CN110003359A - A kind of hydrophily high substituted degree modification of chitosan preparation method and applications - Google Patents
A kind of hydrophily high substituted degree modification of chitosan preparation method and applications Download PDFInfo
- Publication number
- CN110003359A CN110003359A CN201910341460.3A CN201910341460A CN110003359A CN 110003359 A CN110003359 A CN 110003359A CN 201910341460 A CN201910341460 A CN 201910341460A CN 110003359 A CN110003359 A CN 110003359A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- substituted degree
- high substituted
- solution
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Dentistry (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
Abstract
Present invention seek to address that the degree of substitution of the obtained carboxylated modification of chitosan of the preparation method of the prior art is not high, cause its solubility property poor, the problem of application range is restricted, a kind of hydrophily high substituted degree modification of chitosan preparation method is provided, preparation route is as follows: chitosan → alkalization → dropwise addition acid reaction → ultrasonic wave added reaction → alcohol precipitation filtering → suction filtration → drying → carboxylated chitosan.Present invention process step is simple, reaction process is stably and controllable, strong operability, obtained hydrophily high substituted degree modification of chitosan dissolubility significantly improves, with good physical and chemical performance and biology performance, such as dissolubility, wetability, emulsibility, biocidal property, so as to be widely used in cosmetics, food, medical and health and composite functional material etc..
Description
Technical field
The present invention relates to chitin modified technical fields, more particularly, to a kind of hydrophily high substituted degree modification of chitosan system
Preparation Method and its application.
Background technique
Chitosan (chitosan, CS) (β (1-4) -2-amino-2-deoxy-D-Glucose) is through chitin (N- acetyl -
2-amino-2-deoxy-D-Glucose) a kind of resulting natural polymers of N- acetyl group are taken off, chitosan is so far
Unique existing natural alkaline polysaccharide in nature.The biological functionality and compatibility of this natural polymer, blood compatibility,
The excellent performances such as safety, microbic resolvability are by all trades and professions extensive concern, in medicine, food, chemical industry, cosmetics, Shui Chu
The application study of the numerous areas such as reason, METAL EXTRACTION and recycling, biochemistry and biomedical engineering achieves major progress.And shell is poly-
The precursor chitin abundance of sugar, is the second largest renewable resource that cellulose is only second on the earth, is known as human body institute not
The 6th vital principle that can lack.The preparation method of chitosan can be divided into chemical method and enzyme process, but obtain completely deacetylated
Chitosan product is highly difficult, it is considered that, deacetylation (degreeofdeacetylation, DD) is greater than 50% or can be dissolved in
The deacetylated product of diluted acid is referred to as chitosan.
Chitosan is white or faint yellow chip solid, and due to intramolecular, intermolecular there are hydrogen bonds, so that chitosan is presented
Close crystalline structure, so not soluble in water and most of organic solvents, this is extremely limited the use of chitosan.
And have many hydroxyls, amino isoreactivity group on the macromolecular chain of chitosan, so it is easier to react than chitin, it can
It is corresponding modified to carry out carboxylated, hydroxylating, carboxy methylation, graft reaction etc..On 2-C, 3-C and 6-C of known chitosan
Group can become the graft site of reaction, and carboxyl, alkyl chain, amino chain etc. can introduce chitosan by graft reaction
In, to generate the similar derivative of performance.
In order to improve the solubility property of chitosan, expands its application range, hydrophily carboxyl usually is carried out to chitosan
Change and is modified.Carboxylation reaction generally refers to amino or hydroxyl progress substitution reaction on chloro alkanoic acid or glyoxalic acid and chitosan,
Corresponding carboxylated chitosan derivatives (carboxymethylchitosan, CM-CS) are obtained, such as N- carboxymethyl chitosan, N,
The derivatives such as O-CMC or O-CMC.Research shows that the carboxylation reaction of chitosan both can be in amino
On can also be carried out on hydroxyl, and when the degree of substitution of carboxylation reaction is gradually increased, illustrate that the degree of carboxylation reaction is got over
Come higher, water solubility also increases with it, and the degree of substitution size of different the position of substitution is 6 hydroxyl > 3 hydroxyl > amino, but total
The degree of substitution for the carboxylated modification of chitosan that current method obtains for body is not high.
Summary of the invention
The present invention be in order to the obtained carboxylated modification of chitosan of the preparation method for solving the prior art degree of substitution simultaneously
It is not high, cause its solubility property poor, the problem of application range is restricted, it is simple to provide a kind of processing step, reacts
Journey is stably and controllable, strong operability, and the hydrophily that obtained hydrophily high substituted degree modification of chitosan dissolubility significantly improves is high
Degree of substitution modification of chitosan preparation method
To achieve the goals above, the invention adopts the following technical scheme:
A kind of hydrophily high substituted degree modification of chitosan preparation method of the invention, comprising the following steps:
A kind of hydrophily high substituted degree modification of chitosan preparation method, comprising the following steps:
(1) it alkalizes: the sodium hydroxide solution and isopropanol that mass concentration is 30~50% being added in chitosan, shell is poly-
The mass ratio of sugar, sodium hydroxide and isopropanol is 1:(2.30~2.45): (16.6~16.75), water-bath adds under agitation
Heat obtains alkaline solution to 1~3h of quaternization is carried out at this temperature after 30~50 DEG C；
(2) acidification reaction: being slowly added dropwise the chloroethene aqueous acid that mass concentration is 40~60% in alkaline solution, controls shell
Glycan and chloroacetic molar ratio 1:1.5~2.5, by control rate of addition to control reaction temperature less than 50 DEG C；
(3) ultrasonic wave added reacts: solution being warming up to 45~85 DEG C after chloroethene aqueous acid completion of dropwise addition, and warm herein
Lower 1~2h of ultrasonic reaction is spent, ultrasound condition is 200~400W of ultrasonic power, frequency 15kHz；
(4) alcohol precipitation filters: to adjust reaction solution pH to 7~8 after reaction, appropriate dehydrated alcohol is added and is sunk
It forms sediment, the methanol solution that filtered filtration residue is 80% with mass concentration is washed after impregnating, and is filtered；
(5) it filters: being washed after the solid sample obtained after suction filtration is sufficiently impregnated with dehydrated alcohol, filtered；
(6) vacuum drying: the solid sample obtained after suction filtration is dry to perseverance with 80~90 DEG C of temperature under vacuum conditions
Weight is up to hydrophily high substituted degree modification of chitosan.
