CN110256607A - A kind of anionic 2- hydroxypropyltrimethylammonium chloride chitosan and preparation method and application - Google Patents
A kind of anionic 2- hydroxypropyltrimethylammonium chloride chitosan and preparation method and application Download PDFInfo
- Publication number
- CN110256607A CN110256607A CN201910746938.0A CN201910746938A CN110256607A CN 110256607 A CN110256607 A CN 110256607A CN 201910746938 A CN201910746938 A CN 201910746938A CN 110256607 A CN110256607 A CN 110256607A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- anionic
- hydroxypropyltrimethylammonium chloride
- chloride chitosan
- formula
- 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.)
- Granted
Links
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3562—Sugars; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/125—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives containing carbohydrate syrups; containing sugars; containing sugar alcohols; containing starch hydrolysates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
- A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
- A61K31/716—Glucans
- A61K31/722—Chitin, chitosan
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/736—Chitin; Chitosan; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- 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
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Molecular Biology (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Food Science & Technology (AREA)
- Nutrition Science (AREA)
- Medicinal Chemistry (AREA)
- Epidemiology (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Dermatology (AREA)
- Biochemistry (AREA)
- Birds (AREA)
- Mycology (AREA)
- Communicable Diseases (AREA)
- Oncology (AREA)
- Materials Engineering (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Microbiology (AREA)
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention relates to field of food, cosmetic field and biological medicine industries, and in particular to a kind of anionic 2- hydroxypropyltrimethylammonium chloride chitosan and its preparation method and application.Anionic 2- hydroxypropyltrimethylammonium chloride chitosan structural formula is as the formula (1)；It is an advantage of the invention that reaction is simple, target compound yield is high, industrial application easy to spread.The experiment proved that the anionic 2- hydroxypropyltrimethylammonium chloride chitosan is water-soluble good, there is certain biocidal property, and there is fabulous moisture-absorbing moisture-keeping performance, can be widely applied to field of food, cosmetic field and biomedicine field.In formula (1) formula (1)Wherein n indicates the degree of polymerization, and average value range is 50-1000.
Description
Technical field
The present invention relates to field of food, cosmetic field and biological medicine industries, and in particular to a kind of anionic 2- hydroxyl
Hydroxypropyltrimonium chloride chitosan and its preparation method and application.
Background technique
The moisture absorption of moisture-absorption humectant and moisture-retaining capacity depend primarily on the size to hydrone active force, the main packet of application
Include the fields such as food, daily use chemicals.Wherein Sodium Hyaluronate is widely used as a kind of good moisture-absorption humectant, but hyalomitome
Sour sodium preparation process is complicated, at high cost, therefore finds one kind and function similar from a wealth of sources, the lower moisture-absorbing moisture-keeping of price
Agent substitute is an important project.At the same time, moisture-absorption humectant also has application, the parent of carbohydrate in field of food
Outlet capacity size be mostly important food in terms of one of functional character.Moisture-absorption humectant with bacteriostatic activity food,
The fields such as daily use chemicals can play prior effect.
Chitosan has biodegradability, biocompatibility, nontoxicity, film forming, moisture-absorbing moisture-keeping performance and anti-oxidant
Activity, therefore the every field such as medicine, food, agricultural, daily use chemicals can be widely applied to.Although chitosan has certain biology
Activity, but be not enough to that it is supported to develop and use on a large scale.Research has shown that, the 2- hydroxypropyl-trimethyl ammonium chloride shell of high substituted degree
Glycan has good moisture-absorbing moisture-keeping performance, and has certain biocidal property.At the same time, 2- hydroxypropyl-trimethyl ammonium chloride shell
Chloride ion in glycan can be replaced as the activity with highly hygroscopic performance of keeping humidity and bacteriostatic activity by way of ion exchange
Molecule promotes the activity of 2- hydroxypropyltrimethylammonium chloride chitosan.Modified chitosan derivatives have centainly antibacterial
Active and good moisture-absorbing moisture-keeping performance is the good selection for substituting traditional moisture-absorption humectant, simultaneously because its is good antibacterial
Activity and moisture-absorbing moisture-keeping performance, can be used as functional food additives to improve food configuration, enhance the water retaining function of food
And food water activity is adjusted, the Perserving materials of food can also be acted on to realize the fresh-keeping of food.
