CN102321196A - 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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- CN102321196A CN102321196A CN201110306402A CN201110306402A CN102321196A CN 102321196 A CN102321196 A CN 102321196A CN 201110306402 A CN201110306402 A CN 201110306402A CN 201110306402 A CN201110306402 A CN 201110306402A CN 102321196 A CN102321196 A CN 102321196A
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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-chitosan salicylaldehyde 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 notion with green 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.Also inevitable growing to the market requirement of natural anticorrosion antiseptic-germicide.
Domestic and international research result shows that 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 suppressed active basically.Compare with numerous natural extracts with anti-microbial activity, chitosan oligomer possesses numerous potential advantages of exploitation: 1) chitosan has biodegradable, biocompatibility, biological nontoxic property; 2) C on its molecular structure
2-NH
2And C
6-OH all is desirable sites of structural modification, can come further to improve anti-microbial activity through 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 go deep into along with what all cpds was 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
6-OH is last to introduce the phenolic hydroxyl group group with strong bacteriostatic activity, thereby prepares a kind of novel natural bacteriostatic agent with many anti-microbial activities center.
For realizing above-mentioned purpose, 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 the 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 Zhi Huadu 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, this method comprises the steps:
(1) be the mixed solution that 3000~5000 chitosan oligomer places 2 volume %~4 volume % acetums and methyl alcohol with molecular weight; 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 the methyl alcohol; Used methyl alcohol is isopyknic in this methyl alcohol and the step (1), joins after the dissolving in the oligopolymerization chitosan sugar soln that step (1) that swelling accomplishes obtains again, and at room temperature stirs reaction 20~24h down; Wherein, salicylic aldehyde and chitosan oligomer consumption mol ratio (n
(-CHO/-NH2)) be 6~8: 1;
(3) the preparation liquid that obtains in the step (2) is regulated pH and be neutral after-filtration, trapped substance after immersion, washing, filtration and drying, is got the chitosan oligomer schiff base of salicylaldehyde of substitution value greater than 95mol%;
(4) step (3) synthetic chitosan oligomer schiff base of salicylaldehyde is dissolved in methylene dichloride, dissolved concentration is 1.0wt%~5.0wt%; After adding 4-Dimethylamino pyridine and 3A molecular sieve again as dewatering agent as catalyzer; Adding is as the Whitfield's ointment of ornamental equivalent; Behind stirring reaction 10min-15min under the ice-water bath condition, add DCC (N; N '-dicyclohexyl carbimide), esterification 40~52h under condition of ice bath, various amounts of components ratios 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 4-Dimethylamino pyridine is 5~10: 1, and the 3A molecular sieve accounts for 4~6% of total reaction volume;
(5) after the esterification, filter, collecting filtrates to use successively with methylene dichloride and zero(ppm) water washs respectively, adds anhydrous Na after the washing again
2SO
4Siccative, through filtering, 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 with washing with acetone, filter 23~4 time, use NaHCO afterwards
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 under 40 ℃ of conditions, to carry out vacuum-drying.
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 filtrating in step (5) is used successively with methylene dichloride and zero(ppm) water and is distinguished in the washing process; The consumption of each used methylene dichloride or zero(ppm) water respectively with collect the same volume of filtrating, 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 distillatory temperature 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 Zhi Huadu 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 introduced the stronger phenolic hydroxyl group of a plurality of biocidal properties; Not only bacterium has been shown better inhibition effect (before being modification like minimal inhibitory concentration 60~70% of chitosan oligomer) at antibiosis, the mould in the fungi has also been shown stronger restraining effect intestinal bacteria, gold-coloured staphylococci and saccharomyces cerevisiae.
The O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde natural bacteriostatic agent preparation method who provides among the present invention, simple to operate, operation environment safety, gained oligopolymerization chitosan verivate has obtained obvious improvement aspect anti-microbial property.
Description of drawings
Fig. 1 is the apparent proterties figure of chitosan oligomer derivatize process synthetic chitosan oligomer schiff base of salicylaldehyde of the present invention and 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 inhibition effects of various mikrobes of the O-salicylate chitosan oligomer schiff base of salicylaldehyde aqueous solution of oligopolymerization chitosan sugar aqueous solution and the concentration 1wt% of concentration 1wt%.Wherein, the right side figure of Fig. 3-f be the oligopolymerization chitosan sugar aqueous solution of concentration 1wt% to colibacillary inhibition design sketch, 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 design sketch; The right side figure of Fig. 3-g is the inhibition design sketch of the oligopolymerization chitosan sugar aqueous solution of concentration 1wt% to gold-coloured staphylococci, and the left side figure of Fig. 3-g is the inhibition design sketch of the O-salicylate chitosan oligomer schiff base of salicylaldehyde aqueous solution of concentration 1wt% to gold-coloured staphylococci; The right side figure of Fig. 3-h is the inhibition design sketch of the oligopolymerization chitosan sugar aqueous solution of concentration 1wt% to saccharomyces cerevisiae, and the left side figure of Fig. 3-h is the inhibition design sketch of the O-salicylate chitosan oligomer schiff base of salicylaldehyde aqueous solution of concentration 1wt% to saccharomyces cerevisiae; The right side figure of Fig. 3-s is the inhibition design sketch of the oligopolymerization chitosan sugar aqueous solution of concentration 1wt% to the isolating unknown mould in laboratory, and the left side figure of Fig. 3-s is the inhibition design sketch of the O-salicylate chitosan oligomer schiff base of salicylaldehyde aqueous solution of concentration 1wt% to the isolating unknown mould in laboratory.
