CN101649005A - Para aminobenzoyl chitosan and preparing method thereof - Google Patents
Para aminobenzoyl chitosan and preparing method thereof Download PDFInfo
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- CN101649005A CN101649005A CN200910018199A CN200910018199A CN101649005A CN 101649005 A CN101649005 A CN 101649005A CN 200910018199 A CN200910018199 A CN 200910018199A CN 200910018199 A CN200910018199 A CN 200910018199A CN 101649005 A CN101649005 A CN 101649005A
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Abstract
The invention discloses a para aminobenzoyl chitosan and a preparing method thereof. The structure is disclosed as shown on the right, wherein, n is 160-180; after para aminobenzoyl structure is led in on a chitosan molecular chain, the minimal inhibitory concentration of the compound to colibacillus, staphylococcus aureus and aspergillus niger is respectively 0.1%, 0.1% and 1%. The compound has the following physical and chemical indexes: the compound is a pale yellow powder solid, can be dissolved in water and glycol and has the molecular weight of 45-50KD. Para aminobenzoyl chitosan strengthens the antibacterial activity of the chitosan, enlarges the antibiosis range of the chitosan, has favourable antibacterial activity for colibacillus, staphylococcus aureus and aspergillus niger andcan be applied as an antibacterial anticorrosive additive when preparing food.
Description
Technical field
The present invention relates to a kind of functional deriv of chitosan chemical modification, it is applied to food service industry, belongs to chemical field.
Background technology
Chitosan is the deacetylated product of chitin, is that a large amount of exist unique a kind of have a cationic alkaline polysaccharide in the organic sphere.Because of the effect of intramolecularly and intermolecular hydrogen bonding, chitosan only is dissolved in acid and acidic aqueous solution.Contain modifiable groups such as a large amount of hydroxyls, amino on the chitosan molecule chain, can obtain various derivatives, therefore can enlarge its range of application by chemical modification with specific function.For example, chitosan has excellent biodegradability, biocompatibility, film forming characteristics and stronger antibiotic anti-corrosive fresh-keeping ability, is widely used in fields such as foodstuffs industry.Chitosan only can be dissolved in the acidic medium, has limited its range of application.Usually people improve the solvability or the flocculence of chitosan by introduce quaternary ammonium salt, alkyl, mineral acid etc. on chitosan molecule.The p-benzoyl base is grafted on the chitosan molecule chain; obtain the p-benzoyl chitosan derivatives; with intestinal bacteria, streptococcus aureus and aspergillus niger is experimental strain; derivative has been carried out anti-microbial activity research; drawn antibacterial growth curve, be expected to be applied to provide in the food preservatives experimental basis for this product.Prepare the p-benzoyl chitosan derivatives by the acylation reaction of acyl chlorides and chitosan, and it is carried out anti-microbial effect research, do not appear in the newspapers as yet.
Summary of the invention
The objective of the invention is to overcome the water-fast shortcoming of chitosan, a kind of chitosan derivatives with antibacterial effect is provided, can be used as antibiotic anticorrosive additive in the food.
Another object of the present invention provides above-mentioned chitosan derivatives---the preparation method of p-benzoyl chitosan.
The structure of p-benzoyl chitosan of the present invention is:
Wherein, n is between 160-180, and after introducing the p-benzoyl base on the chitosan molecule chain, this compound reaches 0.1%, 0.1% and 1% respectively to the minimum inhibitory concentration of intestinal bacteria, streptococcus aureus and aspergillus niger.The physical and chemical indexes of this compound: yellow powder powder solid, water-soluble and ethylene glycol, molecular weight are 45-50KD.
The present invention prepares p-benzoyl chlorine by para-amino benzoic acid and sulfur oxychloride reaction, prepares the p-benzoyl chitosan with chitosan reaction then.Get para-amino benzoic acid and put into three-necked bottle, add a certain amount of anhydrous diethyl ether, add sulfur oxychloride again, put in the ultrasonic washer of 30 ℃ of water temperatures, reacted 10 minutes; In three-necked bottle, add the certain amount of chitosan acetic acid solution, 5 ℃ of-45 ℃ of following ultra-sonic oscillation 1.5 hours, standing over night then; After reaction is finished, add a large amount of acetone product be precipitated out, filter, soak suction filtration after 24 hours with the mixed solvent of dehydrated alcohol and anhydrous diethyl ether again, again the filter cake behind the suction filtration is carried out Soxhlet with acetone and extracted 24 hours, after the vacuum-drying product.
