CN112262854A - Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent and preparation method thereof - Google Patents
Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent and a preparation method thereof, wherein ATP is used as a carrier, alkyl glycoside quaternary ammonium salt (APGQAS) is used as a surface modifier, Cl-modified GQD is used as a main antibacterial component, and the defect sites of the GQD are increased by modifying the GQD, so that the surface photogeneration-electron recombination is effectively inhibited, and the generation of active oxygen is promoted; then, APGQAS is adopted to carry out surface modification on the acidified attapulgite, and Cl modified GQD quantum dots are adsorbed on the surface of the modified acidified attapulgite by utilizing the bridge action of cationic polymer APGQAS; and finally, adsorbing bacteria to the surface of the Cl-modified GQD/APGQAS/acidified attapulgite nanocomposite by using the huge specific surface area and potential difference, and then synergistically loading the Cl-modified GQD quantum dots (GQD-Cl) and APGQAS between the modified attapulgite surface and the pore channel to play a role in natural antibiosis, thereby playing a role in high efficiency antibiosis. The technical scheme has the advantages of safety, no pollution, high antibacterial efficiency and the like, and the antibacterial rate of the nano composite antibacterial agent prepared by the method at 4mg/ml to escherichia coli can reach 99.01%.
Description
Technical Field
The invention relates to a safe, environment-friendly and efficient antibacterial agent, and particularly relates to a Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent and a preparation method thereof.
Background
In recent years, the mass propagation of germs causes frequent infection and illness of human bodies, and seriously affects normal life and health safety, so people begin to use a large amount of antibiotics, and the 'super bacteria' produced by the antibiotics seriously harms human health. Therefore, the research and development of novel high-efficiency antibacterial materials which are eco-friendly and environment-friendly are urgent.
The novel carbon quantum dot material is favored because of the advantages of good water solubility, low biotoxicity, good conductivity and the like. Relevant studies have shown that: the reactivity generally depends on that the defect or heteroatom site carbon nano material can generate active oxygen through surface reaction under illumination. Graphene quantum dots are used as a novel quantum dot material, and surface functional group modification can be performed by utilizing reaction to obtain different performances. The chlorine atom has larger atomic radius and higher electronegativity than the carbon atom, and the doping of the chlorine atom can cause the corresponding change of the electron density and the charge transfer capacity of the GQD. The prepared Cl-GQD has better fluorescence and photocatalysis characteristics and biocompatibility. Therefore, chlorine atom doping of GQD can realize effective interface charge transfer and inhibit electron hole pair recombination, thereby accelerating generation of active oxygen and improving antibacterial performance of the composite material. However, the small-sized quantum dots are easily agglomerated, and the antibacterial performance thereof is seriously affected.
Attapulgite (ATP) is a natural porous material carrier, the structure of which is in a layer chain crystal shape and shows a fine rod shape and a fiber shape, but the natural attapulgite shows a lower adsorption capacity, so the attapulgite needs to be modified to improve the adsorption performance. An acid activation treatment at an appropriate concentration can remove impurities such as carbonate in the pore channels thereof to increase the specific surface area and pore volume. In addition, the acidified attapulgite has more negative charges than natural attapulgite. Therefore, the acidified attapulgite becomes an ideal carrier of the antibacterial material.
However, both acidified attapulgite and Cl-GQD have negatively charged surfaces and it is difficult to successfully combine them. The alkyl glycoside quaternary ammonium salt surfactant is a quaternary ammonium salt cationic surfactant prepared by quaternizing active groups of raw materials based on alkyl glycoside. The antibacterial agent has the natural, green, low-toxicity, low-irritation and easily biodegradable performances of alkyl glycoside, and also has the bactericidal performance of quaternary ammonium salt, and the performance of cationic positive charge.
Disclosure of Invention
The invention aims to provide a Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent and a preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical solutions.
A preparation method of a Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent comprises the following steps:
the method comprises the following steps: weighing 2-5g of attapulgite, placing into hydrochloric acid solution, heating in water bath, washing the product with distilled water for 3 times, standing each time to remove supernatant, and washing the attapulgite solution to neutrality. And finally, centrifuging, and drying the solid precipitate to obtain the acidified attapulgite.