Embodiment
Embodiment
With the 2.0g relative molecular weight is in the acetum of 5000 the chitosan oligomer 2 volume % that are dissolved in 60ml, places the three-necked flask that whisking appliance is housed; Add 60ml methyl alcohol again, mix back swelling 1h.In reaction system, add the aldehyde (CHO/-NH that is dissolved in 60ml methyl alcohol
2Mol ratio is 8: 1), stirring reaction 24h under the 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 180ml 5wt%NaHCO afterwards
3Solution soaks, stirs 100min under room temperature, filter; Use repeatedly extremely neutral again with washed with de-ionized water.Using the methyl alcohol soaked overnight at last, filter back vacuum-drying under 40 ℃ of conditions and obtain the chitosan oligomer schiff base of salicylaldehyde to constant weight, is 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; Place the 250mL four-necked bottle that whisking appliance and reflux are housed; Add the 6g Whitfield's ointment again; 0.25gDMAP (4-dimethyl pyrimidine) and 3A molecular sieve 5g are adding 6gDCC behind the stirring reaction 10min under the ice-water bath condition, discharging behind the reaction 48h.
Behind the slurry filtration filtrating of collecting is washed respectively 3 times in order to methylene dichloride and zero(ppm) water successively, oil layer is removed with separating funnel in the washing back.The consumption of each methylene dichloride or zero(ppm) water is identical with the volume of collecting filtrating respectively.Add anhydrous Na after washing 3 times
2SO
4Siccative; Filter collection filtrating with separating funnel; Revolve steaming with Rotary Evaporators and remove methylene dichloride, remove in the methylene dichloride process in distillation, the distillatory temperature is 90 ℃; Removing the O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde that obtains pink decorating film behind the methylene dichloride, is 73mol% through measuring its Zhi Huadu.
Wherein the measuring method of Zhi Huadu is:
The O-salicylate chitosan oligomer Schiff's base that accurately takes by weighing 0.5g places the 250mL Erlenmeyer flask, adds 25mL acetone and several phenolphthalein indicators, adds the NaOH standardized solution 25mL of 0.5mol/L behind the mixing, saponification 60min under the induction stirring condition.Be terminal point with concentration 0.5mol/LHCl standard solution titration to red color disappeared, get HCl and consume volume V
1Do blank test with chitosan oligomer, get HCl and consume volume V
2
Zhi Huadu (%)=(1-V
1/ V
2) * 100%
The apparent proterties of chitosan oligomer derivatize process synthetic chitosan oligomer schiff base of salicylaldehyde and O-Whitfield's ointment esterification chitosan oligomer Vanillin Schiff's base is seen Fig. 1.
Can be observed by Fig. 1, flaxen chitosan oligomer powder (shown in Fig. 1-a) is chitosan oligomer schiff base of salicylaldehyde (shown in Fig. 1-b) after synthesizing Schiff's base with salicylic aldehyde, and very big change has taken place apparent colour, is jonquilleous crystal grain.Further be O-salicylate oligopolymerization chitosan sugar vanillin Schiff's base (shown in Fig. 1-c) after the Whitfield's ointment generation esterification, pinkiness smectic solid.Two kinds of verivates are that chitosan oligomer schiff base of salicylaldehyde and O-salicylate oligopolymerization chitosan sugar vanillin Schiff's base all have a little irritating smell.
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 the scope is seen Fig. 2.
The IR of chitosan oligomer and salicylate chitosan oligomer Schiff's base figure can find that the IR spectrogram (shown in Fig. 2-e) of O-salicylate chitosan oligomer Schiff's base is at 1274cm in the comparison diagram 2
-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 taking place 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 taken place 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 effect and the chitosan oligomer contrast of various mikrobes.
Table 1 chitosan oligomer and verivate are to the average diameter of inhibition zone (cm) of mikrobe
Claims (9)
1. O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde is the C on 3000~5000 the 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 Zhi Huadu are 60mol%-75mol%.