The principal reaction that the present invention relates to had two steps:
(1) preparation p-benzoyl chlorine
(2) preparation p-benzoyl chitosan
The preparation method of described p-benzoyl chitosan compound, its preparation process is as follows:
(1) para-amino benzoic acid with weighing is dissolved in the 50-65 ℃ of distilled water hot suction filtration;
(2) filtrate cool to room temperature, at room temperature suction filtration;
(3) get filter cake, vacuum-drying obtains purified para-amino benzoic acid;
(4) para-amino benzoic acid is put in the three-necked bottle, add anhydrous diethyl ether para-amino benzoic acid is dissolved fully, add sulfur oxychloride again, put into water temperature and be in 20-40 ℃ the ultrasonic washer, ultra-sonic oscillation 10-60 minute, reaction product was a p-benzoyl chlorine;
(5) reaction product in cooling (4) step is dissolved in chitosan in the anhydrous acetic acid to 0-30 ℃, again it is added in the three-necked bottle, and at 5-45 ℃ of following ultra-sonic oscillation 1-3.5 hour, standing over night;
(6) the reaction product adding acetone with (5) step is precipitated out suction filtration until product p-benzoyl base chitosan;
(7) the mixed solvent immersion of the precipitation in (6) step being used dehydrated alcohol and anhydrous diethyl ether is after 12-24 hour, and suction filtration is got filter cake;
(8) filter cake that again (7) is gone on foot carries out Soxhlet extraction 24-30 hour with acetone, obtains product p-benzoyl chitosan after the vacuum-drying.
The processing condition of suction filtration are in described (1) step: dried by the fire 1-3 hour in 50-65 ℃ of baking oven with filter flask and B, use water pump suction filtration reaction solution down at 50-65 ℃ again, suction filtration is poured into filtrate in the clean beaker rapidly after finishing;
The processing condition of suction filtration all were during described (2), (6) and (7) went on foot: dried by the fire 1-3 hour in 50-65 ℃ of baking oven with filter flask and B, at room temperature use water pump suction filtration reaction solution again, suction filtration is poured into filtrate in the clean beaker rapidly after finishing.
Described para-amino benzoic acid: sulfur oxychloride: the weight ratio that feeds intake of chitosan is (1-5): (3-9): 1.
The dehydrated alcohol in described (7) step and the volume ratio of anhydrous diethyl ether are 1: (1-10).
The processing condition that the Soxhlet in described (8) step is extracted are: 55-65 ℃ of heating in water bath, extracted 24-30 hour.
The vacuum drying processing condition in described (8) step are: under 30-50 ℃, vacuum tightness is 8 * 10
4Pa, dry 12-24 hour.
Described p-benzoyl chitosan compound is as the application of preparation food preservation additive.
Beneficial effect of the present invention is: the p-benzoyl base is incorporated into the novel chitosan derivative of preparing on the chitosan molecule intestinal bacteria, streptococcus aureus and aspergillus niger are had good antibacterial activity; enlarge the scope of restraining fungi of chitosan, can be used as food preservation additive.
Description of drawings
Fig. 1 is the infrared spectrogram of chitosan.
Fig. 2 is the infrared spectrogram of prepared p-benzoyl chitosan.
Fig. 3 is the uv absorption spectra of chitosan and p-benzoyl chitosan acetic acid solution.
Fig. 4 chitosan and p-benzoyl chitosan are to the restraining effect figure of intestinal bacteria growth.
Fig. 5 chitosan and p-benzoyl chitosan are to the restraining effect figure of staphylococcus aureus growth.
Fig. 6 chitosan and p-benzoyl chitosan are to the restraining effect figure of aspergillus niger growth.
Embodiment
Embodiment 1:
Get the dry para-amino benzoic acid 1g that crosses and put into three-necked bottle, add the anhydrous diethyl ether of 30ml, add the 2ml sulfur oxychloride again, put in the ultrasonic washer of 30 ℃ of water temperatures, reacted 10 minutes.Be cooled to 25 ℃, the 0.5g chitosan is dissolved in the 30ml acetate, it is added in three-necked bottle, and 25 ℃ of following ultra-sonic oscillation 1 hour, standing over night.After reaction is finished, adding 70ml acetone is precipitated out product, suction filtration, be that the mixed solvent of 1: 1 dehydrated alcohol and anhydrous diethyl ether soaks suction filtration after 24 hours with the 50ml volume ratio again, again the filter cake behind the suction filtration is carried out Soxhlet with acetone and extracted 24 hours, get product---p-benzoyl chitosan after the vacuum-drying.