Summary of the invention
In order to solve the above technical problems, the invention proposes a kind of anionic 2- hydroxypropyltrimethylammonium chloride chitosan
And its preparation method and application.
To achieve the above object, the invention adopts a technical scheme as:
A kind of anionic 2- hydroxypropyltrimethylammonium chloride chitosan, anionic 2- hydroxypropyltrimethylammonium chloride chitosan
Structural formula is as the formula (1):
Formula (1)
In formula (1)
Wherein n indicates the degree of polymerization, and average value range is 50-1000.
The preparation method of anionic 2- hydroxypropyltrimethylammonium chloride chitosan:
(1) it disperses chitosan in isopropanol and is swollen, sodium hydrate aqueous solution, the chloro- 2- Hydroxyproyl Trimethyl chlorination of 3- is added
It after ammonium salt solution mixing, is reacted 9-12 hours in metal bath under the conditions of 55 DEG C -75 DEG C, alcohol precipitation dries to arrive 2- hydroxyl after filtering
Hydroxypropyltrimonium chloride chitosan；
(2) above-mentioned 2- hydroxypropyltrimethylammonium chloride chitosan is dissolved in deionized water, pyrrolidone sodium carboxylate is then added
Aqueous solution, sodium lactate aqueous solution or aqueous solutions of betaine retain dialysis in reacting 6-8h under room temperature after mixing after reaction
Afterwards, freeze-drying is to get anionic 2- hydroxypropyltrimethylammonium chloride chitosan shown in formula (1).
The mole of step (1) the 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride is the 3-5 of chitosan mole
Times；The mole of the sodium hydroxide is 1-1.5 times of chitosan mole.
Alcohol precipitation is carried out to reaction product with ethyl alcohol after reacting 9-12 hours in the metal bath, is then through mass fraction again
95% ethanol washing, drying is to get arriving 2- hydroxypropyltrimethylammonium chloride chitosan after suction filtration.
The mole of step (2) the 2- hydroxypropyltrimethylammonium chloride chitosan is connected bioactive molecule (bioactive molecule
For pyrrolidone sodium carboxylate, sodium lactate or glycine betaine) 3-5 times of mole.
After the step (2) reaction by reactant mixed solution be transferred to the bag filter that molecular cut off is 500 spend from
Sub- water dialysis 24-48h freeze-drying is to get anionic 2- hydroxypropyltrimethylammonium chloride chitosan shown in formula (1).
The step (2) could alternatively be after 2- hydroxypropyltrimethylammonium chloride chitosan is completely dissolved in deionized water,
It is transferred in the bag filter that molecular cut off is 500, pyrrolidone sodium carboxylate aqueous solution, sodium lactate aqueous solution or sweet tea is then added
Dish aqueous alkali carries out hemodialysis reaction 12-24 hours, uses deionized water dialysis 24-48h again after reaction, freezes after concentration dry
It is dry to get to anionic 2- hydroxypropyltrimethylammonium chloride chitosan shown in formula (1).
The chitosan is scattered in isopropanol, the final concentration of 10%-25% of chitosan；The Hydroxyproyl Trimethyl chlorination
The concentration that ammonium chitosan is dissolved in deionized water obtained aqueous solution is 5%-20%.
Pyrrolidone sodium carboxylate concentration is 5%-15wt%, in sodium lactate aqueous solution in the pyrrolidone sodium carboxylate aqueous solution
Lactic acid na concn is 5%-15wt%, the concentration of glycine betaine is 5%-15wt% in aqueous solutions of betaine.
The application of anionic 2- hydroxypropyltrimethylammonium chloride chitosan, the anionic 2- Hydroxyproyl Trimethyl chlorine
Change ammonium chitosan answering as antibacterial material, moisture absorption or moisturizer in field of food, cosmetic field or biomedicine field
With.
Compared with prior art, advantageous effects of the invention are as follows:
(1) present invention is to chitosan by modifying to have the moisture-absorption humectant of bacteriostatic activity in bacteriostatic activity and moisture absorbability and moisture retentivity
Energy aspect is superior to hyaluronic acid, and present invention gained has the moisture-absorption humectant water solubility of bacteriostatic activity good, application prospect
More extensively.
(2) present invention gained anionic 2- hydroxypropyltrimethylammonium chloride chitosan preparation process is simple, target product
Yield is high, reaction process material therefor is at low cost, and present invention gained anionic 2- hydroxypropyltrimethylammonium chloride chitosan
It is fabulous with certain bacteriostatic activity, moisture-absorbing moisture-keeping activity, it is suitble to promote industrial application, can be widely applied to food neck
Domain, cosmetic field and biomedicine field.
