CN113501886A - Anhydride esterification modified cellulose, cellulose nano-silver composite material, and preparation method and application thereof - Google Patents
Anhydride esterification modified cellulose, cellulose nano-silver composite material, and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention provides a preparation method of anhydride esterification modified cellulose, which comprises the following steps: s1, performing a synthetic reaction on ethylenediamine tetraacetic acid and acetic anhydride in pyridine to obtain ethylenediamine tetraacetic anhydride; and S2, carrying out esterification modification reaction on cellulose and the ethylene diamine tetraacetic acid anhydride in N, N-dimethylformamide to obtain the anhydride esterification modified cellulose. The invention also provides a preparation method of the cellulose nano-silver composite material, which comprises the following steps: adding the water solution of the anhydride esterification modified cellulose into a silver nitrate solution for chelating reaction, and then adding a reducing agent for reduction reaction to obtain the cellulose nano-silver composite material. The cellulose can be effectively modified, so that the nano-silver has high dispersibility and high associativity on the modified cellulose, and the advantages of the cellulose and the nano-silver are more completely exerted; the cellulose nano-silver composite material provided by the invention can efficiently catalyze and reduce organic pollutants, and has a broad-spectrum antibacterial effect.
Description
Technical Field
The invention relates to preparation of a nano-silver composite material, in particular to a preparation method of an anhydride esterification modified cellulose and cellulose nano-silver composite material.
Background
Silver (Ag) is a metal element of a second subgroup of the fifth period, and the metal is white and glossy, has good extensibility and stable physical and chemical properties. The history of the use of silver for human beings as antibacterial is long, which can be traced back to 2000 b.c. and, with the birth of the last eighties years and the continuous development of the following decades, the novel material of nano silver (AgNPs) is receiving more and more attention, and the nano silver is always an ideal model for researching the catalytic and antibacterial performances. However, a great deal of research shows that the currently prepared nano silver has a high surface area and is easy to aggregate, so that the surface area energy of the nano silver is reduced, and therefore, the dispersibility of the nano silver material is not high, and the disadvantage of the nano silver in the dispersibility becomes a main factor influencing the catalytic and antibacterial properties of the nano silver.
In order to solve the above problems, many studies have been made to utilize modified cellulose as a carrier of nano-silver, and due to the richness and degradability of cellulose and its surface chemistry characteristics, such as high rigidity, low density, low cost and controllable surface chemistry, particle aggregation can be minimized, and catalytic and antibacterial properties of nano-silver composite materials can be improved. For example: at present, there are reports about research on the use of dopamine modified cellulose as a carrier of nano-silver, and according to research in a published paper named "Enhanced chemical activity and antibacterial performance of silver nanoparticles/cellulose nanoparticles", it is shown that dopamine is mainly self-polymerized to coat on cellulose, so as to introduce active groups such as amino groups, chelate silver ions, and then reduce the silver ions into elemental silver in situ, and that the experiment is also performed by using a ratio of 1ml of LB culture solution +1ml of cellulose nano-silver composite material solution at different concentrations +10ul of diluted bacteria solution, and the research result shows that the minimum inhibitory concentration of the dopamine modified cellulose is 4ug/ml for Escherichia coli and 8ug/ml for Bacillus subtilis.
Although the effect and efficacy of nano-silver are improved to a certain extent by the existing research, cellulose is not modified more effectively by the prior art, after dopamine is coated on the cellulose, a strong chemical bond is not formed between the dopamine and the cellulose, the binding force is not strong, and after the dopamine is coated on the cellulose, the dopamine is in a wrapping state, so that the further improvement of the dispersibility of nano-silver particles is greatly limited, and the effect of the cellulose cannot be fully exerted.
In view of the above, there is a need to provide a method for preparing an acid anhydride esterification modified cellulose and a cellulose nano-silver composite material, which solves or at least alleviates the above-mentioned defects of the prior art that cellulose is not modified more effectively.
Disclosure of Invention
The invention mainly aims to provide a preparation method of an anhydride esterification modified cellulose and cellulose nano-silver composite material, and aims to solve the technical problem that cellulose is not modified more effectively in the prior art.
In order to achieve the above object, the present invention provides a method for preparing an anhydride esterification modified cellulose, comprising the steps of:
s1, performing a synthetic reaction on ethylenediamine tetraacetic acid and acetic anhydride in pyridine to obtain ethylenediamine tetraacetic anhydride;
and S2, carrying out esterification modification reaction on cellulose and the ethylene diamine tetraacetic acid anhydride in N, N-dimethylformamide to obtain the anhydride esterification modified cellulose.
Further, the step S1 further includes: and after the synthesis reaction, sequentially cleaning the solid substance obtained by the synthesis reaction with acetic anhydride and petroleum ether, and then drying to obtain the ethylenediamine tetraacetic acid anhydride.