Step two: after 3-6g of Citric Acid (CA) is heated at 210 ℃ to become dark orange, NaOH aqueous solution is added to adjust the pH to be neutral, and GQDs aqueous solution is obtained. And (3) heating 120-150mg of GQD in 50ml of HCl in water bath at the temperature of 60-80 ℃ for 3h to obtain the chlorine modified graphene quantum dot.
Step three: respectively weighing acidified attapulgite and alkyl glycoside quaternary ammonium salt APGQAS (the mass ratio is 1 (0.1-0.4)) to be dispersed in water, mixing and stirring for 3h at 60 ℃, centrifuging and washing for three times by using water, then respectively adding GQD-Cl (the mass ratio of the acidified attapulgite to the GQD-Cl is 1 (0.5-1.5)) into the water, heating the mixture in an oil bath at 50-80 ℃, stirring for 4-7h, finishing the reaction, adding deionized water, standing, cleaning and centrifuging to obtain the Cl-GQD/APGQASP/acidified attapulgite nano composite antibacterial agent.
Further, the concentration of the hydrochloric acid in the step one is 6-9 mol/L.
Further, the temperature of the water bath in the step one is 60-80 ℃, and the reaction time is 15-30 h.
Further, the temperature of the water bath in the second step is 60-80 ℃, and the reaction time is 3 h.
Further, the temperature of the oil bath in the third step is 50-80 ℃, and the reaction time is 4-7 h.
Further, the mass ratio of the acidified attapulgite to the APGQAS in the third step is 1: (0.1-0.4)
The invention has the following beneficial effects:
according to the Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent prepared by the invention, ATP is used as a carrier, APGQAS is used as a surface modifier, Cl-modified GQD is used as a main antibacterial component, and the defect sites of the GQD are increased by modifying the GQD, so that the surface photogeneration-electron recombination is effectively inhibited, and the generation of active oxygen is promoted; and finally, adsorbing bacteria to the surface of the modified attapulgite nano composite material by utilizing the huge specific surface area and potential difference of the Cl-modified GQD/APGQAS/acidified attapulgite nano composite material, and then synergistically loading the Cl-modified GQD quantum dots (GQD-Cl) and APGQAS between the modified attapulgite surface and the pore channel to play a role in natural antibiosis, so as to play a role in high-efficiency antibiosis, and obtain a novel nano composite antibacterial agent which is safe, environment-friendly and high in antibacterial activity.
The GQD quantum dots (GQD-Cl) modified by Cl and having high antibacterial activity are embedded into ATP pore canals and surfaces, so that the defect that the quantum dots are easy to agglomerate is effectively overcome, and Si in attapulgite lattices4+ Ions are very easily isomorphously displaced with other low valent cations to adsorb and kill bacteria. In addition, due to the selection of the APGQAS, on one hand, the combination of the Cl modified GQD quantum dots and ATP is successfully realized, and in addition, the APGQAS has antibacterial activity and can effectively improve the antibacterial performance of the composite material. The preparation method has the advantages of safety, environmental protection, high efficiency and the like.
Drawings
FIG. 1 is a TEM photograph of the Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent prepared in example 1 of the present invention;
FIG. 2 is a graph showing the antibacterial effect of the Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent prepared in example 1 of the present invention;
FIG. 3 is an ESR diagram of the Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent prepared by the invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.
Example 1
Weighing 4g of attapulgite, putting into 7mol/L hydrochloric acid solution, heating in 70 ℃ water bath for 15h, washing the product with distilled water for 3 times, and standing each time to remove supernatant so as to wash the attapulgite solution to neutrality. And finally, centrifuging, and drying the solid precipitate to obtain the acidified attapulgite.
After 3g of Citric Acid (CA) is heated at 210 ℃ for 30min to become dark orange, NaOH aqueous solution is added to adjust the pH to be neutral, and GQDs aqueous solution is obtained. And (3) heating 140mg of GQD in 50ml of HCl in a water bath at 65 ℃ for 3h to obtain the chlorine modified graphene quantum dot.
Respectively weighing 2g of acidified attapulgite and 0.2g of APGQAS, dispersing in 50ml of water, mixing and stirring for 3h at 60 ℃, centrifuging and washing for three times by using water, then adding 3g of chlorine-modified graphene quantum dots, heating by using a 70 ℃ oil bath, stirring for 7h, adding deionized water after the reaction is finished, standing, cleaning and centrifuging to obtain the Cl-modified Cl-GQD/APGQASP/acidified attapulgite nano composite antibacterial agent.