Preferably, deacetylating degree of chitosan >=90% in the step (1).
Preferably, in step (1), the sodium hydroxide solution mass concentration is 40%, chitosan, sodium hydroxide, different
The mass ratio of propyl alcohol three is 1:2.33:16.67, and heating water bath is to 40 DEG C, quaternization 2h.
Preferably, the chloroethene aqueous acid mass concentration is 50%, and chitosan rubs with chloroacetic in step (2)
You compare 1:2.
Preferably, solution is warming up to 65 DEG C after chloroethene aqueous acid completion of dropwise addition, ultrasonic power in step (3)
400W, frequency 15kHz frequency, ultrasonic reaction 1h.
Preferably, using mass concentration to adjust pH to 7~8 for 10% hydrochloric acid solution in step (4), being filtered after filtering
Slag with mass concentration be 80% methanol solution impregnate after washed, filter and in triplicate.
Preferably, the solid sample that the step (5) obtains is washed after sufficiently being impregnated with dehydrated alcohol, filter,
Washing filters.
Preferably, drying temperature is 80 DEG C in the step (6).
Progressive, the invention also discloses a kind of hydrophily high substituted degree modification of chitosan to inhibit answering on bacterial growth
With.
Compared with prior art, the invention has the following beneficial effects:
By the way that the research of carboxyl-chitosan reaction is optimized, processing step is simple, and reaction process is stably and controllable, can operate
Property strong, the modification of chitosan of available high substituted degree so that the dissolubility of chitosan obtains more significantly improving, simultaneously
To high substituted degree carboxylated chitosan also there is excellent physical and chemical performance and biology performance, as wetability, emulsibility,
Biocidal property, Absorptive and Slow-Released Properties, chemical stability etc., so as to be widely used in medicine, food, cosmetics and functional material
Equal fields.
Detailed description of the invention
Fig. 1 is chitosan and hydrophily high substituted degree modification of chitosan obtained in embodiment 1 in 1 alkalinization step of embodiment
Infrared spectrogram.
Fig. 2 is the scanning electron microscopy electron microscope of chitosan in alkalinization step.
Fig. 3 is the scanning electron microscopy electron microscope of hydrophily high substituted degree modification of chitosan obtained in embodiment 1.
Fig. 4 is chitosan and hydrophily high substituted degree modification of chitosan obtained in embodiment 1 in 1 alkalinization step of embodiment
Emulsifying ability changes over time curve graph.
Specific embodiment
The present invention will be further described for 1-4 and specific embodiment with reference to the accompanying drawing.
Embodiment 1
(1) alkalize: in the chitosan of deacetylation >=90% be added mass concentration be 40% sodium hydroxide solution and
Isopropanol, the mass ratio of chitosan, sodium hydroxide and isopropanol are 1:2.33:16.67, under agitation heating water bath to 40
Quaternization 2h is carried out after DEG C at this temperature, obtains alkaline solution；
(2) acidification reaction: being slowly added dropwise the chloroethene aqueous acid that mass concentration is 50% in alkaline solution, controls chitosan
With chloroacetic molar ratio 1:2, by control rate of addition to control reaction temperature less than 50 DEG C；
(3) ultrasonic wave added reacts: solution being warming up to 65 DEG C after chloroethene aqueous acid completion of dropwise addition, and at this temperature
Ultrasonic reaction 1h, ultrasound condition are ultrasonic power 400W, frequency 15kHz；
(4) alcohol precipitation filters: to adjust reaction solution pH to 7~8 after reaction, appropriate dehydrated alcohol is added and is sunk
Form sediment, filtered filtration residue with mass concentration be 80% methanol solution impregnate after washed, filter, wash repeatedly and filter this two
Kind step is three times；
(5) it filters: being washed after the solid sample obtained after suction filtration is sufficiently impregnated with dehydrated alcohol, filtered, repeated
It is secondary；
(6) vacuum drying: the solid sample obtained after suction filtration is dried to constant weight i.e. with 80 DEG C of temperature under vacuum conditions
Obtain hydrophily high substituted degree modification of chitosan.
Property measurement, specific measuring method and knot are carried out to the hydrophily high substituted degree modification of chitosan that embodiment 1 obtains
Fruit is as follows:
(1) degree of substitution measures
The hydrophily high substituted degree modification of chitosan that embodiment 1 obtains is accurately weighed, addition 50mL concentration is 0.1mol/L
Hydrochloric acid solution in sufficiently impregnate 6~8h or more, by clean pH meter insertion solution, then the standard Na0H of 0.1mol/L is added dropwise
Solution stirs, the volume V for the sodium hydroxide solution being added dropwise when writing down pH=2.1 when being added dropwise1ML continues to be added dropwise, writes down pH
The volume V for the sodium hydroxide solution being added dropwise when=4.22ML, each sample are measured in parallel 3 times, are then averaged, by following
The degree of substitution (DegreeofSubstitution, DS) of formula calculating hydrophily high substituted degree modification of chitosan:
Degree of substitution (DS)=0.057A/ (1-0.058A), wherein A=C(NaOH)(V2-V1)/m
C(NaOH)For the concentration of standard NaOH solution, V1Volume by the standard Na0H solution being added dropwise when pH=2.1
(mL), V2Volume (mL) by the standard Na0H solution being added dropwise when pH=4.2, m are hydrophily high substituted degree modification of chitosan
Quality.Each sample is measured in parallel 3 times, is then averaged.