Further, the step S2 further includes: and after the esterification modification reaction, washing, dialyzing and drying the solid substance obtained by the esterification modification reaction in sequence to obtain the anhydride esterification modified cellulose.
Further, in the step S1, an initial ratio of the ethylenediaminetetraacetic acid, the acetic anhydride, and the pyridine is 5 g: 7-10 g: 8-15 ml;
in the step S2, the initial ratio of the cellulose, the ethylenediaminetetraacetic anhydride and the N, N-dimethylformamide is: 1 g: 7-10 g: 40-50 ml.
The invention also provides the anhydride esterification modified cellulose, which is prepared by adopting the preparation method of the anhydride esterification modified cellulose.
The invention also provides a preparation method of the cellulose nano-silver composite material, which comprises the following steps:
s3, preparing the anhydride esterified modified cellulose by adopting the steps of the preparation method of the anhydride esterified modified cellulose;
s4, adding the water solution of the anhydride esterified modified cellulose prepared in the step S3 into a silver nitrate solution for a chelating reaction, and then adding a reducing agent for a reduction reaction to obtain the cellulose nano-silver composite material.
Further, the reducing agent is sodium borohydride.
Further, the mass ratio of the anhydride esterified modified cellulose to the silver nitrate to the sodium borohydride is as follows: 50: 1-3: 50 to 150.
The invention also provides a cellulose nano-silver composite material which is prepared by adopting the preparation method of the cellulose nano-silver composite material.
The invention also provides an application of the cellulose nano-silver composite material in catalytic reduction of organic pollutants and/or bacteriostasis.
Compared with the prior art, the invention has the following advantages:
the preparation method provided by the invention can obtain the anhydride esterified modified cellulose, the anhydride esterified modified cellulose prepared by the method has effective modification on cellulose, and the anhydride esterified modified cellulose can be used for efficiently loading nano-silver materials by obtaining the ethylenediamine tetraacetic acid anhydride and using the cellulose for the esterification modification of the ethylenediamine tetraacetic acid anhydride, so that the anhydride esterified modified cellulose can be used as a nano-silver carrier and a nano-silver stabilizer, the nano-silver has high dispersibility and high associativity on the modified cellulose, and the action and effect of the nano-silver are further improved.
The preparation method provided by the invention can also be used for obtaining a cellulose nano-silver composite material, the cellulose nano-silver composite material prepared by the invention is obtained based on the preparation of anhydride esterification modified cellulose, the cellulose nano-silver composite material is prepared by the preparation method provided by the invention, so that nano-silver particles are uniformly distributed and have strong associativity, and the prepared modified cellulose nano-silver composite material has good dispersibility and large surface area and shows good application prospects in the fields of organic reaction catalysis and broad-spectrum antibiosis; in addition, tests prove that: the cellulose nano-silver composite material has a good inhibition effect on gram-negative bacteria and gram-positive bacteria, the inhibition effect of the cellulose nano-silver composite material is obviously higher than that of the prior art, and the cellulose nano-silver composite material can also efficiently catalyze and reduce organic pollutants, and improve the reduction efficiency of the organic pollutants, such as catalyzing sodium borohydride to efficiently reduce 4-nitrophenol.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a graph showing a comparison of the transmission of the cellulose nano-silver composite of example 1 and the nano-silver of comparative example 1; wherein, (a) is a transmission electron microscope image of the cellulose nano-silver composite material in example 1, and (b) is a transmission electron microscope image of the nano-silver in comparative example 1.
FIG. 2 is an infrared spectrum of the cellulose nano-silver composite material of example 1 before and after synthesis.
Fig. 3 is an XPS spectrum of Ag 3d before and after the synthesis of the cellulose nano-silver composite in example 1.
FIG. 4 is a graph comparing UV-visible absorption spectra of cellulose nano-silver composite in example 1 and nano-silver catalyzed sodium borohydride in comparative example 1 to reduce 4-nitrophenol; wherein, (a) is an ultraviolet-visible absorption spectrum chart of the cellulose nano-silver composite material in example 1 catalyzing sodium borohydride to reduce 4-nitrophenol, and (b) is an ultraviolet-visible absorption spectrum chart of the cellulose nano-silver composite material in comparative example 1 catalyzing sodium borohydride to reduce 4-nitrophenol.
FIG. 5 is a comparison graph of antibacterial performance test of the cellulose nano-silver composite material in example 1 and nano-silver in comparative example 1 on Escherichia coli; wherein, (a) is the antibacterial performance test of the cellulose nano-silver composite material on escherichia coli in example 1, and (b) is the antibacterial performance test of the nano-silver on escherichia coli in comparative example 1.