Embodiment 2:
Get the dry para-amino benzoic acid 1g that crosses and put into three-necked bottle, add the anhydrous diethyl ether of 30ml, add the 2ml sulfur oxychloride again, put in the ultrasonic washer of 30 ℃ of water temperatures, reacted 10 minutes.Be heated to 45 ℃, the 0.5g chitosan is dissolved in the 30ml acetate, again it is added in three-necked bottle, and 45 ℃ of following ultra-sonic oscillation 1 hour, standing over night.After reaction is finished, adding 70ml acetone is precipitated out product, suction filtration, be that the mixed solvent of 1: 1 dehydrated alcohol and anhydrous diethyl ether soaks suction filtration after 24 hours with the 50ml volume ratio again, again the filter cake behind the suction filtration is carried out Soxhlet with acetone and extracted 24 hours, get product---p-benzoyl chitosan after the vacuum-drying.
Embodiment 3:
Get the dry para-amino benzoic acid 1g that crosses and put into three-necked bottle, add the anhydrous diethyl ether of 30ml, add the 2ml sulfur oxychloride again, put in the ultrasonic washer of 30 ℃ of water temperatures, reacted 10 minutes.Be cooled to 5 ℃, the 0.5g chitosan is dissolved in the 30ml acetate, again it is added in three-necked bottle, and 5 ℃ of following ultra-sonic oscillation 1 hour, standing over night.After reaction is finished, adding 70ml acetone is precipitated out product, suction filtration, be that the mixed solvent of 1: 1 dehydrated alcohol and anhydrous diethyl ether soaks suction filtration after 24 hours with the 50ml volume ratio again, again the filter cake behind the suction filtration is carried out Soxhlet with acetone and extracted 24 hours, get product---p-benzoyl chitosan after the vacuum-drying.
Analysis chart 1 and Fig. 2 two width of cloth infrared spectrums as seen, 1597.2cm in the chitosan infrared spectrum
-1The place is amino N-H formation vibration peak, 2875.7cm
-1The place is C-H stretching vibration absorption peak, 3417.7cm
-1The place belongs to the absorption peak of O-H stretching vibration and N-H stretching vibration in the chitosan molecule, 1082.4cm
-1The place is the absorption peak of C-OH; 1735.5cm appears in the product
-1It is the C=O stretching vibration peak; 1602.3cm
-1And 1517.8cm
-1The place is the skeletal vibration absorption peak of phenyl ring; 1082.4cm
-1The C-OH absorption peak at place does not have big variation, can know p-benzoyl chlorine by inference and mainly on the amino of chitosan acylation reaction take place.
Fig. 3 is for being solvent with the acetum of 1g/L, and it is 1 * 10 that chitosan and p-benzoyl chitosan are made concentration
-4The solution of g/mL, the uv absorption spectra that records.Wherein, 2 is the uv absorption spectra of chitosan, and 1 is the uv absorption spectra of p-benzoyl chitosan.As can be seen from the figure, the p-benzoyl base is received on the chitosan molecule, because the influence of chromophores such as acid amides, the two keys of carbon oxygen, phenyl ring, chitosan derivatives has a big absorption peak at the 284nm place, strong ultraviolet radiation absorption peak value is promptly arranged at the 284nm place.
Embodiment 4:
Products therefrom p-benzoyl chitosan of the present invention and chitosan are to colibacillary antibacterial efficient (%)
Embodiment 5:
Products therefrom p-benzoyl chitosan of the present invention and chitosan are to the antibacterial efficient (%) of streptococcus aureus
Embodiment 6:
Products therefrom p-benzoyl chitosan of the present invention and chitosan are to the antibacterial efficient (%) of aspergillus niger
The mensuration of above-mentioned antibacterial efficient: preparation different mass fractional chitosan solution and derivative solution (acetum with 0.5% is a solvent).Sample solution with 0.1mL bacteria suspension and 0.1mL different concns is uniformly coated on the culture medium flat plate respectively, and is blank for not adding the bacteria suspension of sample solution.All flat boards are cultivated 24h in 37 ℃ of constant incubators, take out the bacterial growth situation of observing on each flat board, calculate bacteriostasis rate:
I＝(n
1-n
2)/n
1×100％
Wherein, n
1And n
2Be respectively blank and scribble colony number on the flat board of sample.