The degree of substitution (DS) that hydrophily high substituted degree modification of chitosan is calculated may be up to 79.6%.
(2) infrared spectroscopy detects
Changed with the hydrophily high substituted degree that Fourier infrared spectrograph obtains the chitosan in alkalinization step with embodiment 1
Property Chitosan powder carry out infrared test, using KBr pressed disc method, scanning range 500cm-1~4000cm-1.Obtained infrared light
(a is the chitosan in alkalinization step to spectrogram, and b is that the modified shell of hydrophily high substituted degree that embodiment 1 obtains is poly- as shown in Figure 1
Sugar).
As shown in Figure 1: in 1658cm-1And 1580cm-1There is the characteristic absorption peak of carboxymethyl in place's sample, chitosan without
1580cm-1Absorption peak illustrates that chitosan has carried out carboxymethylation reaction；Wherein in 2922cm-1And 2880cm-1Distinguish at the peak at place
It is-CH and-CH2Stretching vibration peak, the intensity at the peak is enhanced after carboxymethylation reaction, illustrates to draw in the molecule of chitosan
- CH is entered2；In 3416cm-1Place is-OH and-NH in chitosan molecule2Stretching vibration peak, 1028cm-1And 1080cm-1Punishment
It is not the vibration peak of primary hydroxyl and secondary hydroxyl, reaction front and back peak obviously narrows, and remitted its fury illustrates that these groups are reduced.
In summary, carboxymethylation reaction all has occurred on the amino, hydroxyl of chitosan with after chloroacetate reaction in chitosan.
(3) electron-microscope scanning
The chitosan (Fig. 2) in alkalinization step is obtained with embodiment 1 using scanning electron microscopy Electronic Speculum (SEM) hydrophilic
Property high substituted degree modification of chitosan (Fig. 3) mode of appearance scan (since sample is non-conductive, it is necessary to be sprayed to sample after dehydration
Gold processing, i.e., gold-plated), obtained electron microscope is as shown in Figure 2 and Figure 3.
From Fig. 2, Fig. 3 it is found that significant changes have occurred in surface texture after chitosan generation carboxymethylation reaction, shell is poly-
The rigid structure of sugared irregular sheet disappears, and forms relatively uniform finely ground particle substance, this may be due to the research of carboxyl-chitosan
Afterwards, the introducing of-COOH reduces the ability in chitosan molecule with intermolecular formation hydrogen bond, so that chitosan molecule chain is original
Regularity changes, so that the performance of carboxylated chitosan is improved.
(4) solubility test
By the chitosan (CS) and the obtained hydrophily high substituted degree modification shell of embodiment 1 in 1.0g dry alkalinization step
Glycan (CM-CS) is scattered in distilled water respectively, is respectively 0.5mol/LHCl with concentration and NaOH solution adjusts its pH value, room
The lower magnetic agitation 2min of temperature, observes its dissolution situation at different pH, the results are shown in Table 1 for observation.
In experimentation, when NaOH is tuned into pH value of solution=10, chitosan is fairly insoluble, and hydrophily high substituted degree is modified
Chitosan all dissolves, and solution is colorless and transparent；When continuing that HCl solution tune pH=7 is added dropwise into solution, chitosan or insoluble,
But hydrophily high substituted degree modification of chitosan solution starts muddiness, still shows certain dissolubility, illustrates carboxymethylation reaction
Improve the dissolubility of chitosan in neutral conditions；When pH=5, chitosan starts to dissolve, but still has some white precipitate, parent
The solution of aqueous high substituted degree modification of chitosan presents colorless and transparent；When pH continues to be reduced to 3 or so, in chitosan solution
Precipitating all dissolutions, in colorless and transparent, solution is very good for two solution.It can thus be appreciated that-COOH is introduced into chitosan molecule
On, the product of generation shows weaker dissolubility in neutral conditions, and good dissolubility is all shown under acid-base condition
("-" indicates insoluble in table 1, and "+" indicates solvable).
The solubility for the hydrophily high substituted degree modification of chitosan that chitosan and embodiment 1 in 1 alkalinization step of table obtain
Measurement result
The step as it can be seen from table 1 solubility property for the hydrophily high substituted degree modification of chitosan that embodiment 1 obtains relatively alkalizes
Chitosan in rapid makes moderate progress, this is because the introducing of-COOH reduces in chitosan molecule and divides after the research of carboxyl-chitosan
The ability of hydrogen bond is formed between son, while the original regularity of chitosan molecule chain is changed, crystalline structure substantially reduces,
So its water solubility is greatly improved.