FIG. 6 is a comparison graph of antibacterial performance test of the cellulose nano-silver composite material in example 1 and nano-silver in comparative example 1 against Bacillus subtilis; wherein, (a) is the antibacterial performance test of the cellulose nano-silver composite material on bacillus subtilis in example 1, and (b) is the antibacterial performance test of the nano-silver on the bacillus subtilis in comparative example 1.
The implementation, functional features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It should be noted that all the directional indicators (such as the upper and lower … …) in the embodiment of the present invention are only used to explain the relative position relationship, movement, etc. of the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
It should be noted by those skilled in the art that, as a further description of the present invention, the CNC-EDTA mentioned in the specification and the drawings of the specification can be represented as anhydride esterified modified cellulose without affecting the understanding of the technical solution of the present invention; the CNC-EDTA @ AgNPs and the CNC-EDTA @ Ag mentioned in the specification and the drawings of the specification can be expressed as cellulose nano-silver composite materials; in addition, in the drawings of the specification, Wavenumber can be expressed as wave number, Transmittance can be expressed as Transmittance, Binding Energy can be expressed as Binding Energy, Intensity can be expressed as Intensity, and Wavelength can be expressed as Wavelength; it should be noted that, since the original drawings of fig. 2 to 4 in the drawings of the specification are color drawings, the present invention can be understood by combining the text in the specification if the original drawings cannot be clearly recognized from the drawings after color conversion.
In order to obtain a material capable of efficiently loading nano-silver so as to improve the action and the effect of the nano-silver, the invention provides a preparation method of anhydride esterification modified cellulose, which comprises the following steps:
s1, performing a synthetic reaction on ethylenediamine tetraacetic acid and acetic anhydride in pyridine to obtain ethylenediamine tetraacetic anhydride;
wherein, the initial ratio of the ethylenediamine tetraacetic acid, the acetic anhydride and the pyridine may be: 5 g: 7-10 g: 8-15 ml; it is noted that the acetic anhydride is in a liquid state, and the mass of the acetic anhydride can be obtained by weighing; the reaction temperature of the synthesis reaction can be 65-70 ℃, and the reaction time can be 12-24 h.
In addition, after the synthesis reaction, the solid substance obtained by the synthesis reaction can be sequentially washed by acetic anhydride and petroleum ether, and then vacuum drying is carried out, so that the ethylene diamine tetraacetic acid anhydride for standby after washing and drying is obtained.
As a specific description of the step S1, in the specific preparation process, pyridine is used as a solvent, ethylenediamine tetraacetic acid is subjected to dehydration condensation under the action of acetic anhydride and heating and stirring to synthesize ethylenediamine tetraacetic acid anhydride, and then the ethylenediamine tetraacetic acid anhydride to be used is obtained by suction filtration, washing with acetic anhydride and petroleum ether, and drying.
And S2, carrying out esterification modification reaction on cellulose and the ethylene diamine tetraacetic acid anhydride in N, N-dimethylformamide to obtain the anhydride esterification modified cellulose.
Wherein the initial ratio of the cellulose, the ethylenediaminetetraacetic anhydride and the N, N-dimethylformamide may be: 1 g: 7-10 g: 40-50 ml; the reaction temperature of the esterification modification reaction can be 60-65 ℃, and the reaction time can be 12-24 h.
In addition, after the esterification modification reaction, the solid substance obtained by the esterification modification reaction can be washed, dialyzed and dried in sequence to obtain the anhydride esterification modified cellulose for standby.
As a specific description of the step S2, in a specific preparation process, the ethylenediamine tetraacetic acid anhydride prepared in the step S1 is used for esterification modification of cellulose, and the esterification modification is completed by using N, N-Dimethylformamide (DMF) as a solvent and forming an ester group on the cellulose under the action of heating and stirring the ethylenediamine tetraacetic acid anhydride; then carrying out centrifugation, ethanol and pure water washing, pure water drainage dialysis for 48-72h, freeze drying for 36-48h and the like, thereby obtaining the anhydride esterified modified cellulose for standby.
In the embodiment, the prepared ethylene diamine tetraacetic acid anhydride is used for esterifying the modified cellulose, so that the modified cellulose has strong chemical groups inside and the bonding area of the cellulose and the nano-silver is not limited, and therefore, the modified cellulose can be used as a carrier and a stabilizer of the nano-silver, the stability of the nano-silver aqueous solution is improved, and the particle size of the nano-silver is effectively controlled; in addition, the anhydride esterification modified cellulose prepared by the embodiment can overcome the defects of weak bonding between nano silver particles and cellulose, uneven distribution and the like.