Detailed description of the invention
Fig. 1 is the synthetic route of anionic 2- hydroxypropyltrimethylammonium chloride chitosan provided in an embodiment of the present invention
Figure.
The infrared spectrogram of Fig. 2 chitosan；3428 cm-1Place is the hydroxyl absorption peak in chitosan saccharide ring, 2919 cm-1
Place is the saturated alkane C-H stretching vibration absworption peak of chitosan, 1646 cm-1Place is the amino stretching vibration absworption peak of chitosan.
Fig. 3 provides the infrared spectrogram of 2- hydroxypropyltrimethylammonium chloride chitosan for the embodiment of the present invention；1478 cm-1
Place is the vibration absorption peak for the methyl that chitosan introduces quaternary ammonium salt.
Fig. 4 is 1 pyrrolidone sodium carboxylate anionic 2- hydroxypropyltrimethylammonium chloride chitosan of the embodiment of the present invention
Infrared spectrogram；1727 cm-1Locate the vibration absorption peak for C=O in connect pyrrolidone sodium carboxylate anion, 1565 cm-1Place
For the vibration absorption peak of heterocycle in pyrrolidone sodium carboxylate anion.
Fig. 5 is the infrared spectroscopy of 2 sodium lactate anionic 2- hydroxypropyltrimethylammonium chloride chitosan of the embodiment of the present invention
Figure；1416 cm-1Place is the absorption peak of carboxylic acid anion.
Fig. 6 is the infrared spectroscopy of 3 glycine betaine anionic 2- hydroxypropyltrimethylammonium chloride chitosan of the embodiment of the present invention
Figure；1415 cm-1Place is the absorption peak of carboxylic acid anion.
Specific embodiment
A specific embodiment of the invention is described further below in conjunction with example, it is noted that retouch in this place
The specific embodiment stated is simply to illustrate that with the present invention is explained, it is not limited to the present invention.
Gained anionic 2- hydroxypropyltrimethylammonium chloride chitosan preparation process of the invention is simple, target product yield
Height, reaction process material therefor are at low cost, and present invention gained anionic 2- hydroxypropyltrimethylammonium chloride chitosan has
Certain bacteriostatic activity, moisture-absorbing moisture-keeping activity are fabulous, are suitble to promote industrial application, can be widely applied to field of food, change
Cosmetic field and biomedicine field.
The present invention is with chitosan, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, sodium hydroxide, active moisture-absorbing moisture-keeping compound
For raw material, it is prepared for a kind of anionic 2- hydroxypropyltrimethylammonium chloride chitosan.It further says, preparation method is divided into
Two steps: (1) using chitosan as raw material, it is modified using chloro- 2 hydroxypropyl-trimethyl ammonium chloride of 3-, obtains reactivity
Intermediate.(2) based on the mode of ion exchange, it is a series of with life that pyrrolidone sodium carboxylate, sodium lactate and glycine betaine etc. are grafted
The anionic compound of object activity and moisture-absorbing moisture-keeping performance, it is poly- to obtain the anionic 2- hydroxypropyl-trimethyl ammonium chloride shell
Sugar.Preparation process of the present invention is simple, and target product yield is high, reaction process material therefor is at low cost, and present invention gained yin from
Sonization 2- hydroxypropyltrimethylammonium chloride chitosan has certain bacteriostatic activity, moisture-absorbing moisture-keeping activity fabulous, is suitble to promote producing
Industry application can be widely applied to field of food, cosmetic field and biomedicine field.
Embodiment 1
The synthetic route of anionic 2- hydroxypropyltrimethylammonium chloride chitosan as shown in Figure 1, wherein n indicates the degree of polymerization, puts down
Equal value range is 50-1000.
(1) it weighs chitosan (molecular weight about 50,000) 3.38g to be scattered in 30mL isopropanol and be swollen, is added dropwise and quality point is added
Count the sodium hydrate aqueous solution 1.2mL for 40%, the 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution that mass fraction is 60%
19mL reacts under the conditions of 55 DEG C 9 hours in metal bath reaction pot, uses ethanol precipitation and washing after reaction, dries after suction filtration
It does to get 2- hydroxypropyltrimethylammonium chloride chitosan is arrived.