(5) measurement of water suction moisture retention
(1) water imbibition is tested
Take two clean driers, a inside pours into saturation magnesium chloride solution, as relative humidity (RH) 32%
Drier environment；Another pours into saturated ammonium sulfate solution, as the drier environment of relative humidity (RH) 81%.The two is put
Enter in 20 ± 0.1 DEG C of constant incubator, the chitosan in precise 1.0g alkalinization step, hydrophily high substituted degree change respectively
Culture dish is put into drier by property chitosan in clean culture dish, while doing Duplicate Samples, 2,4,6,8, time point for 24 hours
It takes out, weighs quality (W before sample is placed respectively0) and place after quality (W1)。
Water absorption rate (Ra)=(W1-W0)/W0× 100%
(2) moisture retention is tested
The modified shell of hydrophily high substituted degree for being obtained the chitosan (CS) in alkalinization step, embodiment 1 with distilled water is poly-
Sugared (CM-CS) is diluted to 10%, respectively accurately weighs 5.0g in clean culture dish, culture dish is placed in (silicon in two driers
In glue dry environment), standing time 6,12,24,36,48,60,72h weigh quality (H before sample is placed respectively0) and place
Quality (H afterwards1)。
Moisturizing rate (Rr)=(H0-H1)/H0× 100%
After Data Processing in Experiment, after the chitosan and hydrophily high substituted degree modification of chitosan 48h in alkalinization step
Water absorption rate and moisturizing rate are as shown in table 2.
The water absorption rate and moisturizing rate of chitosan and hydrophily high substituted degree modification of chitosan in 2 alkalinization step of table
As can be seen from Table 2, the shell in hydrophily high substituted degree modification of chitosan and alkalinization step that embodiment 1 obtains is poly-
Sugar is compared, and water imbibition and moisture retention have different degrees of raising, illustrates to carry out carboxy methylation, the introducing of-COOH to chitosan
CS intramolecular and the intermolecular ability for forming hydrogen bond are reduced, its water solubility is made to be greatly improved, shell after modified is poly-
The moisture absorption of sugar, performance of keeping humidity greatly improve.
(6) measurement of emulsibility
The sample prepare liquid that 10.0mL atoleine and 10.0mL have been prepared accurately is moved into 25.0mL precision graded tube
It (is put in refrigerator more than for 24 hours, the hydrophily high substituted degree for obtaining chitosan (CS) and embodiment 1 in alkalinization step is modified
Chitosan (CM-CS) sufficiently dissolves), solution is uniformly mixed with identical shaking mode, grease point is observed and recorded after 10min
From situation, every 30min record is primary later, and emulsifiability is calculated as follows: emulsifying ability=emulsion layer volume/total liquid volume,
The case where emulsifying ability changes over time is as shown in Figure 4.
It will be seen that chitosan and hydrophily high substituted degree modification of chitosan have good emulsibility from Fig. 4
Energy.But the emulsibility of hydrophily high substituted degree modification of chitosan is higher than chitosan, this illustrates chitosan through carboxy methylation
Afterwards, emulsifiability is improved, and faster, hydrophily high substituted degree changes the decline of chitosan emulsifying ability as time increases
Property chitosan it is relatively slow, the two formed emulsion layer finally gradually tend towards stability.This is because the shell after carboxy methylation is poly-
Sugar, the introducing of-COOH increase electrostatic repulsion effect mutual between chitosan molecule, and discrete electric double layer at this time is thickeied,
So that the interfacial film of solution is thickened, be just conducive to being sufficiently formed for micella in this way, thus, the emulsibility of sample obtains
Very big raising.
It to sum up analyzes, water-soluble polysaccharide belongs to hydrophilic colloid, has the property of emulsification or stable emulsifying in aqueous solution.
There are many containing in chitosan molecule hydrophilic radical (amino), in acidic environment, hydrophilic group NH2It is converted to NH3 +, make
It obtains hydrophily high substituted degree modification of chitosan molecule and becomes amphiphatic molecule, can be adsorbed on the interface containing grease, because
This chitosan can be used as emulsifier and use in industries such as cosmetics, health food, medicine.
(7) measurement of biocidal property
It takes Clinical isolation Escherichia coli, staphylococcus aureus, Pseudomonas aeruginosa, Candida albicans a little, connects respectively
Kind cultivates 18h at 37 DEG C in broth bouillon.(20% calf serum is added in Pseudomonas aeruginosa broth bouillon) takes
Each bacterial strain nutrient broth culture of 18h culture is made into bacteria suspension for testing.Sterilizing test tubes 11, the 1st are taken respectively
Nutrient broth fluid nutrient medium 9ml is added, 5ml nutrient broth fluid nutrient medium, the 11st addition 10ml battalion is added in 2-10 branch
Meat soup fluid nutrient medium is supported, separately sampled product solution 1ml is added the 1st test tube, takes 5ml to be added the 2nd after mixing, successively
It is diluted to the 10th, the 11st is not added sample as control.Escherichia coli suspension 0.1ml is added in every pipe, trains at a temperature of 37 DEG C
It supports for 24 hours, takes out observation bacterial growth situation.Staphylococcus aureus, Pseudomonas aeruginosa, Candida albicans are raw with above-mentioned Germicidal efficacy
Long situation.If test tube becomes cloudy, that is, indicate bacterial growth, sample is without bacteriostasis；If test tube is limpid, indicate bacterial growth by
To inhibition.It is as shown in table 3 that each sample solution corresponds to last limpid test tube number in bacteriostatic test.
3 each sample solution of table corresponds to last limpid test tube number in bacteriostatic test
Note: "-" indicates not limpid.
As known from Table 3, the hydrophily high substituted degree modification of chitosan (CM-CS) of this method preparation is big to Clinical isolation
Enterobacteria, staphylococcus aureus, Pseudomonas aeruginosa, Candida albicans have stronger bacteriostasis.
By above-mentioned limpid broth tubes and control group transferred species broth agar plates after diluting according to a certain percentage, observation
For 24 hours, the Cmin of no bacterial growth is bacteriocidal concentration, is denoted as C, unit mg/mL, each sample solution sterilization conditions such as table
Shown in 4.