It should be appreciated that, based on the above-described production method, the present invention also provides an acid anhydride esterified modified cellulose produced by the method for producing an acid anhydride esterified modified cellulose according to any of the above-described embodiments. Specifically, the anhydride esterified modified cellulose provided by the invention is ethylenediamine tetraacetic acid anhydride modified cellulose, and the structural formula of the anhydride esterified modified cellulose is as follows:
in order to improve the bacteriostatic action of the cellulose nano-silver composite material, the invention also provides a preparation method of the anhydride esterification modified cellulose nano-silver composite material based on the preparation of the anhydride esterification modified cellulose, which comprises the following steps:
s3, preparing an acid anhydride esterified modified cellulose by the steps of the method for preparing an acid anhydride esterified modified cellulose according to any of the embodiments described above;
s4, adding the water solution of the anhydride esterified modified cellulose prepared in the step S3 into a silver nitrate solution for a chelating reaction, and then adding a reducing agent for a reduction reaction to obtain the cellulose nano-silver composite material.
As a preferable aspect of the above embodiment, the reducing agent may be sodium borohydride, and the addition amounts of the acid anhydride esterification modified cellulose, the silver nitrate, and the sodium borohydride may be, by mass: 50: 1-3: 50 to 150. It should be noted that the mass ratio of the addition amounts of the acid anhydride esterified modified cellulose, the silver nitrate, and the sodium borohydride only represents the ratio between the masses of the respective substances, and the masses of the other components are not taken into account, and particularly, the mass ratio is calculated without taking into account the mass of the corresponding solvent. In addition, the chelating reaction can be carried out under the condition of keeping out of the light, and the magnetic stirring is carried out for 0.5 to 16 hours at the room temperature, so that the chelating reaction is carried out; the reduction reaction process can be carried out by slowly dropwise adding a sodium borohydride solution.
As a specific description of the step S4, in a specific preparation process, the anhydride esterified modified cellulose prepared in the step S3 is ultrasonically dispersed in water, then the aqueous solution of the anhydride esterified modified cellulose is added into a silver nitrate solution, after stirring and reacting for 0.5 to 16 hours in a dark place, a sodium borohydride solution is slowly added dropwise, and a brownish red colloid generated by taking a color change as a reaction end point is the cellulose nano-silver composite material. During specific preparation, the concentration of the aqueous solution of the anhydride esterification modified cellulose can be 0.04-4g/L, the concentration of silver nitrate can be 0.1-1g/L, and the concentration of sodium borohydride can be 0.4-4 g/L.
According to the invention, the esterified and modified nano-cellulose is ultrasonically dispersed in water and added into a silver nitrate solution, so that the excellent characteristics of the anhydride esterified and modified cellulose can be fully utilized to effectively adsorb chelated silver ions, and then, the nano-silver particles can be reduced in situ on the surface of the cellulose by utilizing the reducibility of sodium borohydride, so that the surface of the cellulose is stably coated with the nano-silver particles. By adopting the preparation method provided by the invention, the nano-silver particles are uniformly distributed, the binding property is strong, and the prepared modified cellulose nano-silver composite material has good dispersibility and large surface area, and has good application prospect in the processes of catalyzing organic reactions and the broad-spectrum antibacterial field.
It should be appreciated that the present invention also provides a cellulose nano-silver composite material prepared by the method for preparing a cellulose nano-silver composite material according to any of the above embodiments.
In addition, in order to fully exert the function of the cellulose nano-silver composite material, the invention also provides an application of the cellulose nano-silver composite material in the process of catalyzing organic matter degradation and/or bacteriostasis. The test proves that: the cellulose nano-silver composite material has a good inhibition effect on gram-negative bacteria and gram-positive bacteria, and can efficiently catalyze degradation reactions of organic matters, such as sodium borohydride to efficiently reduce 4-nitrophenol.
It should be noted that in the specific test process, different bacteria dilution ratios are adopted for different bacteria, mainly because the growth characteristics of different microorganisms are different, and when the bacteriostatic effect is judged, the bacteria growth inhibition ratio is mainly judged from the whole bacteria growth inhibition ratio.
To facilitate a further understanding of the above embodiments, the following is illustrated:
example 1
Preparation of cellulose nano-silver composite material
1. To 16ml of pyridine were added 10g of ethylenediaminetetraacetic acid (EDTA), 14g of acetic anhydride, followed by heating at a reaction temperature of 65 ℃ and stirring for 24 hours. And (3) carrying out suction filtration and separation on the solid substance obtained after the reaction, washing the solid substance with acetic anhydride and petroleum ether respectively for 3 times, and carrying out vacuum drying on the product for 24 hours at the temperature of 60 ℃ to obtain the ethylenediaminetetraacetic acid anhydride (EDTAD).