As shown in fig. 1, it can be seen that Cl-modified GQD and APGQAS are distributed on the rod body of attapulgite, indicating that the Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent is successfully prepared.
The Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent (with the concentration of 4 mg/ml) prepared by the technical scheme has the bacteriostasis rate of 99.01 percent on escherichia coli. FIG. 2 a) and FIG. 2 b) are diagrams showing the antibacterial effect of the Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent on Escherichia coli.
FIG. 3 is an ESR diagram of the Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent prepared by the invention, which proves that the prepared antibacterial agent can generate ROS as a bactericidal substance.
Example 2:
weighing 5g of attapulgite, putting the attapulgite into 8mol/L hydrochloric acid solution, heating in water bath at 60 ℃ for 25h, washing the product with distilled water for 3 times, and standing each time to remove supernatant so as to wash the attapulgite solution to neutrality. Finally, the mixture is centrifuged to obtain a mixture,
and drying the solid precipitate to obtain the acidified attapulgite.
After 5g of Citric Acid (CA) is heated at 210 ℃ for 30min to become dark orange, NaOH aqueous solution is added to adjust the pH to be neutral, and GQDs aqueous solution is obtained. And (3) heating 130mg of GQD in 50ml of HCl in a water bath at 60 ℃ for 3h to obtain the chlorine modified graphene quantum dot.
Respectively weighing 2g of acidified attapulgite and 0.8g of APGQAS, dispersing in 50ml of water, mixing and stirring for 3h at 60 ℃, centrifuging and washing for three times by using water, then adding 1g of chlorine modified graphene quantum dots, heating by using an oil bath at 80 ℃, stirring for 8h, adding deionized water after the reaction is finished, standing, cleaning and centrifuging to obtain the Cl-modified Cl-GQD/APGQASP/acidified attapulgite nano composite antibacterial agent.
Example 3:
weighing 2g of attapulgite, putting into 6mol/L hydrochloric acid solution, heating in 80 ℃ water bath for 20h, washing the product with distilled water for 3 times, and standing each time to remove supernatant so as to wash the attapulgite solution to neutrality. And finally, centrifuging, and drying the solid precipitate to obtain the acidified attapulgite.
After 4g of Citric Acid (CA) is heated at 210 ℃ for 30min to become dark orange, NaOH aqueous solution is added to adjust the pH to be neutral, and GQDs aqueous solution is obtained. And (3) heating 120mg of GQD in 50ml of HCl in water bath at 80 ℃ for 3h to obtain the chlorine modified graphene quantum dot.
Respectively weighing 2g of acidified attapulgite and 0.6g of APGQAS, dispersing in 50ml of water, mixing and stirring for 3h at 60 ℃, centrifuging and washing for three times by using water, then adding 2g of chlorine-modified graphene quantum dots, heating in an oil bath at 60 ℃, stirring for 4h, adding deionized water after the reaction is finished, standing, cleaning and centrifuging to obtain the Cl-modified Cl-GQD/APGQASP/acidified attapulgite nano composite antibacterial agent.
Example 4:
weighing 3g of attapulgite, putting into 9mol/L hydrochloric acid solution, heating in 75 ℃ water bath for 30h, washing the product with distilled water for 3 times, and standing each time to remove supernatant so as to wash the attapulgite solution to neutrality. And finally, centrifuging, and drying the solid precipitate to obtain the acidified attapulgite.
After 6g of Citric Acid (CA) is heated at 210 ℃ for 30min to become dark orange, NaOH aqueous solution is added to adjust the pH to be neutral, and GQDs aqueous solution is obtained. And (3) heating 150mg of GQD in 50ml of HCl in a water bath at 70 ℃ for 3h to obtain the chlorine modified graphene quantum dot.
Respectively weighing 2g of acidified attapulgite and 0.4g of APGQAS, dispersing in 50ml of water, mixing and stirring for 3h at 60 ℃, centrifuging and washing for three times by using water, then adding 2.5g of chlorine modified graphene quantum dots, heating by using a 50 ℃ oil bath, stirring for 5h, adding deionized water after the reaction is finished, standing, cleaning and centrifuging to obtain the Cl-modified Cl-GQD/APGQASP/acidified attapulgite nano composite antibacterial agent.