4 each sample solution sterilization conditions of table
| C (Escherichia coli) | C (staphylococcus aureus) | C (Pseudomonas aeruginosa) | C (Candida albicans) | |
| 0.01% stoste | - | - | - | - |
| 0.1% stoste | 7.35 | 7.69 | 8.55 | - |
| 1.0% stoste | 2.68 | 3.13 | 4.66 | 6.91 |
| 2.0% stoste | 1.54 | 1.96 | 2.60 | 2.32 |
| 5.0% stoste | 0.47 | 0.55 | 0.94 | 0.96 |
| Control group | - | - | - | - |
Note: "-" indicates no bactericidal properties.
As known from Table 4, illustrate that the hydrophily high substituted degree modification of chitosan (CM-CS) of this method preparation is normal to being clinically separated
The Bacteria skin infection strain Escherichia coli that see, staphylococcus aureus, Pseudomonas aeruginosa, Candida albicans have stronger sterilization to make
With to play the effect of prevention and conditioning skin discomfort.
To sum up, the hydrophily high substituted degree modification of chitosan (CM-CS) obtained through the invention has good physico
Learn performance and biology performance, such as dissolubility, wetability, emulsibility, biocidal property, so as to be widely used in cosmetics,
Food, medical and health and composite functional material etc..
Embodiment 2
(1) it alkalizes: the sodium hydroxide solution and isopropanol that mass concentration is 30%, chitosan, hydrogen being added in chitosan
The mass ratio of sodium oxide molybdena and isopropanol is 1:2.45:16.70, under agitation heating water bath to after 30 DEG C at this temperature into
Row quaternization 3h, obtains alkaline solution；
(2) acidification reaction: being slowly added dropwise the chloroethene aqueous acid that mass concentration is 40% in alkaline solution, controls chitosan
With chloroacetic molar ratio 1:1.5, by control rate of addition to control reaction temperature less than 50 DEG C；
(3) ultrasonic wave added reacts: solution being warming up to 45 DEG C after chloroethene aqueous acid completion of dropwise addition, and at this temperature
Ultrasonic reaction 2h, ultrasound condition are ultrasonic power 300W, frequency 15kHz；
(4) alcohol precipitation filters: to adjust reaction solution pH to 7~8 after reaction, appropriate dehydrated alcohol is added and is sunk
It forms sediment, the methanol solution that filtered filtration residue is 80% with mass concentration is washed after impregnating, and is filtered；
(5) it filters: being washed after the solid sample obtained after suction filtration is sufficiently impregnated with dehydrated alcohol, filtered；
(6) vacuum drying: the solid sample obtained after suction filtration is dried to constant weight i.e. with 90 DEG C of temperature under vacuum conditions
Obtain hydrophily high substituted degree modification of chitosan.
The property measurement result for the hydrophily high substituted degree modification of chitosan that embodiment 2 obtains is similar to Example 1, therefore not
It repeats herein.
Embodiment 3
(1) it alkalizes: the sodium hydroxide solution and isopropanol that mass concentration is 35%, chitosan, hydrogen being added in chitosan
The mass ratio of sodium oxide molybdena and isopropanol is 1:2.40:16.75, under agitation heating water bath to after 50 DEG C at this temperature into
Row quaternization 2h, obtains alkaline solution；
(2) acidification reaction: be slowly added dropwise in alkaline solution mass concentration be 60% chloroethene aqueous acid, control chitosan with
Chloroacetic molar ratio 1:2.5, by control rate of addition to control reaction temperature less than 50 DEG C；
(3) ultrasonic wave added reacts: solution being warming up to 85 DEG C after chloroethene aqueous acid completion of dropwise addition, and at this temperature
Ultrasonic reaction 1.2h, ultrasound condition are ultrasonic power 200W, frequency 15kHz；
(4) alcohol precipitation filters: to adjust reaction solution pH to 7~8 after reaction, appropriate dehydrated alcohol is added and is sunk
It forms sediment, the methanol solution that filtered filtration residue is 80% with mass concentration is washed after impregnating, and is filtered；
(5) it filters: being washed after the solid sample obtained after suction filtration is sufficiently impregnated with dehydrated alcohol, filtered；
(6) vacuum drying: the solid sample obtained after suction filtration is dried to constant weight i.e. with 85 DEG C of temperature under vacuum conditions
Obtain hydrophily high substituted degree modification of chitosan.
The property measurement result for the hydrophily high substituted degree modification of chitosan that embodiment 3 obtains is similar to Example 1, therefore not
It repeats herein.
Embodiment 4
(1) it alkalizes: the sodium hydroxide solution and isopropanol that mass concentration is 30%, chitosan, hydrogen being added in chitosan
The mass ratio of sodium oxide molybdena and isopropanol is 1:2.30:16.6, under agitation heating water bath to after 45 DEG C at this temperature into
Row quaternization 1.8h, obtains alkaline solution；
(2) acidification reaction: be slowly added dropwise in alkaline solution mass concentration be 60% chloroethene aqueous acid, control chitosan with
Chloroacetic molar ratio 1:2.0, by control rate of addition to control reaction temperature less than 50 DEG C；
(3) ultrasonic wave added reacts: solution being warming up to 70 DEG C after chloroethene aqueous acid completion of dropwise addition, and at this temperature
Ultrasonic reaction 1.5h, ultrasound condition are ultrasonic power 300W, frequency 15kHz；
(4) alcohol precipitation filters: to adjust reaction solution pH to 7~8 after reaction, appropriate dehydrated alcohol is added and is sunk
It forms sediment, the methanol solution that filtered filtration residue is 80% with mass concentration is washed after impregnating, and is filtered；
(5) it filters: being washed after the solid sample obtained after suction filtration is sufficiently impregnated with dehydrated alcohol, filtered；
(6) vacuum drying: the solid sample obtained after suction filtration is dried to constant weight i.e. with 88 DEG C of temperature under vacuum conditions
Obtain hydrophily high substituted degree modification of chitosan.