2. 20ml of N, N-Dimethylformamide (DMF), 0.5g of cellulose (CNC) and 3.5g of ethylenediaminetetraacetic acid anhydride (EDTAD) prepared in step 1 were put into a 100ml volumetric flask, and the mixed system was heated in an oil bath at 60 ℃ under reflux for 24 hours; and then centrifugally separating the solid product, washing the solid product with ethanol and pure water, adding pure water, oscillating and mixing uniformly, pouring the mixture into a dialysis bag for dialysis for 72 hours, and freeze-drying to obtain the anhydride esterified modified nano-cellulose (CNC-EDTA).
3. Ultrasonically dispersing the anhydride esterified modified cellulose obtained in the step 2 in water to obtain dispersion liquid, wherein the concentration of the anhydride esterified modified cellulose in the dispersion liquid is 0.4 g/L; adding 10ml of dispersion into 1ml of 5mmol/L silver nitrate solution, slowly dropwise adding 4g/L sodium borohydride solution after magnetically stirring for 16h, and taking the color change as an end point, wherein the generated red brown colloid substance is cellulose nano-silver composite material (CNC-EDTA @ AgNPs), and after dropwise adding of the sodium borohydride solution is completed, carrying out freeze drying treatment for 24 h.
The TEM of the CNC-EDTA @ AgNPs prepared in this example is shown in part (a) of fig. 1, and the result shows that this example successfully prepared nano silver particles and uniformly dispersed on rod-shaped cellulose.
C obtained in this exampleThe infrared spectrograms before and after the NC-EDTA @ AgNPs composite material is synthesized are shown in figure 2, and it can be seen that the surface of the cellulose has a large number of hydroxyl groups; the esterification reaction is carried out to introduce ester group by adopting ethylene diamine tetraacetic acid anhydride modified cellulose, namely, the ester group is 1700cm-1A characteristic peak of 1340cm and around which-C ═ O appears-1The characteristic peak of-C-O appears nearby, and meanwhile, the peak is 864cm-1The characteristic peak of-NH appears nearby, which proves that EDTAD successfully modifies the cellulose.
XPS spectra of Ag 3d before and after the CNC-EDTA @ AgNPs composite material prepared in the example is shown in FIG. 3, wherein the CNC-EDTA @ AgNPs composite material shows Ag at 366.6eV and 372.6eV0The successful loading of elemental silver is confirmed by the characteristic peaks of (a). Note that CNC-EDTA @ Ag shown in fig. 2 and 3 corresponds to CNC-EDTA @ AgNPs in the present embodiment.
Example 2
Catalytic test of cellulose nano-silver composite
The CNC-EDTA @ AgNPs composite material prepared in example 1 is used as a catalyst, 4-nitrophenol is used as a model compound, and sodium borohydride is used as a reducing agent; and detecting the reaction process by using an ultraviolet-visible spectrophotometry, and inspecting the catalytic efficiency of the CNC-EDTA @ AgNPs composite material.
The method comprises the following specific operations: 1.5ml of a mixed solution of 0.24mM of 4-nitrophenol and 1.5ml of 76mM of sodium borohydride was added to a UV test tube, 200. mu.L of CNC-EDTA @ AgNPs dispersion (the silver content in the dispersion was 2.0. mu.g/ml) was then added to the UV test tube, and after 5 seconds of mixing of the solution, monitoring was carried out by UV-visible spectrophotometry with a scanning range of 250-500nm and a cycle time of 1 minute.
It is to be understood that when 4-nitrophenol is exposed to a sodium borohydride solution, the solution appears yellow-green and will have a strong absorption peak at 400 nm. As the catalytic reduction reaction proceeds, the intensity of the absorption peak at 400nm decreases, and a new representative absorption peak at 297nm appears, which represents-NO2Conversion to-NH2The 4-nitrophenol is gradually converted to 4-aminophenol.
According to the test result, when the CNC-EDTA @ AgNPs composite material is used as the catalyst, the intensity of the absorption peak at 400nm is reduced obviously at a high speed, the reduction degree is high, and the increase speed of the absorption peak at 297nm is also increased obviously at a high speed, and the method can be understood by referring to FIG. 4.
Example 3
Bacteriostatic test of cellulose nano-silver composite material
Due to the fact that AgNPs have broad-spectrum sterilization, the CNC-EDTA @ AgNPs composite material prepared in the embodiment is used as an antibacterial agent, broad-spectrum sterilization effects on gram-positive bacteria and gram-negative bacteria are investigated, and bacillus coli and bacillus subtilis are respectively selected as indicator strains to evaluate antibacterial performance.