With the described O-Whitfield's ointment of claim 1 esterification chitosan oligomer schiff base of salicylaldehyde 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: this method comprises the steps:
(1) be the mixed solution that 3000~5000 chitosan oligomer places 2 volume %~4 volume % acetums and methyl alcohol with molecular weight; 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 the methyl alcohol; Used methyl alcohol is isopyknic in this methyl alcohol and the step (1), joins after the dissolving in the oligopolymerization chitosan sugar soln that step (1) that swelling accomplishes obtains again, and at room temperature stirs reaction 20~24h down; Wherein, salicylic aldehyde and chitosan oligomer consumption mol ratio (n
(-CHO/-NH2)) be 6~8: 1;
(3) the preparation liquid that obtains in the step (2) is regulated pH and be neutral after-filtration, trapped substance after immersion, washing, filtration and drying, is got the chitosan oligomer schiff base of salicylaldehyde of substitution value greater than 95mol%;
(4) step (3) synthetic chitosan oligomer schiff base of salicylaldehyde is dissolved in methylene dichloride, dissolved concentration is 1.0wt%~5.0wt%; After adding 4-Dimethylamino pyridine and 3A molecular sieve again as dewatering agent as catalyzer; Adding is as the Whitfield's ointment of ornamental equivalent; Behind stirring reaction 10min-15min under the ice-water bath condition, add DCC (N; N '-dicyclohexyl carbimide), esterification 40~52h under condition of ice bath, various amounts of components ratios 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 4-Dimethylamino pyridine is 5~10: 1, and the 3A molecular sieve accounts for 4~6% of total reaction volume;
(5) after the esterification, filter, collecting filtrates to use successively with methylene dichloride and zero(ppm) water washs respectively, adds anhydrous Na after the washing again
2SO
4Siccative, through filtering, 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 with washing with acetone, filter 23~4 time, use NaHCO afterwards
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 under 40 ℃ of conditions, to carry out vacuum-drying.
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 filtrating in step (5) is used successively with methylene dichloride and zero(ppm) water and is distinguished in the washing process; The consumption of each used methylene dichloride or zero(ppm) water respectively with collect the same volume of filtrating, 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 is characterized in that: in described step (5), remove in the methylene dichloride process in distillation, the distillatory temperature 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 Zhi Huadu that obtains yellow O-Whitfield's ointment esterification chitosan oligomer schiff base of salicylaldehyde is 60~75mol%.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017016022A1 (en) * | 2015-07-24 | 2017-02-02 | 江南大学 | Chito-oligosaccharide-o-kojic acid-mannich base derivative antibacterial agent and preparation method thereof |
CN106967184A (en) * | 2017-04-10 | 2017-07-21 | 江南大学 | A kind of chitosan oligosaccharide O spiceleaf 01 derivatives and its production and use |
CN108503725A (en) * | 2017-04-24 | 2018-09-07 | 聂鑫 | A kind of synthetic method and its product of non-steroidal anti-inflammatory drugs-chitosan |
CN113501909A (en) * | 2021-07-28 | 2021-10-15 | 西北师范大学 | Preparation method of antibacterial microspheres of polypropylene ester-loaded Schiff base metal complex |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1687142A (en) * | 2005-03-30 | 2005-10-26 | 中国科学院海洋研究所 | Shiff base derivative of carboxymerhyl chitosan and preparation method |
CN1982339A (en) * | 2005-12-14 | 2007-06-20 | 河南省科学院河南省发展计划委员会地理研究所 | Salicylic acid and chitin-2-6-bit graft and its production |
CN101259285A (en) * | 2008-04-23 | 2008-09-10 | 河南中医学院 | Application of 2-chitosan salicylic acid graft compound in anticoagulant and long-acting ease pain |
CN101314622A (en) * | 2008-06-26 | 2008-12-03 | 浙江大学 | Salicylic-g-chitosan oligosaccharide grafts and synthesizing process |
-
2011
- 2011-10-11 CN CN 201110306402 patent/CN102321196B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1687142A (en) * | 2005-03-30 | 2005-10-26 | 中国科学院海洋研究所 | Shiff base derivative of carboxymerhyl chitosan and preparation method |
CN1982339A (en) * | 2005-12-14 | 2007-06-20 | 河南省科学院河南省发展计划委员会地理研究所 | Salicylic acid and chitin-2-6-bit graft and its production |
CN101259285A (en) * | 2008-04-23 | 2008-09-10 | 河南中医学院 | Application of 2-chitosan salicylic acid graft compound in anticoagulant and long-acting ease pain |
CN101314622A (en) * | 2008-06-26 | 2008-12-03 | 浙江大学 | Salicylic-g-chitosan oligosaccharide grafts and synthesizing process |
Non-Patent Citations (1)
Title |
---|
韩永萍等: "DCC缩合酯化法合成水杨酸低聚壳聚糖酯及抑菌性研究", 《化学世界》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017016022A1 (en) * | 2015-07-24 | 2017-02-02 | 江南大学 | Chito-oligosaccharide-o-kojic acid-mannich base derivative antibacterial agent and preparation method thereof |
CN106967184A (en) * | 2017-04-10 | 2017-07-21 | 江南大学 | A kind of chitosan oligosaccharide O spiceleaf 01 derivatives and its production and use |
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 |
CN108503725A (en) * | 2017-04-24 | 2018-09-07 | 聂鑫 | A kind of synthetic method and its product of non-steroidal anti-inflammatory drugs-chitosan |
CN113501909A (en) * | 2021-07-28 | 2021-10-15 | 西北师范大学 | Preparation method of antibacterial microspheres of polypropylene ester-loaded Schiff base metal complex |
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