The property measurement result for the hydrophily high substituted degree modification of chitosan that embodiment 4 obtains is similar to Example 1, therefore not
It repeats herein.
Embodiment 5
(1) it alkalizes: the sodium hydroxide solution and isopropanol that mass concentration is 45%, chitosan, hydrogen being added in chitosan
The mass ratio of sodium oxide molybdena and isopropanol is 1:2.38:16.73, under agitation heating water bath to after 39 DEG C at this temperature into
Row quaternization 2.8h, obtains alkaline solution；
(2) acidification reaction: be slowly added dropwise in alkaline solution mass concentration be 56% chloroethene aqueous acid, control chitosan with
Chloroacetic molar ratio 1:2.2, by control rate of addition to control reaction temperature less than 50 DEG C；
(3) ultrasonic wave added reacts: solution being warming up to 82 DEG C after chloroethene aqueous acid completion of dropwise addition, and at this temperature
Ultrasonic reaction 1.9h, ultrasound condition are ultrasonic power 200W, frequency 15kHz；
(4) alcohol precipitation filters: to adjust reaction solution pH to 7~8 after reaction, appropriate dehydrated alcohol is added and is sunk
It forms sediment, the methanol solution that filtered filtration residue is 80% with mass concentration is washed after impregnating, and is filtered；
(5) it filters: being washed after the solid sample obtained after suction filtration is sufficiently impregnated with dehydrated alcohol, filtered；
(6) vacuum drying: the solid sample obtained after suction filtration is dried to constant weight i.e. with 82 DEG C of temperature under vacuum conditions
Obtain hydrophily high substituted degree modification of chitosan.
The property measurement result for the hydrophily high substituted degree modification of chitosan that embodiment 5 obtains is similar to Example 1, therefore not
It repeats herein.
Embodiment 6
(1) it alkalizes: the sodium hydroxide solution and isopropanol that mass concentration is 48%, chitosan, hydrogen being added in chitosan
The mass ratio of sodium oxide molybdena and isopropanol is 1:2.44:16.63, under agitation heating water bath to after 39 DEG C at this temperature into
Row quaternization 1.1h, obtains alkaline solution；
(2) acidification reaction: be slowly added dropwise in alkaline solution mass concentration be 46% chloroethene aqueous acid, control chitosan with
Chloroacetic molar ratio 1:1.7, by control rate of addition to control reaction temperature less than 50 DEG C；
(3) ultrasonic wave added reacts: solution being warming up to 53 DEG C after chloroethene aqueous acid completion of dropwise addition, and at this temperature
Ultrasonic reaction 1.3h, ultrasound condition are ultrasonic power 400W, frequency 15kHz；
(4) alcohol precipitation filters: to adjust reaction solution pH to 7~8 after reaction, appropriate dehydrated alcohol is added and is sunk
It forms sediment, the methanol solution that filtered filtration residue is 80% with mass concentration is washed after impregnating, and is filtered；
(5) it filters: being washed after the solid sample obtained after suction filtration is sufficiently impregnated with dehydrated alcohol, filtered；
(6) vacuum drying: the solid sample obtained after suction filtration is dried to constant weight i.e. with 85 DEG C of temperature under vacuum conditions
Obtain hydrophily high substituted degree modification of chitosan.
The property measurement result for the hydrophily high substituted degree modification of chitosan that embodiment 6 obtains is similar to Example 1, therefore not
It repeats herein.
Embodiment 7
(1) it alkalizes: the sodium hydroxide solution and isopropanol that mass concentration is 40%, chitosan, hydrogen being added in chitosan
The mass ratio of sodium oxide molybdena and isopropanol is 1:2.30:16.73, under agitation heating water bath to after 40 DEG C at this temperature into
Row quaternization 2.5h, obtains alkaline solution；
(2) acidification reaction: be slowly added dropwise in alkaline solution mass concentration be 50% chloroethene aqueous acid, control chitosan with
Chloroacetic molar ratio 1:2.0, by control rate of addition to control reaction temperature less than 50 DEG C；
(3) ultrasonic wave added reacts: solution being warming up to 85 DEG C after chloroethene aqueous acid completion of dropwise addition, and at this temperature
Ultrasonic reaction 2.0h, ultrasound condition are ultrasonic power 300W, frequency 15kHz；
(4) alcohol precipitation filters: to adjust reaction solution pH to 7~8 after reaction, appropriate dehydrated alcohol is added and is sunk
It forms sediment, the methanol solution that filtered filtration residue is 80% with mass concentration is washed after impregnating, and is filtered；
(5) it filters: being washed after the solid sample obtained after suction filtration is sufficiently impregnated with dehydrated alcohol, filtered；
(6) vacuum drying: the solid sample obtained after suction filtration is dried to constant weight i.e. with 85 DEG C of temperature under vacuum conditions
Obtain hydrophily high substituted degree modification of chitosan.
The property measurement result for the hydrophily high substituted degree modification of chitosan that embodiment 7 obtains is similar to Example 1, therefore not
It repeats herein.