Adopt the dry weight method to measure the antibacterial efficient of chitosan and derivative for aspergillus niger.Preparation different mass fractional chitosan solution and derivative solution (acetum with 0.5% is a solvent).Sample solution with 1mL black-koji mould suspension and 2mL different concns adds in the sabouraud culture medium respectively, and blank is the bacteria suspension that does not add sample solution, cultivates 48h in 28 ℃ of constant-temperature shaking culture casees, suction filtration, the dry dry cell weight that also claims, calculate bacteriostasis rate:
I＝(m
1-m
2)/m
1×100％
Wherein, m
1And m
2Be respectively and do not add in the sample nutrient solution and add mycelia dry weight in the sample cultivation liquid.
The bacteriostatic activity experiment: adopt turbidimetry for bacterium, add certain amount of chitosan solution and derivative solution respectively in the liquid nutritional broth culture, making sample concentration is 0.01%, and inserting 0.2mL concentration respectively is 10
7The bacteria suspension of individual/mL, 37 ℃ of constant-temperature shaking culture, timing sampling is measured absorbance, reflects the variation of bacterial number with the variation of absorbance.With the incubation time is X-coordinate, and the absorbancy OD value of different incubation time bacterial suspensions under 620nm is ordinate zou, draws the growth curve and the antibacterial curve of identical bacterial classification after adding chitosan or derivative of bacterium.With the liquid nutritional broth culture of inoculated bacteria not is blank.
Adopt the dry cell weight method for black-koji mould, add certain amount of chitosan solution and derivative solution respectively in the sabouraud culture medium, making the sample quality mark is 0.01%, inserts aspergillus niger suspension 1mL, 28 ℃ of constant-temperature shaking culture.Timing sampling is used the B suction filtration, and drying also claims dry cell weight.With the incubation time is X-coordinate, and the dry cell weight of different incubation times is an ordinate zou, draws the growth curve and the antibacterial curve of identical bacterial classification after adding chitosan or derivative of mould.Resulting chitosan and p-benzoyl chitosan are to restraining effect curve such as Fig. 4, Fig. 5 and Fig. 6 of intestinal bacteria, streptococcus aureus and aspergillus niger.
Fig. 4 and Fig. 5 are respectively chitosan and the product restraining effect curve to intestinal bacteria and staphylococcus aureus growth.The existence of chitosan and p-benzoyl chitosan has suppressed the growth of intestinal bacteria and streptococcus aureus significantly as we know from the figure.Intestinal bacteria and streptococcus aureus just begin breeding after cultivating 4h, absorbancy increases, and after adding chitosan, the growth adaptation phase all is extended for 8h; After adding the p-benzoyl chitosan, the bacteria growing in the 40h in the substratum is suppressed in a lower level, has played the good restraining effect.Show that chitosan and p-benzoyl chitosan are all inhibited to the growth of intestinal bacteria and streptococcus aureus, and the fungistatic effect of p-benzoyl chitosan is better than chitosan.
Fig. 6 is the restraining effect curve that chitosan and p-benzoyl chitosan are grown to aspergillus niger.Chitosan does not only have restraining effect to aspergillus niger, helps its growth on the contrary.Reason may be that aspergillus niger belongs to Mycophyta, the cell walls of fungi contains chitosan, and higher chitosan content is just arranged in the aspergillus niger, make aspergillus niger certain resistance be arranged to the anti-microbial property of chitosan, determine chitosan that aspergillus niger is not suppressed ability, may be used to promote the growth and the breeding of cell on the contrary.After adding the p-benzoyl chitosan, the dry cell weight of aspergillus niger reduces to some extent than control group, illustrates that product can suppress the growth of aspergillus niger effectively, has enlarged the scope of restraining fungi of chitosan.
Those of ordinary skill in the art can understand, and in protection scope of the present invention, makes amendment for the foregoing description, and it all is possible adding and replacing, and it does not all exceed protection scope of the present invention.
Claims (8)
1, p-benzoyl chitosan is characterized in that: this derivative has structure shown in the following formula:
Wherein, n is between 160-180.
2, a kind of preparation method of the chitosan of p-benzoyl according to claim 1, it is characterized in that: described preparation process is as follows:
(1) para-amino benzoic acid with weighing is dissolved in the 50-65 ℃ of distilled water hot suction filtration;
(2) filtrate cool to room temperature, at room temperature suction filtration;
(3) get filter cake, vacuum-drying obtains purified para-amino benzoic acid;
(4) getting purified para-amino benzoic acid puts in the three-necked bottle, add anhydrous diethyl ether para-amino benzoic acid is dissolved fully, add sulfur oxychloride again, put into water temperature and be in 20-40 ℃ the ultrasonic washer, ultra-sonic oscillation 10-60 minute, reaction product was a p-benzoyl chlorine;
(5) reaction product in cooling (4) step is dissolved in chitosan in the anhydrous acetic acid to 0-30 ℃, again it is added in the three-necked bottle, and at 5-45 ℃ of following ultra-sonic oscillation 1-3.5 hour, standing over night;
(6) the reaction product adding acetone with (5) step is precipitated out suction filtration until product p-benzoyl base chitosan;
(7) use the mixed solvent of dehydrated alcohol and anhydrous diethyl ether to soak after 12-24 hour again, suction filtration is got filter cake;
(8) this filter cake that again (7) is gone on foot carries out Soxhlet extraction 24-30 hour with acetone, gets p-benzoyl chitosan product after the vacuum-drying.