1. The antibacterial test evaluation of the CNC-EDTA @ AgNPs composite material on escherichia coli specifically operates as follows:
(1) and (3) bacterial activation: dipping a small amount of bacterial liquid from a storage tube placed in a refrigerator at minus 80 ℃, streaking a plate, and placing the plate in a constant temperature incubator at 35 ℃ for culture.
(2) And (3) bacterial culture: and (3) picking a single colony and placing the single colony in an LB nutrient medium, and placing the medium in a temperature-controlled shaking table for culturing for 12 hours at 35 ℃.
(3) Expanding culture: and (3) putting 0.5ml of the bacterial liquid obtained in the step (2) into 100ml of sterilized LB culture medium, and putting the culture medium into a shaking table to culture for 3-4 hours at 35 ℃ to obtain the bacterial liquid with the OD value of about 1.
(4) Diluting: sampling from the bacterial liquid with the OD value of 1 in the step (3), and diluting the sampled bacterial liquid by 103And (4) doubling.
(5) Preparing an antibacterial solution: CNC-EDTA @ AgNPs were prepared at concentrations of 0.5-32. mu.g/mL.
(6) Hatching: mixing 1.0ml of LB culture medium, 1.0ml of CNC-EDTA @ AgNPs solution with different concentrations obtained in the step (5) and 10 microliter of bacterial liquid obtained by dilution in the step (4), and placing the mixture into a sterilized 10ml centrifuge tube. The solution was incubated for 4h at 35 ℃ in a shaker at 150 rpm.
(7) Evaluation of antibacterial property: after incubation, 0.1ml of the inoculum was transferred to the surface of agar plates in a sterile environment, and the surface of the plates was covered with the inoculum uniformly (3 plates per solution set) using sterile glass rods. Photographs of colony growth at different CNC-EDTA @ AgNPs concentrations are shown in part (a) of FIG. 5, with a minimum inhibitory concentration of 2ug/ml for Escherichia coli.
2. The CNC-EDTA @ AgNPs composite material specifically performs the following operations on the antibacterial test evaluation of the bacillus subtilis:
(1) and (3) bacterial activation: dipping a small amount of bacterial liquid from a storage tube placed in a refrigerator at minus 80 ℃, streaking a plate, and placing the plate in a constant temperature incubator at 30 ℃ for culture.
(2) And (3) bacterial culture: and (3) picking a single colony and placing the single colony in an LB liquid culture medium, and placing the culture medium in a temperature-controlled shaking table for culturing for 12 hours at the temperature of 30 ℃.
(3) Expanding culture: and (3) putting 3ml of the bacterial liquid obtained in the step (2) into 100ml of sterilized LB culture medium, and putting the culture medium into a shaking table to culture for 3-4 hours at the temperature of 30 ℃ to obtain the bacterial liquid with the OD value of about 1.
(4) Diluting: sampling from the bacterial liquid with the OD value of 1 in the step (3), and diluting the sampled bacterial liquid by 104And (4) doubling.
(5) Preparing an antibacterial solution: CNC-EDTA @ AgNPs were prepared at concentrations of 0.5-32. mu.g/mL.
(6) Hatching: mixing 1.0ml of LB culture medium, 1.0ml of CNC-EDTA @ AgNPs solution with different concentrations obtained in the step (5) and 10 microliter of bacterial liquid obtained by dilution in the step (4), and placing the mixture into a sterilized 10ml centrifuge tube. The solution was incubated for 4h at 30 ℃ in a shaker at 150 rpm.
(7) Evaluation of antibacterial property: after incubation, 0.1ml of the inoculum was transferred to the surface of agar plates in a sterile environment, and the surface of the plates was covered with the inoculum uniformly using a sterile glass rod (3 plates were coated with each solution group). all plates were placed in an incubator and incubated overnight at 30 ℃. Photographs of colony growth at different CNC-EDTA @ AgNPs concentrations are shown in part (a) of fig. 6, with a minimum inhibitory concentration for bacillus subtilis of 4 ug/ml.
Comparative example 1
Preparation of nano silver particles
The acid anhydride esterified modified cellulose in step 1 of example was replaced with pure water. The method specifically comprises the following steps: adding 10ml of pure water into 1ml of 5mmol/L silver nitrate solution, magnetically stirring for 16h, and slowly dropwise adding a sodium borohydride solution with the concentration of 4g/L, wherein the dropwise adding amount of the sodium borohydride is required to be consistent with that of the sodium borohydride in example 1, so as to obtain pure nano silver particles, which are marked as AgNPs, and after the dropwise adding of the sodium borohydride solution is completed, carrying out freeze drying for 24 h.
The TEM of the nano silver particles obtained in this comparative example is shown in part (b) of fig. 1, and it can be seen that the pure nano silver particles are agglomerated.