Embodiment described above is a kind of preferable scheme of the invention, not makees limit in any form to the present invention
System, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (10)
1. a kind of hydrophily high substituted degree modification of chitosan preparation method, which comprises the following steps:
(1) it alkalizes: the sodium hydroxide solution and isopropanol that mass concentration is 30~50%, chitosan, hydrogen being added in chitosan
The mass ratio of sodium oxide molybdena and isopropanol is 1:(2.30~2.45): (16.6~16.75), under agitation heating water bath to 30
1~3h of quaternization is carried out after~50 DEG C at this temperature, obtains alkaline solution；
(2) acidification reaction: being slowly added dropwise the chloroethene aqueous acid that mass concentration is 40~60% in alkaline solution, controls chitosan
With chloroacetic molar ratio 1:1.5~2.5, by control rate of addition to control reaction temperature less than 50 DEG C；
(3) ultrasonic wave added reacts: solution being warming up to 45~85 DEG C after chloroethene aqueous acid completion of dropwise addition, and at this temperature
1~2h of ultrasonic reaction, ultrasound condition are 200~400W of ultrasonic power, frequency 15kHz；
(4) alcohol precipitation filters: to adjust reaction solution pH to 7~8 after reaction, appropriate dehydrated alcohol is added and is precipitated, mistake
The methanol solution that filter residue is 80% with mass concentration after filter is washed after impregnating, and is filtered；
(5) it filters: being washed after the solid sample obtained after suction filtration is sufficiently impregnated with dehydrated alcohol, filtered；
(6) vacuum drying: the solid sample obtained after suction filtration is dried to constant weight i.e. with 80~90 DEG C of temperature under vacuum conditions
Obtain hydrophily high substituted degree modification of chitosan.
2. hydrophily high substituted degree modification of chitosan preparation method as described in claim 1, which is characterized in that the step
(1) deacetylating degree of chitosan is not less than 90% in.
3. hydrophily high substituted degree modification of chitosan preparation method as claimed in claim 1 or 2, which is characterized in that step (1)
In, the sodium hydroxide solution mass concentration be 40%, chitosan, sodium hydroxide, isopropanol three mass ratio be 1:2.33:
16.67, heating water bath is to 40 DEG C, quaternization 2h.
4. hydrophily high substituted degree modification of chitosan preparation method as described in claim 1, which is characterized in that in step (2),
The chloroethene aqueous acid mass concentration is 50%, chitosan and chloroacetic molar ratio 1:2.
5. hydrophily high substituted degree modification of chitosan preparation method as described in claim 1, which is characterized in that in step (3),
Solution is warming up to 65 DEG C, ultrasonic power 400W after chloroethene aqueous acid completion of dropwise addition, frequency 15kHz frequency, ultrasonic reaction
1h。
6. hydrophily high substituted degree modification of chitosan preparation method as described in claim 1, which is characterized in that in step (4),
Mass concentration is used to adjust pH to 7~8 for 10% hydrochloric acid solution, the methanol that filtered filter residue mass concentration is 80% is molten
Liquid is washed after impregnating, and is filtered and is washed in triplicate, and step is filtered.
7. hydrophily high substituted degree modification of chitosan preparation method as described in claim 1, which is characterized in that the step
(5) solid sample obtained is washed after sufficiently being impregnated with dehydrated alcohol, is filtered, and is washed, and is filtered.
8. hydrophily high substituted degree modification of chitosan preparation method as described in claim 1, which is characterized in that the step
(6) drying temperature is 80 DEG C in.
9. a kind of parent as made from hydrophily high substituted degree modification of chitosan preparation method according to any one of claims 1 to 8
Aqueous high substituted degree modification of chitosan is inhibiting the application on bacterial growth.
10. hydrophily high substituted degree modification of chitosan as claimed in claim 9 is in the application of antibacterial aspect, which is characterized in that
The bacterium is the Escherichia coli being clinically separated, staphylococcus aureus, Pseudomonas aeruginosa, Candida albicans.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910341460.3A CN110003359A (en) | 2019-04-26 | 2019-04-26 | A kind of hydrophily high substituted degree modification of chitosan preparation method and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910341460.3A CN110003359A (en) | 2019-04-26 | 2019-04-26 | A kind of hydrophily high substituted degree modification of chitosan preparation method and applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110003359A true CN110003359A (en) | 2019-07-12 |
Family
ID=67174367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910341460.3A Pending CN110003359A (en) | 2019-04-26 | 2019-04-26 | A kind of hydrophily high substituted degree modification of chitosan preparation method and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110003359A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110564074A (en) * | 2019-09-05 | 2019-12-13 | 天津市亚泰富通金属制品有限公司 | Polyvinyl chloride regenerated plastic particles and preparation process thereof |