(2) it weighs above-mentioned 2- hydroxypropyltrimethylammonium chloride chitosan 3g to be dissolved in 60mL deionized water, then by quality
The pyrrolidone sodium carboxylate aqueous solution 30mL of score 15% is added dropwise to the former, in reacting 6h under room temperature, then by mixed solution
It is transferred to the bag filter deionized water dialysis that molecular cut off is 500 for 24 hours, is freeze-dried to get pyrrolidines shown in formula one
Keto carboxylic acid sodium anionic 2- hydroxypropyltrimethylammonium chloride chitosan, n 300-320.
Embodiment 2
Difference from Example 1 is:
(1) it weighs chitosan (molecular weight about 100,000) 3.38g to be scattered in 25mL isopropanol and be swollen, addition mass fraction, which is added dropwise, is
40% sodium hydrate aqueous solution 1.4mL, mass fraction is 60% 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution 25mL, 60
It is reacted in metal bath under the conditions of DEG C 10 hours, uses ethanol precipitation and washing after reaction, dried after suction filtration to get 2- hydroxyl is arrived
Hydroxypropyltrimonium chloride chitosan.
(2) it after weighing 2- hydroxypropyltrimethylammonium chloride chitosan 3g is completely dissolved in 30mL deionized water, is transferred to and cuts
It stays in the bag filter that molecular weight is 500, sodium lactate aqueous solution hemodialysis reaction 12 hours that concentration is 10%, after reaction again
For 24 hours with deionized water dialysis, it is freeze-dried after concentration to get sodium lactate anionic 2- Hydroxyproyl Trimethyl chlorine shown in formula one is arrived
Change ammonium chitosan, n 600-630.
Embodiment 3
Difference from Example 1 is:
(1) it weighs chitosan (molecular weight about 150,000) 3.38g to be scattered in 15mL isopropanol and be swollen, addition mass fraction, which is added dropwise, is
40% sodium hydrate aqueous solution 1.6mL, mass fraction is 60% 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution 30mL, 75
It is reacted in metal bath under the conditions of DEG C 12 hours, uses ethanol precipitation and washing after reaction, dried after suction filtration to get 2- hydroxyl is arrived
Hydroxypropyltrimonium chloride chitosan.
(2) it weighs above-mentioned 2- hydroxypropyltrimethylammonium chloride chitosan 3g to be dissolved in 20mL deionized water, is transferred to retention
In the bag filter that molecular weight is 500, aqueous solutions of betaine hemodialysis reaction 12 hours that concentration is 15%, use again after reaction
Deionized water dialysis 48h is freeze-dried to get glycine betaine anionic 2- Hydroxyproyl Trimethyl chlorination shown in formula one is arrived after concentration
Ammonium chitosan, n 920-950.
Application examples 1
The active measurement of moisture absorption
It is surveyed respectively under saturated ammonium sulfate solution (relative humidity 81%) and saturated sodium carbonate solution (relative humidity 43%) environment
The moisture absorption activity of material sample is tried, wherein material sample is respectively that chitosan, commercial clear matter acid sodium and embodiment prepare
Pyrrolidone sodium carboxylate anionic 2- hydroxypropyltrimethylammonium chloride chitosan, sodium lactate anionic 2- Hydroxyproyl Trimethyl
Ammonium chloride chitosan, glycine betaine anionic 2- hydroxypropyltrimethylammonium chloride chitosan:
By above-mentioned sample material respectively at 65 DEG C under the conditions of dry 48h to constant weight after, weigh 0.20g respectively and be placed in dry title
In measuring bottle, the weighing bottle for filling sample material is placed in the drier that relative humidity is 81% and relative humidity is 43%,
The quality for weighing a weighing bottle at regular intervals, calculates the moisture absorption activity of sample, and all experimentss are repeated once.