Comparative example 2
Catalytic testing of nanosilver particles
AgNPs prepared in comparative example 1 are used as a catalyst, 4-nitrophenol is used as a model compound, and sodium borohydride is used as a reducing agent. And detecting the reaction process by using an ultraviolet-visible spectrophotometry, and inspecting the catalytic efficiency of AgNPs.
The method comprises the following specific operations: 1.5ml of a mixed solution of 0.24mM of 4-nitrophenol and 1.5ml of 76mM of sodium borohydride was added to a UV tube, 200. mu.L of AgNPs dispersion (silver content: 2.0. mu.g/ml) was then added to the UV tube, and after 5 seconds of mixing of the solution, monitoring was performed by UV-visible spectrophotometry with a scanning range of 250 and 500nm and a cycle time of 1 minute.
It is to be understood that when 4-nitrophenol is exposed to a sodium borohydride solution, the solution appears yellow-green and will have a strong absorption peak at 400 nm. As the catalytic reduction reaction proceeds, the intensity of the absorption peak at 400nm decreases, and a new representative absorption peak at 297nm appears, which represents-NO2Conversion to-NH2The 4-nitrophenol is gradually converted to 4-aminophenol.
According to the test results, when AgNPs are used as the catalyst, the decrease rate and the decrease degree of the absorption peak intensity at 400nm are obviously lower than those of CNC-EDTA @ AgNPs in the example 2, and the increase rate and the increase degree of the absorption peak at 297nm are obviously lower than those of CNC-EDTA @ AgNPs in the example 2, which can be understood by referring to FIG. 4.
Therefore, the catalytic effect of the CNC-EDTA @ AgNPs is far better than that of pure AgNPs, which is probably because the nano silver particles have high binding property and dispersity on the carrier of the anhydride esterification modified cellulose, so that the CNC-EDTA @ AgNPs have higher activity. In conclusion, the addition of the anhydride esterification modified cellulose enhances the dispersibility and dispersion stability of AgNPs, thereby enhancing the catalytic activity.
Comparative example 3
The AgNPs prepared in the comparative example 1 are used as an antibacterial agent, broad-spectrum bactericidal effects on gram-positive bacteria and gram-negative bacteria are considered, and bacillus coli and bacillus subtilis are respectively selected as indicator strains to evaluate antibacterial performance.
1. The specific operation of the AgNPs for the evaluation of the antibacterial test of the escherichia coli is as follows:
(1) and (3) bacterial activation: dipping a small amount of bacterial liquid from a storage tube placed in a refrigerator at minus 80 ℃, streaking a plate, and placing the plate in a constant temperature incubator at 35 ℃ for culture.
(2) And (3) bacterial culture: and (3) picking a single colony and placing the single colony in an LB nutrient medium, and placing the medium in a temperature-controlled shaking table for culturing for 12 hours at 35 ℃.
(3) Expanding culture: and (3) putting 0.5ml of the bacterial liquid obtained in the step (2) into 100ml of sterilized LB culture medium, and putting the culture medium into a shaking table to culture for 3-4 hours at 35 ℃ to obtain the bacterial liquid with the OD value of about 1.
(4) Diluting: sampling from the bacterial liquid with the OD value of 1 in the step (3), and diluting the sampled bacterial liquid by 103And (4) doubling.
(5) Preparing an antibacterial solution: AgNPs are prepared at concentrations of 0.5-32. mu.g/mL.
(6) Hatching: and (3) mixing 1.0ml of LB culture medium, 1.0ml of AgNPs solution with different concentrations obtained in the step (5) and 10 microliter of bacterial liquid obtained by dilution in the step (4), and placing the mixture in a sterilized 10ml centrifuge tube. The solution was incubated for 4h at 35 ℃ in a shaker at 150 rpm.
(7) Evaluation of antibacterial property: after incubation, 0.1ml of the inoculum was transferred to the surface of agar plates in a sterile environment, and the surface of the plates was covered with the inoculum uniformly using a sterile glass rod (3 plates were coated with each solution group). all plates were placed in an incubator and incubated overnight at 35 ℃. Photographs of colony growth at different AgNPs concentrations are shown in FIG. 5 (b), and the minimum inhibitory concentration of AgNPs against E.coli is 8 ug/ml.
Obviously, it can be seen that: the bacteriostatic effect of AgNPs on escherichia coli is lower than that of silver nanoparticles prepared by taking modified cellulose as a stabilizer and a carrier.
2. The specific operation of the AgNPs composite material for the antibacterial test evaluation of the bacillus subtilis is as follows:
(1) and (3) bacterial activation: dipping a small amount of bacterial liquid from a storage tube placed in a refrigerator at minus 80 ℃, streaking a plate, and placing the plate in a constant temperature incubator at 30 ℃ for culture.
