value is:
The O-salicylate chitosan oligomer Schiff's base that accurately takes 0.5g is placed in the 250mL Erlenmeyer flask, adds 25mL acetone and several phenolphthalein indicators, adds the NaOH standardized solution 25mL of 0.5mol/L after mixing, saponification 60min under the induction stirring condition.Be titrated to red the disappearance with concentration 0.5mol/LHCl standardized solution and be terminal point, get HCl and consume volume V
1Do blank test with chitosan oligomer, get HCl and consume volume V
2
Gamma value (%)=(1-V
1/ V
2) * 100%
The chitosan oligomer schiff base of salicylaldehyde that chitosan oligomer derivatize process is synthetic and the apparent proterties of O-Whitfield's ointment esterification chitosan oligomer Vanillin Schiff's base are seen Fig. 1.
Can be observed by Fig. 1, flaxen chitosan oligomer powder (as shown in Fig. 1-a) is chitosan oligomer schiff base of salicylaldehyde (as shown in Fig. 1-b) after synthesizing Schiff's base with salicylic aldehyde, very large change has occured in apparent colour, is jonquilleous crystal grain.Further be O-salicylate oligopolymerization chitosan sugar vanillin Schiff's base (as shown in Fig. 1-c) after Whitfield's ointment generation esterification, pinkiness smectic solid.Two kinds of derivatives are all irritating smells slightly of chitosan oligomer schiff base of salicylaldehyde and O-salicylate oligopolymerization chitosan sugar vanillin Schiff's base.
Adopt the KBr pressed disc method, at 4000～400cm
-1The IR collection of illustrative plates of measuring chitosan oligomer and O-salicylate chitosan oligomer Schiff's base in scope is seen Fig. 2.
In comparison diagram 2, the IR figure of chitosan oligomer and salicylate chitosan oligomer Schiff's base can find, the IR spectrogram (as shown in Fig. 2-e) of O-salicylate chitosan oligomer Schiff's base is at 1274cm
-1The characteristic peak of phenolic hydroxyl group has appearred in the place, at 1648cm
-1The characteristic peak that the C=N Schiff's base occurs is at 1120cm
-1And 1180cm
-1The characteristic peak of ester group has appearred in the place.And at 1072cm
-1The C of place
6-OH characteristic absorbance peak intensity diminishes, and 3446cm
-1The place-the OH absorption peak obviously narrows down, supposition be because on a large amount of sugar ring-OH participates in occuring due to esterification reduces.1580,1498 and 1461cm
-1The phenyl ring charateristic avsorption band that the place occurs has confirmed that further Whitfield's ointment and salicylic aldehyde with chitosan oligomer, esterification have occured respectively and Schiff's base is modified.
The O-salicylate chitosan oligomer schiff base of salicylaldehyde of 1wt% (its solvent is deionized water) is seen Fig. 3 and table 1 to inhibition and the chitosan oligomer contrast of various microorganisms.
Table 1 chitosan oligomer and the derivative average diameter of inhibition zone (cm) to microorganism
Claims (9)
1. O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde is the C on 3000～5000 chitosan molecular structure at molecular weight
2-NH
2Be modified into the formation Schiff's base with salicylic aldehyde, wherein, the Schiff's base substitution value is greater than 95mol%; And the C in described chitosan molecular structure
6-OH and Whitfield's ointment esterification, its gamma value are 60mol%-75mol%.
With O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde claimed in claim 1 as fungistat.
3. fungistat according to claim 2, described fungistat is inhibited to intestinal bacteria, gold-coloured staphylococci and saccharomyces cerevisiae.