Hydroscopicity (%)=(W1-W0) × 100/W0
W0And W1Respectively sample places forward and backward quality (g)
Table 1, moisture absorption of the material sample in RH=81% are active (%)
Table 2, moisture absorption of the material sample in RH=43% are active (%)
Application examples 2
The active measurement of moisturizing
In saturated ammonium sulfate solution (relative humidity 81%), saturated sodium carbonate solution (relative humidity 43%) and dry silica gel environment
The lower moisturizing activity for testing material sample respectively simultaneously compares:
Wherein material sample is respectively chitosan, commercial clear matter acid sodium and pyrrolidone sodium carboxylate anionic 2- hydroxypropyl three
Ammonio methacrylate chitosan, sodium lactate anionic 2- hydroxypropyltrimethylammonium chloride chitosan, glycine betaine anionic 2- hydroxyl
Hydroxypropyltrimonium chloride chitosan:
By above-mentioned raw materials sample respectively at 65 DEG C under the conditions of dry 48h to constant weight after, weigh 0.50g respectively and be placed in dry title
In measuring bottle, and 50 μ L deionized waters are added, the weighing bottle for filling sample is placed in relative humidity is 81%, relative humidity is
43% and dry silica gel drier in, weigh the quality of a weighing bottle at regular intervals, the moisturizing for calculating sample is living
Property, all experimentss are repeated once.
Moisturizing rate (%)=100 × Hn/H0
H0、HnRespectively place the quality (g) of front and back moisture
Table 3, moisturizing of the material sample in RH=81% are active (%)
Table 4, moisturizing of the material sample in RH=43% are active (%)
Table 5, moisturizing of material sample under the conditions of dry silica gel are active (%)
Application examples 3
Antibacterial Activity
Using mycelial growth rate method measurement material sample to the inhibiting effect of the pathogen of Botrytis cinerea.Concrete operations are as follows: by raw material sample
After product vacuum freeze drying to constant weight, with water as solvent, after being configured to the sample aqueous solution of 6 mg/mL, 0.2 mL is taken respectively, 1
It is to shake up and take advantage of in the commercially available fungi culture medium of 11.8 mL, 11 mL and 10 mL that mL and 2 mL sample solutions, which are added to volume,
Heat pour into diameter be 6 cm batch cultur ware in cooled and solidified, sample ultimate density be 0.1 mg/mL, 0.5 mg/mL and
1.0 mg/mL.After its completely solidification, bacteria cake is carefully inoculated in the solid medium center of solidification with aseptic nipper,
28 °C, cultivate 48h under 60% damp condition.Using the carbendazim of isoconcentration as positive control, sample is replaced with isometric sterile water
As blank control.Then it using the diameter of crossing method measurement mycelia formation zone, is averaged.The bacteriostasis rate of sample
Calculation formula is as follows:
Bacteriostasis rate (%)=[1- (DSample-5)/(DBlank-5)]×100
Wherein DSampleFor sample sets mycelia growth diameter, DBlankFor blank group mycelia growth diameter
Wherein material sample is respectively chitosan, commercial clear matter acid sodium and pyrrolidone sodium carboxylate anionic 2- hydroxypropyl three
Ammonio methacrylate chitosan, sodium lactate anionic 2- hydroxypropyltrimethylammonium chloride chitosan, glycine betaine anionic 2- hydroxyl
Hydroxypropyltrimonium chloride chitosan:
Table 6, the bacteriostatic activity (%) of material sample
Experimental result: anionic 2- hydroxypropyltrimethylammonium chloride chitosan and chitosan, hyalomitome synthesized by the present invention
As shown in tables 1 to 5, bacteriostatic activity is as shown in table 6 for the moisture-absorbing moisture-keeping performance of sour sodium.Research has shown that the moisture absorption of chitosan is protected in experiment
Wet performance will be far below Sodium Hyaluronate, but after introducing pyrrolidone sodium carboxylate, sodium lactate and glycine betaine anion, moisture absorption
Performance of keeping humidity has significant raising, the results showed that pyrrolidone sodium carboxylate anionic 2- hydroxypropyl-trimethyl ammonium chloride shell
Glycan, sodium lactate anionic 2- hydroxypropyltrimethylammonium chloride chitosan, glycine betaine anionic 2- Hydroxyproyl Trimethyl chlorine
The moisture-absorbing moisture-keeping performance for changing ammonium chitosan is higher by the moisture-absorbing moisture-keeping performance of control Sodium Hyaluronate, glycine betaine anionic 2- hydroxyl
The moisture-absorbing moisture-keeping performance of hydroxypropyltrimonium chloride chitosan is best.At the same time, compared with Sodium Hyaluronate, the present invention is closed
At moisture-absorption humectant have apparent bacteriostatic activity.In addition, the cost of the above-mentioned target compound prepared is far below saturating
Bright matter acid sodium, and moisture-absorbing moisture-keeping activity is significantly higher than Sodium Hyaluronate, is provided simultaneously with certain bacteriostatic activity, this is just a kind of new
The exploitation of type moisture-absorption humectant or antibacterial material provides technical support and considerable development potentiality.