3, according to the preparation method of the described p-benzoyl chitosan of claim 2, it is characterized in that: the processing condition of suction filtration are in described (1) step: dried by the fire 1-3 hour in 50-65 ℃ of baking oven with filter flask and B, use water pump suction filtration reaction solution down at 50-65 ℃ again, suction filtration is poured into filtrate in the clean beaker rapidly after finishing; (2), the processing condition of suction filtration all are in (6) and (7) step: dried by the fire 1-3 hour in 50-65 ℃ of baking oven with filter flask and B, at room temperature use water pump suction filtration reaction solution again, suction filtration is poured into filtrate in the clean beaker rapidly after finishing.
4, according to the preparation method of the described p-benzoyl chitosan of claim 2, it is characterized in that: described para-amino benzoic acid: sulfur oxychloride: the weight ratio that feeds intake of chitosan is (1-5): (3-9): 1.
5, according to the preparation method of the described p-benzoyl chitosan of claim 2, it is characterized in that: the dehydrated alcohol in described (7) step and the volume ratio of anhydrous diethyl ether are 1: (1-10).
6, according to the preparation method of the described p-benzoyl chitosan of claim 2, it is characterized in that: the processing condition that the Soxhlet in described (8) step is extracted are: 55-65 ℃ of heating in water bath, extracted 24-30 hour.
7, according to the preparation method of the described p-benzoyl chitosan of claim 2, it is characterized in that: the vacuum drying processing condition in described (8) step are: under 30-50 ℃, vacuum tightness is 8 * 10
4Pa, dry 12-24 hour.
8, according to of the application of the described p-benzoyl chitosan of claim 1 as the preparation food preservation additive.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102153674A (en) * | 2011-03-15 | 2011-08-17 | 中国海洋大学 | Chitosan ester p-aminobenzoate and preparation method thereof |
| CN105399862A (en) * | 2015-12-11 | 2016-03-16 | 中国海洋大学 | Preparation method for chitosan acetic ester |
| CN113717595A (en) * | 2021-07-14 | 2021-11-30 | 安徽南都华拓新能源科技有限公司 | Carbon-coated current collector coating and preparation method thereof |
| CN114958132A (en) * | 2022-07-01 | 2022-08-30 | 漳州市和兴涂料有限公司 | Plastic coating for bathroom accessories and production process and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100721752B1 (en) * | 2000-01-24 | 2007-05-25 | 쿠라레 메디카루 가부시키가이샤 | Water-swellable polymer gel and process for preparing the same |
| CN100463923C (en) * | 2006-06-29 | 2009-02-25 | 中国海洋大学 | P-acetyl amino benzoyl chitosan compound and its preparing method |
| CN101255202B (en) * | 2007-12-12 | 2011-12-07 | 中国海洋大学 | p-benzoyl amido benzoyl chitosan and preparation thereof |
-
2009
- 2009-09-09 CN CN200910018199XA patent/CN101649005B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153674A (en) * | 2011-03-15 | 2011-08-17 | 中国海洋大学 | Chitosan ester p-aminobenzoate and preparation method thereof |
| CN102153674B (en) * | 2011-03-15 | 2012-11-07 | 中国海洋大学 | P-aminobenzoate chitosan ester and preparation method thereof |
| CN105399862A (en) * | 2015-12-11 | 2016-03-16 | 中国海洋大学 | Preparation method for chitosan acetic ester |
| CN105399862B (en) * | 2015-12-11 | 2018-06-08 | 中国海洋大学 | A kind of preparation method of chitosan acetate |
| CN113717595A (en) * | 2021-07-14 | 2021-11-30 | 安徽南都华拓新能源科技有限公司 | Carbon-coated current collector coating and preparation method thereof |
| CN114958132A (en) * | 2022-07-01 | 2022-08-30 | 漳州市和兴涂料有限公司 | Plastic coating for bathroom accessories and production process and application thereof |
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