(2) And (3) bacterial culture: and (3) picking a single colony and placing the single colony in an LB liquid culture medium, and placing the culture medium in a temperature-controlled shaking table for culturing for 12 hours at the temperature of 30 ℃.
(3) Expanding culture: and (3) putting 3ml of the bacterial liquid obtained in the step (2) into 100ml of sterilized LB culture medium, and putting the culture medium into a shaking table to culture for 3-4 hours at the temperature of 30 ℃ to obtain the bacterial liquid with the OD value of about 1.
(4) Diluting: sampling from the bacterial liquid with the OD value of 1 in the step (3), and diluting the sampled bacterial liquid by 104And (4) doubling.
(5) Preparing an antibacterial solution: AgNPs are prepared at concentrations of 0.5-32. mu.g/mL.
(6) Hatching: and (3) mixing 1.0ml of LB culture medium, 1.0ml of AgNPs solution with different concentrations obtained in the step (5) and 10 microliter of bacterial liquid obtained by dilution in the step (4), and placing the mixture in a sterilized 10ml centrifuge tube. The solution was incubated for 4h at 30 ℃ in a shaker at 150 rpm.
(7) Evaluation of antibacterial property: after incubation, 0.1ml of the inoculum was transferred to the surface of agar plates in a sterile environment, and the surface of the plates was covered with the inoculum uniformly using a sterile glass rod (3 plates were coated with each solution group). all plates were placed in an incubator and incubated overnight at 30 ℃. Photographs of colony growth at different AgNPs concentrations are shown in part (b) of FIG. 6, and the minimum inhibitory concentration against Bacillus subtilis is 16 ug/ml.
Obviously, it can be seen that: the bacteriostatic effect of AgNPs on the bacillus subtilis is lower than that of silver nanoparticles prepared by taking modified cellulose as a stabilizer and a carrier.
In the above technical solutions, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention include the claims of the present invention, which are directly or indirectly applied to other related technical fields by using the equivalent structural changes made in the content of the description and the drawings of the present invention.
Claims (10)
1. A preparation method of anhydride esterification modified cellulose is characterized by comprising the following steps:
s1, performing a synthetic reaction on ethylenediamine tetraacetic acid and acetic anhydride in pyridine to obtain ethylenediamine tetraacetic anhydride;
and S2, carrying out esterification modification reaction on cellulose and the ethylene diamine tetraacetic acid anhydride in N, N-dimethylformamide to obtain the anhydride esterification modified cellulose.
2. The method for preparing an acid anhydride esterified modified cellulose according to claim 1, wherein said step S1 further comprises: and after the synthesis reaction, sequentially cleaning the solid substance obtained by the synthesis reaction with acetic anhydride and petroleum ether, and then drying to obtain the ethylenediamine tetraacetic acid anhydride.
3. The method for preparing an acid anhydride esterified modified cellulose according to claim 1, wherein said step S2 further comprises: and after the esterification modification reaction, washing, dialyzing and drying the solid substance obtained by the esterification modification reaction in sequence to obtain the anhydride esterification modified cellulose.
4. The method for producing an acid anhydride esterified modified cellulose according to any one of claims 1 to 3, wherein in step S1, the initial ratio of ethylenediamine tetraacetic acid, acetic anhydride, and pyridine is: 5 g: 7-10 g: 8-15 ml;
in the step S2, the initial ratio of the cellulose, the ethylenediaminetetraacetic anhydride and the N, N-dimethylformamide is: 1 g: 7-10 g: 40-50 ml.
5. An acid anhydride esterified cellulose produced by the method for producing an acid anhydride esterified cellulose according to any one of claims 1 to 4.
6. A preparation method of a cellulose nano-silver composite material is characterized by comprising the following steps:
s3, preparing the anhydride esterified modified cellulose by the steps of the method for preparing the anhydride esterified modified cellulose according to any one of claims 1 to 4;
s4, adding the water solution of the anhydride esterified modified cellulose prepared in the step S3 into a silver nitrate solution for a chelating reaction, and then adding a reducing agent for a reduction reaction to obtain the cellulose nano-silver composite material.
7. The method for preparing the cellulose nano-silver composite material according to claim 6, wherein the reducing agent is sodium borohydride.
8. The preparation method of the cellulose nano-silver composite material according to claim 7, wherein the mass ratio of the acid anhydride esterified modified cellulose to the silver nitrate to the sodium borohydride is as follows: 50: 1-3: 50 to 150.
9. A cellulose nano-silver composite material, characterized by being produced by the method for producing a cellulose nano-silver composite material according to any one of claims 6 to 8.
10. Use of the cellulose nanosilver composite of claim 9 in catalytic reduction of organic pollutants and/or bacteriostasis.
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