Claims (10)
1. a kind of anionic 2- hydroxypropyltrimethylammonium chloride chitosan, it is characterised in that: anionic 2- hydroxypropyl trimethylammonium
Ammonium chloride chitosan structure formula is as the formula (1):
Formula (1)
In formula (1)
Wherein n indicates the degree of polymerization, and average value range is 50-1000.
2. the preparation method of anionic 2- hydroxypropyltrimethylammonium chloride chitosan as described in claim 1, it is characterised in that:
(1) it disperses chitosan in isopropanol and is swollen, sodium hydrate aqueous solution, the chloro- 2- Hydroxyproyl Trimethyl chlorination of 3- is added
It after ammonium salt solution mixing, is reacted 9-12 hours in metal bath under the conditions of 55 DEG C -75 DEG C, alcohol precipitation dries to arrive 2- hydroxyl after filtering
Hydroxypropyltrimonium chloride chitosan；
(2) above-mentioned 2- hydroxypropyltrimethylammonium chloride chitosan is dissolved in deionized water, pyrrolidone sodium carboxylate is then added
Aqueous solution, sodium lactate aqueous solution or aqueous solutions of betaine retain dialysis in reacting 6-8h under room temperature after mixing after reaction
Afterwards, freeze-drying is to get anionic 2- hydroxypropyltrimethylammonium chloride chitosan shown in formula (1).
3. the preparation method of anionic 2- hydroxypropyltrimethylammonium chloride chitosan as claimed in claim 2, feature exist
In: the mole of step (1) the 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride is 3-5 times of chitosan mole；It is described
The mole of sodium hydroxide is 1-1.5 times of chitosan mole.
4. the preparation method of anionic 2- hydroxypropyltrimethylammonium chloride chitosan as claimed in claim 2, feature exist
In: after reacting 9-12 hours in the metal bath alcohol precipitation is carried out to reaction product with ethyl alcohol, through mass fraction is again then 95%
Ethanol washing, drying is to get arriving 2- hydroxypropyltrimethylammonium chloride chitosan after suction filtration.
5. the preparation method of anionic 2- hydroxypropyltrimethylammonium chloride chitosan as claimed in claim 2, feature exist
In: the mole of step (2) the 2- hydroxypropyltrimethylammonium chloride chitosan is 3-5 times of connected bioactive molecule mole.
6. the preparation method of anionic 2- hydroxypropyltrimethylammonium chloride chitosan as claimed in claim 2, feature exist
In: it is saturating that reactant mixed solution is transferred to the bag filter deionized water that molecular cut off is 500 after the step (2) reaction
24-48h freeze-drying is analysed to get anionic 2- hydroxypropyltrimethylammonium chloride chitosan shown in formula (1).
7. the preparation method of the anionic 2- hydroxypropyltrimethylammonium chloride chitosan as described in claim 2 or 6, feature
Be: the step (2) could alternatively be transfer after 2- hydroxypropyltrimethylammonium chloride chitosan is completely dissolved in deionized water
In the bag filter for being 500 to molecular cut off, pyrrolidone sodium carboxylate aqueous solution, sodium lactate aqueous solution or glycine betaine is then added
Aqueous solution carries out hemodialysis reaction 12-24 hours, uses deionized water dialysis 24-48h again after reaction, is freeze-dried after concentration,
Obtain anionic 2- hydroxypropyltrimethylammonium chloride chitosan shown in formula (1).
8. the preparation method of anionic 2- hydroxypropyltrimethylammonium chloride chitosan as claimed in claim 2, feature exist
In: the chitosan is scattered in isopropanol, the final concentration of 10%-25% of chitosan；The hydroxypropyl-trimethyl ammonium chloride shell
The concentration that glycan is dissolved in deionized water obtained aqueous solution is 5%-20%.
9. the preparation method of anionic 2- hydroxypropyltrimethylammonium chloride chitosan as claimed in claim 2, feature exist
In: in the pyrrolidone sodium carboxylate aqueous solution pyrrolidone sodium carboxylate concentration be 5%-15wt%, lactic acid in sodium lactate aqueous solution
Na concn is 5%-15wt%, the concentration of glycine betaine is 5%-15wt% in aqueous solutions of betaine.