4. the preparation method of an O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde, it is characterized in that: the method comprises the steps:
(1) with molecular weight be the mixed solution that 3000～5000 chitosan oligomer is placed in 2 volume %～4 volume % acetums and methyl alcohol, wherein, acetum and methyl alcohol are equal-volume, and the mass concentration of chitosan oligomer in the mixed solution of acetum and methyl alcohol is 4%～8%, swelling 1h-2h;
(2) salicylic aldehyde is dissolved in methyl alcohol, in this methyl alcohol and step (1), methyl alcohol used is isopyknic, join again after dissolving in the oligopolymerization chitosan sugar soln that step (1) that swelling completes obtains, at room temperature stir lower reaction 20～24h, wherein, salicylic aldehyde and chitosan oligomer consumption mol ratio (n
(-CHO/-NH2)) be 6～8: 1;
(3) the preparation liquid that obtains in step (2) is regulated pH and be neutral rear the filtration, trapped substance after immersion, washing, filtration and drying, is got substitution value greater than the chitosan oligomer schiff base of salicylaldehyde of 95mol%;
(4) the chitosan oligomer schiff base of salicylaldehyde that step (3) is synthetic is dissolved in methylene dichloride, and the concentration of dissolving is 1.0wt%～5.0wt%; After adding again the DMAP and the 3A molecular sieve as dewatering agent as catalyzer, add the Whitfield's ointment as ornamental equivalent, add DCC (N after stirring reaction 10min-15min under the ice-water bath condition, N '-dicyclohexyl carbimide), esterification 40～52h under condition of ice bath, various ratio of components are: the mass ratio of chitosan oligomer schiff base of salicylaldehyde, Whitfield's ointment and DCC is 1: 4～5: 4～5; The mass ratio of chitosan oligomer schiff base of salicylaldehyde and DMAP is 5～10: 1, and the 3A molecular sieve accounts for 4～6% of total reaction volume;
(5) after esterification, filter, collection filtrate is used successively with methylene dichloride and distilled water and is washed respectively, adds anhydrous Na after washing again
2SO
4Siccative, after filtration, the collecting precipitation thing is dry, removes methylene dichloride through distillation and obtains yellow O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde.
5. the preparation method of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde according to claim 4, it is characterized in that: in described step (3) to trapped substance through soaking, washing, filtering detailed process for being use washing with acetone, filter 23～4 time, use afterwards NaHCO
3Solution soaks under room temperature, stirs, and filters; Extremely neutral with washed with de-ionized water again; Soak with methyl alcohol more at last.
6. the preparation method of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde according to claim 4, is characterized in that: in described step (3), in drying process, be to carry out vacuum-drying under 40 ℃ of conditions.
7. the preparation method of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde according to claim 4, it is characterized in that: in described step (5), collection filtrate in step (5) is used successively with methylene dichloride and distilled water and is distinguished in washing process, the consumption of each methylene dichloride used or distilled water respectively with collect the same volume of filtrate, and wash respectively 2～5 times.
8. the preparation method of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde according to claim 4, it is characterized in that: in described step (5), remove in the methylene dichloride process in distillation, the temperature of distillation is 90 ℃.
9. the preparation method of O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde according to claim 4, it is characterized in that: in described step (5), the gamma value that obtains yellow O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde is 60～75mol%.
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| CN105218700B (en) * | 2015-07-24 | 2018-03-06 | 江南大学 | A kind of chitosan oligosaccharide O kojic acids Mannich base derivative antibacterial agent and preparation method thereof |
| CN106967184B (en) * | 2017-04-10 | 2019-09-06 | 江南大学 | A kind of chitosan oligosaccharide-O- spiceleaf 01 derivatives and its preparation method and application |
| CN107184986A (en) * | 2017-04-24 | 2017-09-22 | 佛山科学技术学院 | The synthetic method and its product of a kind of NSAIDs chitosan |
| CN113501909B (en) * | 2021-07-28 | 2023-01-03 | 西北师范大学 | Preparation method of Schiff base metal complex-loaded antibacterial microspheres |
| CN116554365A (en) * | 2023-05-08 | 2023-08-08 | 微著生物科技(东营)有限责任公司 | Preparation method of metal-chitosan catalyst, prepared catalyst and application thereof |
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