CN112315826A - A kind of functionalized graphene quantum dot antibacterial hand sanitizer and preparation method thereof - Google Patents

A kind of functionalized graphene quantum dot antibacterial hand sanitizer and preparation method thereof Download PDF

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CN112315826A
CN112315826A CN202011289500.3A CN202011289500A CN112315826A CN 112315826 A CN112315826 A CN 112315826A CN 202011289500 A CN202011289500 A CN 202011289500A CN 112315826 A CN112315826 A CN 112315826A
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graphene quantum
quantum dot
functionalized graphene
hand sanitizer
chlorogenic acid
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李在均
王娜
李瑞怡
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Jiangnan University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
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    • AHUMAN NECESSITIES
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    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
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    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005Antimicrobial preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/08Anti-ageing preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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Abstract

The invention discloses a functionalized graphene quantum dot antibacterial hand sanitizer and a preparation method thereof, wherein the antibacterial hand sanitizer comprises the following components in parts by mass: 0.1-2% of chlorogenic acid functionalized graphene quantum dot bactericide, 9-18% of nonionic surfactant, 0.5-1% of ethylene glycol distearate, 1-3% of glycerol, 0.5-3% of sodium hyaluronate, 0.45-0.8% of pH regulator, 0.1-0.2% of chelating agent, 1-1.4% of thickening agent and the balance of deionized water. The functionalized graphene quantum dot antibacterial hand sanitizer is stable in sterilization performance and free of irritation to skin.

Description

Functionalized graphene quantum dot antibacterial hand sanitizer and preparation method thereof
Technical Field
The invention relates to the technical field of hand sanitizer, and particularly relates to a functionalized graphene quantum dot antibacterial hand sanitizer and a preparation method thereof.
Background
It has been shown that most diseases are "introduced" by hand, and many pathogens are introduced into the mouth by hand, or by hand contact with the nose, eyes, etc., in a virtual manner, and thus, hand washing is the most effective way to prevent diseases. The hand sanitizer is used as a cleaning and nursing article specially used for washing hands, so that the cross infection risk of the traditional hand sanitizer can be greatly reduced, and the hand sanitizer is endowed with a plurality of new functions along with the technical progress; the hand sanitizer is developed from the initial cleaning to multi-functional, and most consumers pay attention to the bacteriostatic or bactericidal function when purchasing the hand sanitizer.
The bactericide added in the current commercial bacteriostatic hand sanitizer mainly comprises trichlorohydroxydiphenyl ether, Parachlorometaxylenol (PCMX), zinc pyrithione (ZTP) and benzalkonium chloride; although these substances have a bactericidal function, they have problems of bacterial resistance and health risks, and their addition amounts are extremely strictly controlled by health regulatory authorities.
The search for healthier and more efficient antibacterial substances is very necessary for reducing the health risk of the hand sanitizer and solving the drug resistance of bacteria, and is one of the key technologies for the technical development of the hand sanitizer.
Disclosure of Invention
The invention aims to provide a functionalized graphene quantum dot antibacterial hand sanitizer which is stable in sterilization performance and has no irritation to skin.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a functionalized graphene quantum dot antibacterial hand sanitizer, which comprises the following components in parts by mass: 0.1-2% of chlorogenic acid functionalized graphene quantum dot bactericide, 9-18% of nonionic surfactant, 0.5-1% of ethylene glycol distearate, 1-3% of glycerol, 0.5-3% of sodium hyaluronate, 0.45-0.8% of pH regulator, 0.1-0.2% of chelating agent, 1-1.4% of thickening agent and the balance of deionized water.
Further, the chlorogenic acid functionalized graphene quantum dot bactericide is prepared by the method (i) or (ii):
(i) heating the mixed solution of chlorogenic acid and graphene quantum dots at 90 ℃ for 10-30min, carrying out amidation reaction on amino groups of the graphene quantum dots and carboxyl groups of the chlorogenic acid, and dialyzing to remove unreacted substances after the reaction is finished, so as to obtain the chlorogenic acid functionalized graphene quantum dot bactericide;
(ii) carrying out chemical co-bond grafting on the graphene quantum dots and chlorogenic acid by EDC/NHS crosslinking reaction, which specifically comprises the following steps: adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into a chlorogenic acid solution, stirring for 1-2 hours at room temperature to activate carboxyl, and mixing a graphene quantum dot solution with N-hydroxysuccinimide; then adding a chlorogenic acid solution into the quantum dot solution to perform a chemical grafting reaction; dialyzing to remove unreacted substances after the reaction is finished to obtain the chlorogenic acid functionalized graphene quantum dot bactericide
Further, the molar ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, the N-hydroxysuccinimide and the chlorogenic acid is 1:1: 1.
Further, the graphene quantum dots are prepared by heating citric acid and diamine compounds serving as raw materials at 160-180 ℃ for 2-3 hours.
Further, the diamine compound is ethylenediamine and/or lysine.
Further, dialysis was performed for 24 hours using a 1000DA dialysis bag to remove unreacted materials.
Further, the nonionic surfactant comprises one or more of alkyl glucoside APG1214, fatty alcohol-polyoxyethylene ether (AEO-9) and cocamide DEA. Further, in the hand sanitizer, the weight ratio of the components of the surfactant is as follows: alkyl glucoside APG 12140-18%, fatty alcohol-polyoxyethylene ether (AEO-9) 0-18%, and cocamide DEA 0-18%.
Further, the pH regulator is citric acid.
Further, the chelating agent is disodium ethylene diamine tetraacetate.
Further, the thickener is sodium chloride.
The invention provides a preparation method of the functionalized graphene quantum dot antibacterial hand sanitizer, which comprises the following steps:
mixing the functionalized graphene quantum dot bactericide, the nonionic surfactant, the ethylene glycol distearate, the glycerol, the sodium hyaluronate, the chelating agent and deionized water according to the formula ratio, and uniformly stirring at 60-70 ℃; cooling to room temperature, adjusting the pH value of the solution to 6-6.5, and adding a thickening agent to obtain the hand sanitizer.
Compared with the prior art, the invention has the beneficial effects that:
1. chlorogenic acid is an antibacterial and antiviral effective component of plants such as honeysuckle and eucommia, and has the functions of resisting inflammation, resisting tumor, scavenging free radicals, resisting oxidation and preventing aging besides excellent antibacterial and antiviral functions. According to the invention, chlorogenic acid is used as a functional reagent to functionally modify graphene quantum dots, and the obtained functionalized graphene quantum dot bactericide is formed by combining chemical bonds, so that the bactericide has stable sterilization performance and is not easy to decompose in the processing process; and the graphene quantum dots and the chlorogenic acid generate a synergistic effect, and the bacteriostatic ability is still strong at low concentration.
2. Compared with other bactericides used in the antibacterial hand sanitizer, the graphene quantum dots, the chlorogenic acid and the compound thereof used in the invention are more friendly to human health, and the health risk of the antibacterial hand sanitizer is greatly reduced.
3. The hand sanitizer disclosed by the invention uses various nonionic surfactants, has good detergency, good affinity to skin, no stimulation and higher biodegradation rate, and greatly improves the affinity and environmental friendliness of the hand sanitizer.
4. The hand sanitizer disclosed by the invention is simple in preparation method, convenient to implement and convenient for industrial production.
Drawings
Fig. 1 is a flow chart of a synthesis process of a chlorogenic acid functionalized graphene quantum dot;
fig. 2 is a transmission electron microscope image of a chlorogenic acid functionalized graphene quantum dot.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used therein are commercially available without otherwise specified.
Example 1
1. Preparing the chlorogenic acid functionalized graphene quantum dots:
1) and (2) taking citric acid as a carbon source, weighing 5g of citric acid and 2g of ethylenediamine, adding into a beaker, and heating in an oven at 170 ℃ for 3 hours to prepare the Graphene Quantum Dots (GQD).