10. anionic 2- hydroxypropyltrimethylammonium chloride chitosan as described in claim 1, it is characterised in that: the yin
2- hydroxypropyltrimethylammonium chloride chitosan is ionized in field of food, cosmetic field or biomedicine field as antibacterial
Material, moisture absorption or the application of moisturizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910746938.0A CN110256607B (en) | 2019-08-14 | 2019-08-14 | Anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910746938.0A CN110256607B (en) | 2019-08-14 | 2019-08-14 | Anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110256607A true CN110256607A (en) | 2019-09-20 |
| CN110256607B CN110256607B (en) | 2022-03-08 |
Family
ID=67912043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910746938.0A Active CN110256607B (en) | 2019-08-14 | 2019-08-14 | Anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110256607B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627920A (en) * | 2019-10-08 | 2019-12-31 | 中国科学院烟台海岸带研究所 | Moisture absorption humectant with antioxidant activity and preparation method and application thereof |
| CN112190502A (en) * | 2020-09-21 | 2021-01-08 | 山东省药学科学院 | Hyaluronic acid quaternary ammonium salt compound |
| CN113773412A (en) * | 2021-09-18 | 2021-12-10 | 中国科学院烟台海岸带研究所 | Process for the preparation of anionic polysaccharide derivatives |
| CN114904496A (en) * | 2022-05-10 | 2022-08-16 | 安徽潜隆机电科技有限公司 | Activated carbon gas mask material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003012494A (en) * | 2001-07-05 | 2003-01-15 | Arkray Inc | Moisture-retaining agent |
| CN101177461A (en) * | 2007-12-04 | 2008-05-14 | 盐城工学院 | Preparation of quaternary ammonium N-carboxyetbyl chitosan |
| CN101613420A (en) * | 2009-08-06 | 2009-12-30 | 浙江澳兴生物科技有限公司 | A kind of preparation method of 2-HACC |
| CN107163160A (en) * | 2017-07-03 | 2017-09-15 | 中国科学院烟台海岸带研究所 | A kind of Ascorbic acid chitosan quaternary ammonium salt and its preparation method and application |
| CN108623708A (en) * | 2018-06-01 | 2018-10-09 | 中国科学院烟台海岸带研究所 | A kind of chitosan quaternary ammonium salt and its preparation method and application containing halogenated acetic acids |
| CN108752501A (en) * | 2018-06-01 | 2018-11-06 | 中国科学院烟台海岸带研究所 | A kind of chitosan quaternary ammonium salt and its preparation method and application containing acylate |
| CN109400754A (en) * | 2018-11-05 | 2019-03-01 | 中国科学院烟台海岸带研究所 | A kind of chitosan-active acid complex salt and its preparation method and application |
| CN109762078A (en) * | 2019-04-09 | 2019-05-17 | 中国科学院烟台海岸带研究所 | A kind of hydroxypropyltrimethylammonium chloride chitosan-carboxylated polysaccharide complex salt and preparation method and application |
-
2019
- 2019-08-14 CN CN201910746938.0A patent/CN110256607B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003012494A (en) * | 2001-07-05 | 2003-01-15 | Arkray Inc | Moisture-retaining agent |
| CN101177461A (en) * | 2007-12-04 | 2008-05-14 | 盐城工学院 | Preparation of quaternary ammonium N-carboxyetbyl chitosan |
| CN101613420A (en) * | 2009-08-06 | 2009-12-30 | 浙江澳兴生物科技有限公司 | A kind of preparation method of 2-HACC |
| CN107163160A (en) * | 2017-07-03 | 2017-09-15 | 中国科学院烟台海岸带研究所 | A kind of Ascorbic acid chitosan quaternary ammonium salt and its preparation method and application |
| CN108623708A (en) * | 2018-06-01 | 2018-10-09 | 中国科学院烟台海岸带研究所 | A kind of chitosan quaternary ammonium salt and its preparation method and application containing halogenated acetic acids |
| CN108752501A (en) * | 2018-06-01 | 2018-11-06 | 中国科学院烟台海岸带研究所 | A kind of chitosan quaternary ammonium salt and its preparation method and application containing acylate |
| CN109400754A (en) * | 2018-11-05 | 2019-03-01 | 中国科学院烟台海岸带研究所 | A kind of chitosan-active acid complex salt and its preparation method and application |
| CN109762078A (en) * | 2019-04-09 | 2019-05-17 | 中国科学院烟台海岸带研究所 | A kind of hydroxypropyltrimethylammonium chloride chitosan-carboxylated polysaccharide complex salt and preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| 宋丽雅等: "《化妆品植物功效添加剂的研究与开发》", 30 September 2011, 中国轻工业出版社 * |