| CN111363064A (en) * | 2020-04-28 | 2020-07-03 | 东华大学 | Preparation method of carboxymethyl chitosan with high substitution degree and high molecular weight |
| CN111714409A (en) * | 2020-06-28 | 2020-09-29 | 厦门伟礼沐浴用品有限公司 | Antibacterial and antiviral hand sanitizer and preparation method thereof |
| CN114176115A (en) * | 2021-11-19 | 2022-03-15 | 浙江工商大学 | Carboxymethyl chitosan Schiff base and preparation and application thereof |
| EP3981798A1 (en) * | 2020-10-10 | 2022-04-13 | Shandong Eton New Material Co., Ltd. | Modified chitosan, preparation method thereof, and additive for tile adhesive and use thereof |
| CN117618624A (en) * | 2023-11-15 | 2024-03-01 | 扬州景怡医疗科技有限公司 | Medical polymer bandage convenient for biodegradation and preparation method thereof |
-
2019
- 2019-04-26 CN CN201910341460.3A patent/CN110003359A/en active Pending
Non-Patent Citations (11)
| Title |
|---|
| 于广利等: "《糖药物学》", 31 October 2012, 中国海洋大学出版社 * |
| 付君善等: ""高取代度羧甲基壳聚糖的制备工艺研究"", 《精细石油化工进展》 * |
| 何丽等: ""壳聚糖和羧甲基壳聚糖对口腔五种常见致病菌的抑菌活性研究"", 《陕西医学杂志》 * |
| 吴月兰等: ""壳聚糖的羧甲基化及其产物在化妆中的应用"", 《大观周刊》 * |
| 林友文等: ""羧甲壳多糖的制备及其吸湿、保湿性能"", 《福建医科大学学报》 * |
| 林友文等: ""超声波辐射制备羧甲基壳聚糖"", 《离子交换与吸附》 * |
| 汪多仁: "《有机食品表面活性剂》", 30 April 2009, 科学技术文献出版社 * |
| 王洪振等: ""水溶性羧甲基壳聚糖的制备及其应用"", 《华东纸业》 * |
| 罗序燕等: ""超声波合成羧甲基壳聚糖及表征"", 《江西理工大学学报》 * |
| 蒋挺大编著: "《壳聚糖》", 31 March 2001, 化学工业出版社 * |
| 陈凌云等: ""羧甲基壳聚糖的取代度及保湿性"", 《应用化学》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110564074A (en) * | 2019-09-05 | 2019-12-13 | 天津市亚泰富通金属制品有限公司 | Polyvinyl chloride regenerated plastic particles and preparation process thereof |
| CN111363064A (en) * | 2020-04-28 | 2020-07-03 | 东华大学 | Preparation method of carboxymethyl chitosan with high substitution degree and high molecular weight |
| CN111363064B (en) * | 2020-04-28 | 2022-03-15 | 东华大学 | Preparation method of carboxymethyl chitosan with high substitution degree and high molecular weight |
| CN111714409A (en) * | 2020-06-28 | 2020-09-29 | 厦门伟礼沐浴用品有限公司 | Antibacterial and antiviral hand sanitizer and preparation method thereof |
| EP3981798A1 (en) * | 2020-10-10 | 2022-04-13 | Shandong Eton New Material Co., Ltd. | Modified chitosan, preparation method thereof, and additive for tile adhesive and use thereof |
| CN114176115A (en) * | 2021-11-19 | 2022-03-15 | 浙江工商大学 | Carboxymethyl chitosan Schiff base and preparation and application thereof |
| CN117618624A (en) * | 2023-11-15 | 2024-03-01 | 扬州景怡医疗科技有限公司 | Medical polymer bandage convenient for biodegradation and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110003359A (en) | A kind of hydrophily high substituted degree modification of chitosan preparation method and applications | |
| Wahid et al. | Synthesis and characterization of antibacterial carboxymethyl Chitosan/ZnO nanocomposite hydrogels | |
| CA2475258C (en) | Cell wall derivatives from biomass and preparation thereof | |
| Grace et al. | Copper alginate-cotton cellulose (CACC) fibers with excellent antibacterial properties | |
| Kaya et al. | New chitin, chitosan, and O-carboxymethyl chitosan sources from resting eggs of Daphnia longispina (Crustacea); with physicochemical characterization, and antimicrobial and antioxidant activities | |
| Peniche et al. | Chitin and chitosan: major sources, properties and applications | |
| Akakuru et al. | The chemistry of chitin and chitosan justifying their nanomedical utilities | |
| EP2310422B1 (en) | Nanocomposite materials based on metallic nanoparticles stabilized with branched polysaccharides | |
| Xia et al. | A novel chitosan oligosaccharide derivative: Synthesis, antioxidant and antibacterial properties | |
| Ul-Islam et al. | Chitosan-based nanostructured biomaterials: Synthesis, properties, and biomedical applications | |
| Walke et al. | Physicochemical and functional characterization of chitosan prepared from shrimp shells and investigation of its antibacterial, antioxidant and tetanus toxoid entrapment efficiency | |
| WO2020108495A1 (en) | Beta-glucan solid dispersion and preparation method therefor | |
| Omer et al. | Preparation of Isatin/chitosan schiff base as novel antibacterial biomaterials | |
| CN106496430A (en) | There is the antimicrobial macromolecule of biocompatibility | |
| CN108324731B (en) | Preparation method and application of biological polysaccharide particles for improving antioxidant activity and enhancing bacteriostatic action | |
| Huang et al. | Preparation, characterization, and antibacterial activity of oleic acid-grafted chitosan oligosaccharide nanoparticles | |
| CN104740672A (en) | Chitosan gold nano-particle compound as well as preparation method and application thereof | |
| CN106804624A (en) | A kind of nanometer of preparation method of chitosan oligosaccharide/silver co-induction anti-biotic material | |
| CN113813396B (en) | Kanamycin grafted cellulose-based antibacterial material and preparation method thereof | |
| Jothi et al. | Identification and isolation of chitin and chitosan from cuttle bone of Sepia prashadi Winckworth, 1936 | |
| Hasan et al. | Chitin and Chitosan | |
| Rizwan et al. | Novel chitosan derivative based composite scaffolds with enhanced angiogenesis; potential candidates for healing chronic non-healing wounds | |
| JPH03204804A (en) | Skin cosmetic | |
| KR20220037562A (en) | Edible antibacterial composite beads containing chitosan and nanocellulose and method for manufacturing the same | |
| Pati et al. | Chitosan from the carapace of Indian horseshoe crab (Tachypleus gigas, müller): Isolation and its characterization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190712 |