2) Carrying out chemical co-bond grafting on the graphene quantum dots and chlorogenic acid by EDC/NHS crosslinking reaction, adding 0.02g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) into 20mL of solution containing 0.05g of chlorogenic acid, and stirring for 1h at room temperature to activate carboxyl; meanwhile, 0.02g N-hydroxysuccinimide (NHS) is added into 80mL of solution containing 0.5g of graphene quantum dots; and then adding a chlorogenic acid solution into the quantum dot solution to perform a chemical grafting reaction, and dialyzing by using a 1000DA dialysis bag for 24 hours after the reaction is finished to remove unreacted substances, thereby obtaining the chlorogenic acid functionalized graphene quantum dot bactericide.
2. Preparation of hand sanitizer
1) According to the total amount of 100g, 0.2g of chlorogenic acid functionalized graphene quantum dots, alkyl glucoside APG 12149%, 8% of fatty alcohol-polyoxyethylene ether (AEO-9), 8% of cocamide DEA 5%, 0.5% of ethylene glycol distearate, 2% of glycerol, 2% of sodium hyaluronate, 0.1% of disodium ethylene diamine tetraacetate (EDTA-2Na) and deionized water are added to 100 g;
2) stirring the mixed solution uniformly at 60 ℃;
3) cooling the mixed solution to room temperature;
4) adjusting the pH of the solution to 6-6.5 by using a citric acid solution;
5) and adding sodium chloride into the solution for thickening to obtain the hand sanitizer.
Example 2
1. Preparing the chlorogenic acid functionalized graphene quantum dots:
1) and (2) taking citric acid as a carbon source, weighing 5g of citric acid and 2g of ethylenediamine, adding into a beaker, and putting into an oven to heat at 180 ℃ for 3 hours to prepare the Graphene Quantum Dots (GQD).
2) Heating 0.05g of chlorogenic acid and 0.5g of graphene quantum dot mixed solution at 90 ℃ for 30min, carrying out amidation reaction on amino groups of the graphene quantum dots and carboxyl groups of the chlorogenic acid, dialyzing by using a 1000DA dialysis bag for 24h after the reaction is finished, and removing unreacted substances to obtain the chlorogenic acid functionalized graphene quantum dot bactericide.
2. Preparation of hand sanitizer
1) According to the total amount of 100g, 0.2g of chlorogenic acid functionalized graphene quantum dots, alkyl glucoside APG 12149%, 5% of fatty alcohol-polyoxyethylene ether (AEO-9), 5% of cocamide DEA 8%, 1% of ethylene glycol distearate, 1% of glycerol, 2% of sodium hyaluronate, 0.2% of disodium ethylene diamine tetraacetate (EDTA-2Na) and deionized water are added to 100 g;
2) stirring the mixed solution uniformly at 60 ℃;
3) cooling the mixed solution to room temperature;
4) adjusting the pH of the solution to 6-6.5 by using a citric acid solution;
5) and adding sodium chloride into the solution for thickening to obtain the hand sanitizer.
Example 3
1. Preparing the chlorogenic acid functionalized graphene quantum dots:
1) and (2) taking citric acid as a carbon source, weighing 5g of citric acid and 2g of ethylenediamine, adding into a beaker, and putting into an oven to heat at 180 ℃ for 2.5 hours to prepare the Graphene Quantum Dots (GQD).
2) Carrying out chemical co-bond grafting on the graphene quantum dots and chlorogenic acid by EDC/NHS crosslinking reaction, adding 0.02g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) into 20mL of solution containing 0.05g of chlorogenic acid, and stirring for 1h at room temperature to activate carboxyl; meanwhile, 0.02g N-hydroxysuccinimide (NHS) is added into 80mL of solution containing 0.6g of graphene quantum dots; and then adding a chlorogenic acid solution into the quantum dot solution to perform a chemical grafting reaction, and dialyzing by using a 1000DA dialysis bag for 24 hours after the reaction is finished to remove unreacted substances, thereby obtaining the chlorogenic acid functionalized graphene quantum dot bactericide.
2. Preparation of hand sanitizer
1) According to the total amount of 100g, 0.4g of chlorogenic acid functionalized graphene quantum dots, alkyl glucoside APG 12149%, 8% of fatty alcohol-polyoxyethylene ether (AEO-9), 8% of cocamide DEA 5%, 0.5% of ethylene glycol distearate, 2% of glycerol, 2% of sodium hyaluronate, 0.1% of disodium ethylene diamine tetraacetate (EDTA-2Na) and deionized water are added to 100 g;
2) stirring the mixed solution uniformly at 60 ℃;
3) cooling the mixed solution to room temperature;
4) adjusting the pH of the solution to 6-6.5 with a citric acid solution;
5) and adding sodium chloride into the solution for thickening to obtain the hand sanitizer.
Comparative example 1
1. Preparing graphene quantum dots:
1) using citric acid as a carbon source, weighing 5g of citric acid and 2g of ethylenediamine, adding into a beaker, placing into an oven, heating at 180 ℃ for 3 hours to prepare Graphene Quantum Dots (GQD)
2. Preparation of hand sanitizer
1) According to the total amount of 100g, 0.5g of graphene quantum dots, alkyl glucoside APG 12149%, 8% of fatty alcohol-polyoxyethylene ether (AEO-9), 8% of cocamide DEA 5%, 0.5% of ethylene glycol distearate, 2% of glycerol, 2% of sodium hyaluronate, 0.1% of disodium ethylene diamine tetraacetate (EDTA-2Na) and deionized water are added to 100 g;
2) stirring the mixed solution uniformly at 60 ℃;
3) cooling the mixed solution to room temperature;
4) adjusting the pH of the solution to 6-6.5 with a citric acid solution;
5) and adding sodium chloride into the solution for thickening to obtain the hand sanitizer.
Comparative example 2
Preparation of hand sanitizer without addition of bactericide
1) According to the total amount of 100g, adding 100g of deionized water into alkyl glucoside APG 121411, 9% of fatty alcohol-polyoxyethylene ether (AEO-9), 6% of cocamide DEA, 0.5% of ethylene glycol distearate, 2% of glycerol, 2% of sodium hyaluronate, 0.1% of disodium ethylene diamine tetraacetate (EDTA-2 Na);
2) stirring the mixed solution uniformly at 60 ℃;
3) cooling the mixed solution to room temperature;
4) adjusting the pH of the solution to 6-6.5 with a citric acid solution;
5) and adding sodium chloride into the solution for thickening to obtain the hand sanitizer.
Test of antibacterial Property
The hand sanitizer of the embodiment 1-3 and the comparative example 1-2 are tested according to the light industry standard QB/T2738-2012 evaluation method for antibacterial and bacteriostatic effects of daily chemical products, the selected method is a suspension quantitative method, and the selected strains are staphylococcus aureus, escherichia coli, pseudomonas aeruginosa and candida albicans. The results obtained are shown in the following table.
Figure BDA0002783419840000081
The results show that the hand sanitizer samples in the embodiments 1 to 3 have the bacteriostasis rate of not less than 99% on staphylococcus aureus, the bacteriostasis rate of not less than 99% on escherichia coli, the bacteriostasis rate of not less than 99% on pseudomonas aeruginosa and the bacteriostasis rate of not less than 90% on candida albicans, and meet the requirement that the bacteriostasis rate of the special hand sanitizer GB l987.1.2005 is not less than 50%. The hand sanitizer samples of comparative examples 1-2 have unsatisfactory bacteriostatic effects, which indicates that the graphene quantum dots and the chlorogenic acid have bacteriostatic functions, and the graphene quantum dots and the chlorogenic acid generate synergistic effects in the invention, and when the addition amount is the same, the chlorogenic acid functionalized quantum dots have more excellent bactericidal performance than when one bacteriostatic agent is added alone.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims (10)

1. The functionalized graphene quantum dot antibacterial hand sanitizer is characterized by comprising the following components in parts by mass: 0.1-2% of chlorogenic acid functionalized graphene quantum dot bactericide, 9-18% of nonionic surfactant, 0.5-1% of ethylene glycol distearate, 1-3% of glycerol, 0.5-3% of sodium hyaluronate, 0.45-0.8% of pH regulator, 0.1-0.2% of chelating agent, 1-1.4% of thickening agent and the balance of deionized water.
2. The functionalized graphene quantum dot bacteriostatic hand sanitizer according to claim 1, wherein the chlorogenic acid functionalized graphene quantum dot bactericide is prepared by the method (i) or (ii):
(i) heating the mixed solution of chlorogenic acid and graphene quantum dots at 90 ℃ for 10-30min, carrying out amidation reaction on amino groups of the graphene quantum dots and carboxyl groups of the chlorogenic acid, and dialyzing to remove unreacted substances after the reaction is finished, so as to obtain the chlorogenic acid functionalized graphene quantum dot bactericide;
(ii) adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into a chlorogenic acid solution, stirring for 1-2 hours at room temperature to activate carboxyl, and mixing a graphene quantum dot solution with N-hydroxysuccinimide; then adding a chlorogenic acid solution into the quantum dot solution to perform a chemical grafting reaction; and dialyzing to remove unreacted substances after the reaction is finished, thereby obtaining the chlorogenic acid functionalized graphene quantum dot bactericide.
3. The functionalized graphene quantum dot antibacterial hand sanitizer according to claim 2, wherein the molar ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, the N-hydroxysuccinimide and the chlorogenic acid is 1:1: 1.
4. The functionalized graphene quantum dot antibacterial hand sanitizer according to claim 2, wherein the graphene quantum dot is prepared by heating citric acid and diamine compounds serving as raw materials at 160-180 ℃ for 2-3 hours.
5. The functionalized graphene quantum dot antibacterial hand sanitizer according to claim 4, wherein the diamine compound is ethylenediamine and/or lysine.
6. The functionalized graphene quantum dot bacteriostatic hand sanitizer according to claim 1, wherein the nonionic surfactant comprises one or more of alkyl glucoside APG1214, fatty alcohol-polyoxyethylene ether (AEO-9) and cocamide DEA.
7. The functionalized graphene quantum dot bacteriostatic hand sanitizer according to claim 1, wherein the pH regulator is citric acid.
8. The functionalized graphene quantum dot antibacterial hand sanitizer according to claim 1, wherein the chelating agent is disodium ethylenediaminetetraacetate.
9. The functionalized graphene quantum dot bacteriostatic hand sanitizer according to claim 1, wherein the thickener is sodium chloride.
10. The preparation method of the functionalized graphene quantum dot bacteriostatic hand sanitizer according to any one of claims 1 to 9, which is characterized by comprising the following steps:
mixing the functionalized graphene quantum dot bactericide, the nonionic surfactant, the ethylene glycol distearate, the glycerol, the sodium hyaluronate, the chelating agent and deionized water according to the formula ratio, and uniformly stirring at 60-70 ℃; cooling to room temperature, adjusting the pH value of the solution to 6-6.5, and adding a thickening agent to obtain the hand sanitizer.
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CN101766543A (en) * 2010-02-10 2010-07-07 北京欧凯纳斯科技有限公司 Hand sanitizer containing chlorine dioxide
CN110101870A (en) * 2019-05-23 2019-08-09 江南大学 Long-chain alkyl lycine-graphene quantum dot complex antimicrobials and preparation method thereof
CN110100839A (en) * 2019-05-24 2019-08-09 江苏敖广日化集团股份有限公司 A kind of bacteriostatic agent combination and preparation method thereof and the application in antibacterial tableware washing detergent liquid
CN110150277A (en) * 2019-05-24 2019-08-23 江苏敖广日化集团股份有限公司 A kind of bacteriostatic agent combination and preparation method thereof and the application in Antibacterial laundry detergent
CN111437206A (en) * 2020-05-27 2020-07-24 珠海纳金科技有限公司 Antibacterial and disinfectant hand sanitizer containing nano-silver and preparation method thereof

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Application publication date: 20210205