Finally, it is to be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (7)
1. A preparation method of a Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent is characterized by comprising the following steps:
the method comprises the following steps: weighing 2-5g of attapulgite, placing into a hydrochloric acid solution, heating in water bath, washing the product with distilled water for 3 times, standing each time to remove supernatant, washing the attapulgite solution with water to neutrality, centrifuging, and drying the solid precipitate to obtain acidified attapulgite;
step two: heating 3-6g of citric acid CA at 210 ℃ to become dark orange, and adding NaOH aqueous solution to adjust the pH to be neutral to obtain GQDs aqueous solution; then, heating 120-150mg GQD in 40ml HCl in water bath at 60-80 ℃ for 3h to obtain the chlorine modified graphene quantum dots;
step three: respectively weighing the components in a mass ratio of 1: dispersing 0.1-0.4 of acidified attapulgite and alkyl glycoside quaternary ammonium salt APGQAS in water, mixing and stirring for 3h at 60 ℃, centrifuging and washing for three times by using water, then respectively adding GQD-Cl into the water, wherein the mass ratio of the attapulgite to the GQD-Cl is 1: 0.5-1.5, heating by using an oil bath at 50-80 ℃, stirring for 4-7h, finishing the reaction, adding deionized water, standing, washing and centrifuging to obtain the Cl-modified GQD/APGQASP/acidified attapulgite nano composite antibacterial agent.
2. The method for preparing the Cl-modified GQD/APGQASP/acidified attapulgite nano composite antibacterial agent according to claim 1, wherein the method comprises the following steps: the concentration of the hydrochloric acid in the step one is 6-9 mol/L.
3. The method for preparing the Cl-modified GQD/APGQASP/acidified attapulgite nano composite antibacterial agent according to claim 1, wherein the method comprises the following steps: in the first step, the water bath temperature is 60-80 ℃, and the reaction time is 15-30 h.
4. The method for preparing the Cl-modified GQD/APGQASP/acidified attapulgite nano composite antibacterial agent according to claim 1, wherein the method comprises the following steps: in the second step, the temperature of the water bath is 60-80 ℃, and the reaction time is 2 h.
5. The method for preparing the Cl-modified GQD/APGQASP/acidified attapulgite nano composite antibacterial agent according to claim 1, wherein the method comprises the following steps: in the third step, the oil bath temperature is 50-80 ℃, and the reaction time is 4-7 h.
6. The method for preparing the Cl-modified GQD/APGQASP/acidified attapulgite nano composite antibacterial agent according to claim 1, wherein the method comprises the following steps: in the third step, the mass ratio of the acidified attapulgite to the APGQAS is 1: 0.1 to 0.4.
7. The Cl-modified GQD/APGQAS/acidified attapulgite nano composite antibacterial agent prepared by the preparation method of claims 1-6.
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Citations (3)
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| EP2889399A1 (en) * | 2013-12-24 | 2015-07-01 | SAPPI Netherlands Services B.V. | Method for producing a nanocrystalline cellulose (CNC) - reinforced cellulosic fibre or filament |
| CN105600780A (en) * | 2016-02-29 | 2016-05-25 | 昆明物理研究所 | Co-combustion preparation method of chlorine doped graphene quantum dots |
| CN108795421A (en) * | 2018-04-11 | 2018-11-13 | 北京科技大学 | A kind of Preparation method and use of chlorine doped graphene quantum dot |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2889399A1 (en) * | 2013-12-24 | 2015-07-01 | SAPPI Netherlands Services B.V. | Method for producing a nanocrystalline cellulose (CNC) - reinforced cellulosic fibre or filament |
| CN105600780A (en) * | 2016-02-29 | 2016-05-25 | 昆明物理研究所 | Co-combustion preparation method of chlorine doped graphene quantum dots |
| CN108795421A (en) * | 2018-04-11 | 2018-11-13 | 北京科技大学 | A kind of Preparation method and use of chlorine doped graphene quantum dot |
Non-Patent Citations (1)
| Title |
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| ZHU, WEI: ""Graphene quantum dots/LaCoO3/attapulgite heterojunction photocatalysts with improved photocatalytic activity"", 《APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING》 * |
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