| 章苏宁等: "《妆品工艺学》", 30 September 2007 * |
| 路艳华等: "《壳聚糖及纳米材料在杵蚕丝功能改性中的应用》", 31 August 2012 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627920A (en) * | 2019-10-08 | 2019-12-31 | 中国科学院烟台海岸带研究所 | Moisture absorption humectant with antioxidant activity and preparation method and application thereof |
| CN110627920B (en) * | 2019-10-08 | 2022-05-17 | 中国科学院烟台海岸带研究所 | Moisture absorption humectant with antioxidant activity and preparation method and application thereof |
| CN112190502A (en) * | 2020-09-21 | 2021-01-08 | 山东省药学科学院 | Hyaluronic acid quaternary ammonium salt compound |
| CN113773412A (en) * | 2021-09-18 | 2021-12-10 | 中国科学院烟台海岸带研究所 | Process for the preparation of anionic polysaccharide derivatives |
| CN114904496A (en) * | 2022-05-10 | 2022-08-16 | 安徽潜隆机电科技有限公司 | Activated carbon gas mask material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110256607B (en) | 2022-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110256607A (en) | A kind of anionic 2- hydroxypropyltrimethylammonium chloride chitosan and preparation method and application | |
| JP2020527643A (en) | New water-soluble natural polysaccharide antibacterial material and its preparation method | |
| CN104672348B (en) | Chitosan quaternary ammonium salt derivatives with good aqueous solubility and antibacterial activity and preparation method thereof | |
| CN108623708A (en) | A kind of chitosan quaternary ammonium salt and its preparation method and application containing halogenated acetic acids | |
| CN105085709B (en) | Chitosan oligosaccharide quaternary ammonium salt derivative and method for preparing nanometer silver through same | |
| CN106995502B (en) | Bifunctional group modified chitosan derivative and preparation method thereof | |
| CN101624427A (en) | Arginine-chitosan with high degree of substitution, preparation method and application thereof | |
| CN107043432A (en) | A kind of both sexes carboxymethyl chitosan guanidine salt derivative and preparation method thereof | |
| CN110003359A (en) | A kind of hydrophily high substituted degree modification of chitosan preparation method and applications | |
| CN105820333A (en) | Preparation method of polyhexamethyleneguanidine hydrochloride | |
| WO2017016022A1 (en) | Chito-oligosaccharide-o-kojic acid-mannich base derivative antibacterial agent and preparation method thereof | |
| CN107344971A (en) | A kind of poly- ε-lysine modified chitosan and preparation method thereof | |
| CN100494223C (en) | Synthesis of quaternary ammonium salt modified nucleophilic NO donor | |
| Jou | Antibacterial activity and cytocompatibility of chitosan-N-hydroxy-2, 3-propyl-N methyl-N, N-diallylammonium methyl sulfate | |
| CN112480288A (en) | Ionized chitosan and preparation method and application thereof | |
| CN108864324B (en) | Triazole-based chitosan biquaternary ammonium salt and preparation method and application thereof | |
| JP2023548948A (en) | Use of hyaluronic acid or a salt thereof and/or trehalose in stabilizing ergothioneine and ergothioneine compositions containing hyaluronic acid or a salt thereof and/or trehalose | |
| CN108359089A (en) | A kind of antibiotic property poly(aryl ether ketone) material and preparation method thereof | |
| CN102382206B (en) | Chitooligosaccharide quaternary ammonium salt and preparation method thereof | |
| CN110183546B (en) | Gel polysaccharide water-soluble antibacterial derivative and preparation method thereof | |
| CN102153673A (en) | N-parabenzyloxycarboxymethyl chitosan quaternary ammonium salt and preparation method thereof | |
| CN104358123B (en) | A kind of preparation method of propionyloxyethyl trimethyl ammonium chloride chitin fiber | |
| CN111548388B (en) | PH-responsive non-helix transition antibacterial polypeptide and preparation method thereof | |
| CN110627920B (en) | Moisture absorption humectant with antioxidant activity and preparation method and application thereof | |
| CN112442142B (en) | Halogenated benzene-containing carboxymethyl chitosan and preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |