CN107519842B - Modified oxidized single-walled carbon nanohorn, preparation method and application thereof, and method for adsorbing antibiotics - Google Patents

Modified oxidized single-walled carbon nanohorn, preparation method and application thereof, and method for adsorbing antibiotics Download PDF

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CN107519842B
CN107519842B CN201710588729.9A CN201710588729A CN107519842B CN 107519842 B CN107519842 B CN 107519842B CN 201710588729 A CN201710588729 A CN 201710588729A CN 107519842 B CN107519842 B CN 107519842B
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walled carbon
carbon nanohorn
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CN107519842A (en
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李囡囡
黄越
纪兴华
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Wuhu Institute of Technology
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    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention discloses a modified oxidized single-walled carbon nanohorn, a preparation method and application thereof, and a method for adsorbing antibiotics, wherein the modified oxidized single-walled carbon nanohorn contains a modifier and an oxidized single-walled carbon nanohorn modified by the modifier; the modifier is prepared through amidation reaction, wherein an amine group source is chitosan oligosaccharide, and an acyl group source is one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid. The acyl source in the modifier plays the characteristics of hydrophobicity and strong affinity to the oxidized single-walled carbon nanohorn, and is accumulated and wound on the oxidized single-walled carbon nanohorn, the chitosan oligosaccharide end in the modifier plays the hydrophilic role, so that the hydrophilic degree of the modified oxidized single-walled carbon nanohorn is improved, the agglomeration of the oxidized single-walled carbon nanohorn is inhibited, and the modified oxidized single-walled carbon nanohorn is favorably dispersed in aqueous solution.

Description

Modified oxidized single-walled carbon nanohorn, preparation method and application thereof, and method for adsorbing antibiotics
Technical Field
The invention relates to a modified oxidized single-walled carbon nanohorn, in particular to a modified oxidized single-walled carbon nanohorn, a preparation method and application thereof, and a method for adsorbing antibiotics.
Background
Antibiotics are a novel class of organic environmental pollutants and mainly come from antibiotic production industry, medical sanitation industry, animal husbandry industry, aquaculture industry and the like. Antibiotics cannot be completely absorbed by human bodies and livestock, most of the antibiotics can be discharged into the environment in the form of drug prototypes or metabolites thereof, not only antibiotic-resistant strains can be induced to be generated, but also the ecological environment and the human health can be harmed. Ciprofloxacin is a synthesized third-generation quinolone antibacterial drug, has broad-spectrum antibacterial activity and good bactericidal effect, fifty percent of antibiotics are discharged into the environment through urine and excrement in a prototype form after being used, and the antibiotics are accumulated in a water environment due to the characteristics of high hydrophilicity and difficult volatilization. At present, the research on the antibiotic wastewater treatment method mainly focuses on an advanced oxidation method, special biodegradation, photolysis, a combined process and the like, but the cost is high, and secondary pollution is possibly generated. The adsorption method for treating antibiotics is a non-destructive method, has the advantages of low cost, convenient operation, high pollutant removal rate, no high-toxicity metabolite and the like, and becomes one of the most application prospects in the environmental pollutant treatment technology.
In recent years, oxidized single-walled carbon nanohorns have attracted great interest, and are novel carbon nanomaterials, similar to truncated carbon nanotubes, with a unique pyramidal closed structure at one end. The carbon nanohorn has excellent physicochemical properties such as large specific surface area, high conductivity, good mechanical properties, large length-diameter ratio and the like, so scientists compete to research the application of the carbon nanohorn in the fields of sensors, catalyst carriers, drug carriers and the like. The specific surface area of the carbon nanohorn can reach 400 square meters per gram, and after oxidation treatment, the specific surface area reaches 1300-1400 square meters per gram. In addition, the oxidized single-wall carbon nanohorn has a hollow structure and strong adsorption performance, and the unique structure and property enable the oxidized single-wall carbon nanohorn to have good affinity with organic compounds. Thus, the oxidized single-walled carbon nanohorns can be used as adsorbents. However, the oxidized single-walled carbon nanohorn is a hydrophobic material, has poor dispersion degree in water, is easy to aggregate, and limits the application of the oxidized single-walled carbon nanohorn as an adsorbent in an aqueous solution.
Disclosure of Invention
The invention aims to provide a modified oxidized single-walled carbon nanohorn, a preparation method and application thereof, and a method for adsorbing antibiotics. The electronic structure of the surface of the oxidized single-walled carbon nanohorn is not changed in the process, and the property of the oxidized single-walled carbon nanohorn is kept.
In order to achieve the above object, the present invention provides a modified oxidized single-walled carbon nanohorn comprising a modifier and an oxidized single-walled carbon nanohorn modified with the modifier; the modifier is prepared through amidation reaction, wherein an amine group source is chitosan oligosaccharide, and an acyl group source is one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid.
The present invention also provides a method for preparing the modified oxidized single-walled carbon nanohorns as described above, comprising the steps of: (1) dissolving an acyl source compound in ethanol by ultrasonic waves, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide, stirring in a dark place, and carrying out an activation reaction to obtain an activated acyl source compound, wherein the acyl source is one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid; (2) dissolving chitosan oligosaccharide in water, adding an activated acyl source compound, heating for reaction, adding ethanol after the reaction is finished, centrifuging, and removing impurities to obtain a modifier; (3) mixing the oxidized single-walled carbon nanohorn with water, adding a modifier, performing ultrasonic treatment, centrifuging to remove supernatant, and retaining precipitate.
In addition, the invention also provides application of the modified oxidized single-walled carbon nanohorn in adsorption of antibiotics.
Furthermore, the present invention provides a method for adsorbing antibiotics, comprising the step of mixing the modified oxidized single-walled carbon nanohorns described above with a solution containing an antibiotic.
According to the technical scheme, the modified oxidized single-walled carbon nanohorn is prepared by modifying the oxidized single-walled carbon nanohorn by using the modifying agent, wherein the modifying agent is obtained through amidation reaction, the amine group source is chitosan oligosaccharide, and the acyl group source is one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid. Thus, the acyl source in the modifier: stearic acid or deoxycholic acid or linolenic acid or oleic acid or palmitic acid exerts the characteristics of hydrophobicity and strong affinity to the oxidized single-walled carbon nanohorn, the stearic acid or deoxycholic acid or linolenic acid or oleic acid or palmitic acid is piled and wound on the oxidized single-walled carbon nanohorn, the chitosan oligosaccharide end in the modifier exerts the hydrophilic effect, the hydrophilic degree of the modified oxidized single-walled carbon nanohorn is greatly improved, the agglomeration of the oxidized single-walled carbon nanohorn is inhibited, the dispersibility of the oxidized single-walled carbon nanohorn is improved, and the modified oxidized single-walled carbon nanohorn is favorably dispersed in an aqueous solution. In the process, the electronic structure of the surface of the oxidized single-walled carbon nanohorn is not changed, and the properties of the oxidized single-walled carbon nanohorn are kept.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1(A) is a transmission electron micrograph of oxidized single-walled carbon nanohorns;
FIG. 1(B) is a transmission electron micrograph of modified oxidized single-walled carbon nanohorns in example 1;
FIG. 2 is a thermogravimetric analysis chart in detection example 3;
FIG. 3 is a UV spectrum analysis chart in detection example 4.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a modified oxidized single-walled carbon nanohorn, which contains a modifier and an oxidized single-walled carbon nanohorn modified by the modifier; the modifier is prepared through amidation reaction, wherein an amine group source is chitosan oligosaccharide, and an acyl group source is one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid.
According to the technical scheme, the modified oxidized single-walled carbon nanohorn is prepared by modifying the oxidized single-walled carbon nanohorn by using the modifying agent, wherein the modifying agent is obtained through amidation reaction, the amine group source is chitosan oligosaccharide, and the acyl group source is one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid. Thus, the acyl source in the modifier: stearic acid or deoxycholic acid or linolenic acid or oleic acid or palmitic acid exerts the characteristics of hydrophobicity and strong affinity to the oxidized single-walled carbon nanohorn, the stearic acid or deoxycholic acid or linolenic acid or oleic acid or palmitic acid is piled and wound on the oxidized single-walled carbon nanohorn, the chitosan oligosaccharide end in the modifier exerts the hydrophilic effect, the hydrophilic degree of the modified oxidized single-walled carbon nanohorn is greatly improved, the agglomeration of the oxidized single-walled carbon nanohorn is inhibited, the dispersibility of the oxidized single-walled carbon nanohorn is improved, and the modified oxidized single-walled carbon nanohorn is favorably dispersed in an aqueous solution. In the process, the electronic structure of the surface of the oxidized single-walled carbon nanohorn is not changed, and the properties of the oxidized single-walled carbon nanohorn are kept.
In the above technical scheme, the method for preparing the modifier can be realized by various methods, as long as the amidation reaction is carried out on the chitosan oligosaccharide serving as the amine source and one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid serving as the acyl source.
Of course, the mass ratio of the oxidized single-walled carbon nanohorn to the modifier in the modified oxidized single-walled carbon nanohorn can be adjusted in a wide range, and in order to improve the hydrophilicity of the modified oxidized single-walled carbon nanohorn while maintaining the strong adsorption effect of the original oxidized single-walled carbon nanohorn, preferably, the mass ratio of the oxidized single-walled carbon nanohorn to the modifier in the modified oxidized single-walled carbon nanohorn is 1: 0.9-1.1.
In the technical scheme, the number average molecular weight of the chitosan oligosaccharide can be selected in a wide range, and in order to improve the hydrophilicity of the modified oxidized single-walled carbon nanohorn, the number average molecular weight of the chitosan oligosaccharide is preferably 500-5000.
In the above technical solution, the zeta potential of the modified single-walled oxide carbon nanohorn may be adjusted in a wide range, and in order to improve the hydrophilicity of the modified single-walled oxide carbon nanohorn while maintaining the adsorbability of the modified single-walled oxide carbon nanohorn, the zeta potential of the modified single-walled oxide carbon nanohorn is preferably 4.8 to 33.7 mV.
In order to improve the hydrophilicity of the modified single-walled oxide carbon nanohorn and maintain the adsorbability of the modified single-walled oxide carbon nanohorn, further, the zeta potential of the modified single-walled oxide carbon nanohorn is 23 to 33.7 mV.
The present invention also provides a method for preparing the modified oxidized single-walled carbon nanohorns as described above, comprising the steps of: (1) dissolving an acyl source compound in ethanol by ultrasonic waves, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide, stirring in a dark place, and carrying out an activation reaction to obtain an activated acyl source compound, wherein the acyl source is one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid; (2) dissolving chitosan oligosaccharide in water, adding an activated acyl source compound, heating for reaction, adding ethanol after the reaction is finished, centrifuging, and removing impurities to obtain a modifier; (3) mixing the oxidized single-walled carbon nanohorn with water, adding a modifier, performing ultrasonic treatment, centrifuging to remove supernatant, and retaining precipitate.
According to the technical scheme, the modified oxidized single-walled carbon nanohorn is prepared by modifying the oxidized single-walled carbon nanohorn by the modifier, wherein the amine group source of the modifier is chitosan oligosaccharide, and the acyl group source is one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid. Thus, the acyl source in the modifier: stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid play a role in hydrophobicity and strong affinity to the oxidized single-walled carbon nanohorn, are piled and wound on the oxidized single-walled carbon nanohorn, and the chitosan oligosaccharide end in the modifier plays a role in hydrophilicity, so that the hydrophilic degree of the modified oxidized single-walled carbon nanohorn is greatly improved, and the modified oxidized single-walled carbon nanohorn is favorably dispersed in an aqueous solution. In the process, the electronic structure of the surface of the oxidized single-walled carbon nanohorn is not changed, and the properties of the oxidized single-walled carbon nanohorn are kept.
In the technical scheme, the number average molecular weight of the chitosan oligosaccharide can be selected in a wide range, and in order to improve the hydrophilicity of the modified oxidized single-walled carbon nanohorn, the number average molecular weight of the chitosan oligosaccharide is preferably 500-5000.
In the above-mentioned technical means, the amount of each original use may be selected from a wide range, and in order to increase the conversion rate of the modifier, it is preferable that the amount of the acyl source compound is 3 to 5 parts, the amount of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 6 to 10 parts, the amount of N-hydroxysuccinimide is 3 to 5 parts, the amount of chitosan oligosaccharide is 4 to 6 parts, and the amount of water used in step (2) is 7 to 9 parts, in parts by weight, relative to 100 parts by weight of ethanol.
In the above technical solution, the mass ratio of the oxidized single-walled carbon nanohorn to the modifying agent to water may be selected within a wide range, and in order to increase the conversion rate of the reaction, it is preferable that in step (3), the mass ratio of the oxidized single-walled carbon nanohorn to the modifying agent to water is 1: 1-22: 3800-4200.
In a more preferred embodiment herein, in order to increase the conversion rate of the reaction, further, in step (3), the mass ratio of the oxidized single-walled carbon nanohorns, the modifier and the water is 1: 18-22: 3800-4000.
In the above technical scheme, the activation reaction in step (1) may be performed under various conditions, and in order to increase the activity of the acyl source compound to promote the amidation reaction with chitosan oligosaccharide, it is preferable that the activation time in step (1) is 0.8-1.2 h.
In the above technical scheme, the heating reaction conditions in the step (2) can be adjusted within a wide range, and in order to promote the amidation reaction of the acyl source compound and the chitosan oligosaccharide, it is preferable that the heating reaction temperature in the step (2) is 78-82 ℃ and the heating reaction time is 4-6 h.
Of course, the amidation reaction may be carried out in various ways, for example, direct water bath heating is possible, and in order to increase the conversion of the modifier, it is preferable to carry out the heating reaction in a reflux reaction.
In the above technical scheme, ethanol in the step (1) is a solvent, so the concentration of ethanol can be selected in a wide range, and preferably, anhydrous ethanol with the volume fraction of 99.97% is selected.
In the above technical solution, the addition of ethanol and centrifugation are performed to remove impurities, so the addition amount of ethanol and the number of centrifugation can be flexibly adjusted, and in a preferred embodiment herein, 8 to 10 parts by mass of ethanol is selectively added to 1 part by volume of the reaction mixture, followed by centrifugation, and then repeated addition of ethanol and further centrifugation for 2 to 5 times.
In the above technical solution, the ultrasonic conditions for preparing the modified oxidized single-walled carbon nanohorn may be adjusted in a wide range, and in order to increase the conversion rate of the modified oxidized single-walled carbon nanohorn, the modifying agent is wound or deposited on the oxidized single-walled carbon nanohorn, preferably, the ultrasonic conditions in step (3) include: the ultrasonic time is 0.5-1.5 h;
in order to improve the conversion rate of the modified oxidized single-walled carbon nanohorn, the modifier is wound or stacked on the oxidized single-walled carbon nanohorn, and more preferably, the temperature of the ultrasonic treatment in the step (3) is 25-40 ℃.
Further, in order to increase the conversion rate of the modified oxidized single-walled carbon nanohorn, the modifier is wound or deposited on the oxidized single-walled carbon nanohorn, and preferably, the ultrasonic frequency in the step (3) is 40 to 60 kHZ.
In the above technical solution, the mixing conditions of the single-walled carbon oxide nanohorn and water may be in various manners, such as stirring, vibration, shaking, etc., and in order to improve the dispersion degree of the single-walled carbon oxide nanohorn in water, preferably, the mixing manner is ultrasonic mixing, and the ultrasonic frequency is 40 to 60 kHZ.
Wherein, the mixing time of the oxidized single-wall carbon nanohorn and the water can be selected in a wide range, and in order to improve the dispersion degree of the oxidized single-wall carbon nanohorn, the mixing time is preferably 0.5 to 1.5 h.
Wherein, the mixing temperature of the nanometer angle of the single-wall carbon oxide and the water can be selected in a wide range, and in order to improve the dispersion degree of the nanometer angle of the single-wall carbon oxide, the mixing temperature is preferably 25-40 ℃.
In the technical scheme, the centrifugation condition can be adjusted in a wider range, and in order to improve the purity of the modified oxidized single-walled carbon nanohorn and remove unreacted modifying agent, the centrifugation speed is preferably 8000-15000rpm/min, and the centrifugation time is preferably 10-20 min. The centrifugation times can be flexibly adjusted, and preferably, in order to improve the purity of the modified oxidized single-walled carbon nanohorn and avoid reducing the content of the modifier in the modified oxidized single-walled carbon nanohorn, the centrifugation times are preferably 2-4 times.
The invention also provides application of the modified oxidized single-walled carbon nanohorn in adsorption of antibiotics.
As mentioned above, the modified oxidized single-walled carbon nanohorn has better hydrophilicity, which is beneficial to the dispersion of the modified oxidized single-walled carbon nanohorn in aqueous solution. In the process, the electronic structure of the surface of the oxidized single-walled carbon nanohorn is kept, and the property of strong adsorbability of the oxidized single-walled carbon nanohorn is kept. The antibiotic is treated by using the modified oxidized single-walled carbon nanohorn, and the method has the advantages of strong adsorbability, high removal rate, low cost, convenient operation, high pollutant removal rate, no high-toxicity metabolite and the like.
When the modified oxidized single-walled carbon nanohorn is used for adsorbing antibiotics, the fed modified oxidized single-walled carbon nanohorn can be selected in a wide range, and in order to improve the adsorption rate of the antibiotics and save raw materials, the amount of the antibiotics adsorbed by each milligram of the modified oxidized single-walled carbon nanohorn is preferably 0.9-1.1 mg.
Furthermore, the present invention provides a method for adsorbing antibiotics, comprising the step of mixing the modified oxidized single-walled carbon nanohorns described above with a solution containing an antibiotic.
The antibiotic is treated by using the modified oxidized single-walled carbon nanohorn, and the method has the advantages of strong adsorbability, high removal rate, low cost, convenient operation, high pollutant removal rate, no high-toxicity metabolite and the like.
In the technical scheme, the mass concentration of the modified oxidized single-walled carbon nanohorn in the mixed solution can be selected in a wide range, and in order to improve the adsorption rate of antibiotics and save raw materials, the mass concentration of the modified oxidized single-walled carbon nanohorn in the mixed solution is preferably 0.2-0.5mg/m L.
In the technical scheme, the mass concentration of the modified oxidized single-walled carbon nanohorn in the mixed solution can be selected in a wide range, and in order to improve the adsorption rate of antibiotics and save raw materials, the mass concentration of the modified oxidized single-walled carbon nanohorn in the mixed solution is preferably 0.3-0.4mg/m L.
In the above technical solution, the mixing temperature can be selected in a wide range, and in order to increase the adsorption rate of the antibiotic, the mixing temperature is preferably 10-55 ℃.
In the above technical solution, the pH of the mixed solution can be selected within a wide range, and in order to increase the adsorption rate of the antibiotic, the pH of the mixed solution is preferably 5 to 9.
The present invention will be described in detail below by way of examples.
In the following examples, the number average molecular weight of chitosan oligosaccharide is 1000, purchased from Shenzhen Antai Biotech, Inc.; oxidized single-walled carbon nanohorns with a purity of greater than 85%, japan electrical products ltd; activated carbon, 200 mesh powder, Liyang chemical test; ciprofloxacin hydrochloride 99%, date yang zhen far chemical limited; the ethanol is AR absolute ethanol; the others are conventional reagents; desktop high speed centrifuge TG16-W, Changshan Intelligent centrifuge instruments Inc.; constant temperature oscillator HZ-C, Taicang City laboratory facilities; ultrasonic cleaner XO-3200DT, manufactured by Nanjing Europe instruments Ltd; electronic balance BS 124S, beijing sidoris instruments systems ltd; UV-1800 UV-visible spectrophotometer, Shimadzu corporation, Japan; pH meter PHS-25, Shanghai precision scientific instruments, Inc.
Example 1
Preparing modified oxidized single-walled carbon nanohorns:
(1) ultrasonically dissolving 0.531g of stearic acid in 13.27g of ethanol, adding 1.061g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 0.531g N-hydroxysuccinimide, stirring in the dark, and carrying out activation reaction for 1.0h to obtain activated stearic acid;
(2) dissolving 0.664g of chitosan oligosaccharide in 1.062g of water, adding activated stearic acid, reacting for 5 hours at 80 ℃ in a reflux reaction mode, adding ethanol after the reaction is finished, centrifuging, and removing impurities to obtain a modifier;
(3) ultrasonically mixing the oxidized single-walled carbon nanohorn and water at the ultrasonic frequency of 50kHZ and the temperature of 32 ℃ for 1h, and then adding a modifier, wherein the mass ratio of the oxidized single-walled carbon nanohorn to the modifier to the water is 1: 18: 4000, then sonicated at 32 ℃ for 1.0h at 50kHZ, and centrifuged at 11000rpm/min for 15min to remove the supernatant, leaving the precipitate.
Example 2
Preparing modified oxidized single-walled carbon nanohorns:
(1) ultrasonically dissolving 0.664g of stearic acid in 13.27g of ethanol, adding 1.327g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 0.664g N-hydroxysuccinimide, stirring in a dark place, and carrying out an activation reaction for 1.2h to obtain activated stearic acid;
(2) dissolving 0.796g of chitosan oligosaccharide in 1.194g of water, adding activated stearic acid, reacting for 6 hours at 78 ℃ in a reflux reaction mode, adding ethanol after the reaction is finished, centrifuging, and removing impurities to obtain a modifier;
(3) ultrasonically mixing the oxidized single-walled carbon nanohorn with water at the ultrasonic frequency of 60kHZ and the temperature of 40 ℃ for 1.5h, and then adding a modifier, wherein the mass ratio of the oxidized single-walled carbon nanohorn to the modifier to the water is 1: 22: 4200, then sonicated at 40 deg.C for 1.5h at 60kHZ, and centrifuged at 15000rpm/min for 20min to remove the supernatant, leaving the pellet.
Example 3
Preparing modified oxidized single-walled carbon nanohorns:
(1) dissolving 0.398g of stearic acid in 13.27g of ethanol by ultrasonic, adding 0.796g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 0.398g N-hydroxysuccinimide, stirring in the dark, and carrying out activation reaction for 0.8h to obtain activated stearic acid;
(2) dissolving 0.531g of chitosan oligosaccharide in 0.929g of water, adding activated stearic acid, reacting for 4 hours at 82 ℃ in a reflux reaction mode, adding ethanol after the reaction is finished, centrifuging, and removing impurities to obtain a modifier;
(3) ultrasonically mixing the oxidized single-walled carbon nanohorn with water, wherein the ultrasonic frequency is 40kHZ, the temperature is 25 ℃, mixing for 0.5h, and then adding a modifier, wherein the mass ratio of the oxidized single-walled carbon nanohorn to the modifier to the water is 1: 1: 3800, sonicating at 25 deg.C for 0.5h at 40kHZ, and centrifuging at 8000rpm/min for 10min to remove supernatant and retain the precipitate.
Example 4
Modified oxidized single-walled carbon nanohorns were prepared as in example 1, except that deoxycholic acid was used in place of stearic acid.
Example 5
Modified oxidized single-walled carbon nanohorns were prepared as in example 1, except that linolenic acid was used instead of stearic acid.
Example 6
Modified oxidized single-wall carbon nanohorns were prepared as in example 1, except that oleic acid was used instead of stearic acid.
Example 7
Modified oxidized single-walled carbon nanohorns were prepared as in example 1, except that palmitic acid was used instead of stearic acid.
Detection example 1
Transmission electron microscope scanning analysis was performed on the modified oxidized single-walled carbon nanohorns and the oxidized single-walled carbon nanohorns in example 1, and as shown in fig. 1(B) and fig. 1(a), the individual carbon nanohorns aggregated into spherical aggregates of 80 to 100nm, and the surface thereof had some angular projections, which were shaped like "dahlia". The carbon nanohorn modified with stearic acid-chitosan oligosaccharide has a layer of fuzzy smog on the surface, the edge is smooth, and angular protrusions cannot be seen, which can indicate that the stearic acid-chitosan oligosaccharide is successfully modified on the carbon nanohorn.
Detection example 2
The Zeta potential value of the oxidized single-walled carbon nanohorn is-25.4 +/-3.6 mV, the average aggregation particle size in water is 263.3 +/-13.0 nm, and the particle size and the Zeta potential are measured, so that for the modified oxidized single-walled carbon nanohorn prepared in the example 1, after the modification of the stearic acid-chitosan oligosaccharide serving as the modifier, the Zeta potential becomes a positive value, the maximum value is 33.7mV, and the aggregation particle size in water is not more than 200nm, which shows that the modifier is successfully wound on the single-walled carbon nanohorn, and the dispersibility of the oxidized single-walled carbon nanohorn is improved.
Detection shows that the zeta potentials of the modified oxidized single-walled carbon nanohorns prepared in the examples 2 to 7 are positive values, and the aggregation particle size in water of the modified oxidized single-walled carbon nanohorns is not more than 200 nm.
Detection example 3
Thermogravimetric analysis was performed on the modified oxidized single-walled carbon nanohorn (oxSWNHs-SA-CS), stearic acid-chitosan oligosaccharide (SA-CS), oxidized single-walled carbon nanohorn (oxSWNHs) in example 1, as shown in fig. 2, whereby the amount of stearic acid-chitosan oligosaccharide as a modifier on the oxidized single-walled carbon nanohorn was calculated, and 1.02mg of stearic acid-chitosan oligosaccharide was modified per mg of oxidized single-walled carbon nanohorn upon detection.
The amount of the corresponding modifier modified by the modified oxidized single-walled carbon nanohorns prepared in examples 2-7 was determined to be at least 0.92mg per mg.
Detection example 4
As a result of uv spectrum analysis of the modified oxidized single-walled carbon nanohorn (oxSWNHs-SA-CS), stearic acid-chitosan oligosaccharide (SA-CS), and oxidized single-walled carbon nanohorn (oxSWNHs) in example 1, the oxidized single-walled carbon nanohorn had a relatively broad absorption peak at 268nm and stearic acid-chitosan oligosaccharide had an absorption peak at 275nm, as shown in fig. 3. The stearic acid-chitosan oligosaccharide absorption peak appears in the modified oxidized single-walled carbon nanohorn, and the absorption peak is shifted to the long wave direction by 4nm, because the stearic acid-chitosan oligosaccharide is wound on the oxidized single-walled carbon nanohorn to cause the shift of the absorption wavelength. This also demonstrates the successful winding of stearic acid-chitosan oligosaccharide on oxidized single-walled carbon nanohorns.
Application example 1
Adding 600 mu L1 mg/m L modified oxidized single-walled carbon nanohorn dispersion liquid, 500 mu L0.5.5 mg/m L ciprofloxacin solution and 1900 mu L distilled water into a series of 5m L EP tubes respectively, enabling the pH value of the mixed solution to be 8, placing the mixed solution into a constant-temperature oscillator, oscillating at 25 ℃ at 100r/min, taking out the mixed solution after 60min, centrifuging at 12000r/min at a high speed for 5min, passing through a membrane (0.22 mu m), taking the filtrate to measure the absorbance, calculating the concentration of the residual ciprofloxacin in the filtrate according to a standard curve equation, calculating the adsorption rate as follows:
q＝100％×(C0-Ct)/C0
in the formula, C0And CtThe mass concentrations of ciprofloxacin initially and remaining after adsorption in the solution are respectively.
The adsorption rates of the modified oxidized single-walled carbon nanohorns prepared in example 1, example 4 to example 7 and the adsorption rates of activated carbon and oxidized single-walled carbon nanohorns were measured by the methods described above, and the results are shown in table 1.
TABLE 1
Figure BDA0001354217130000131
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (17)

1. A modified oxidized single-walled carbon nanohorn comprising a modifier and an oxidized single-walled carbon nanohorn modified with the modifier;
the modifier is prepared through amidation reaction, wherein an amine group source is chitosan oligosaccharide, and an acyl group source is one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid; the modified oxidized single-walled carbon nanohorn is obtained by modifying the oxidized single-walled carbon nanohorn by a non-covalent modification method, and the hydrophobic part of the modifier is accumulated or wound with the hydrophobic pipe wall of the oxidized single-walled carbon nanohorn;
wherein the modified oxidized single-walled carbon nanohorn is prepared by the following steps:
(1) dissolving an acyl source compound in ethanol by ultrasonic waves, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide, stirring in a dark place, and carrying out an activation reaction to obtain an activated acyl source compound, wherein the acyl source is one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid;
(2) dissolving chitosan oligosaccharide in water, adding an activated acyl source compound, heating for reaction, adding ethanol after the reaction is finished, centrifuging, and removing impurities to obtain a modifier;
(3) mixing the oxidized single-walled carbon nanohorn with water, adding a modifier, performing ultrasonic treatment, centrifuging to remove supernatant, and retaining precipitate.
2. The modified oxidized single-walled carbon nanohorn of claim 1, wherein the modified oxidized single-walled carbon nanohorn has a mass ratio of oxidized single-walled carbon nanohorn to modifier of 1: 0.9-1.1;
and/or the number average molecular weight of the chitosan oligosaccharide is 500-5000.
3. The modified oxidized single-walled carbon nanohorn of claim 1, wherein the zeta potential of the modified oxidized single-walled carbon nanohorn is 4.8 to 33.7 mV.
4. The modified oxidized single-walled carbon nanohorn of claim 3, wherein the zeta potential of the modified oxidized single-walled carbon nanohorn is 23 to 33.7 mV.
5. A method of making the modified oxidized single-walled carbon nanohorns of any one of claims 1 to 4, comprising the steps of:
(1) dissolving an acyl source compound in ethanol by ultrasonic waves, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide, stirring in a dark place, and carrying out an activation reaction to obtain an activated acyl source compound, wherein the acyl source is one or more of stearic acid, deoxycholic acid, linolenic acid, oleic acid and palmitic acid;
(2) dissolving chitosan oligosaccharide in water, adding an activated acyl source compound, heating for reaction, adding ethanol after the reaction is finished, centrifuging, and removing impurities to obtain a modifier;
(3) mixing the oxidized single-walled carbon nanohorn with water, adding a modifier, performing ultrasonic treatment, centrifuging to remove supernatant, and retaining precipitate.
6. The method according to claim 5, wherein the acyl source compound is used in an amount of 3 to 5 parts, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is used in an amount of 6 to 10 parts, N-hydroxysuccinimide is used in an amount of 3 to 5 parts, chitosan oligosaccharide is used in an amount of 4 to 6 parts, and water in step (2) is used in an amount of 7 to 9 parts, based on 100 parts by weight of ethanol.
7. The method as claimed in claim 5, wherein, in the step (3), the mass ratio of the oxidized single-walled carbon nanohorn, the modifier and the water is 1: 1-22: 3800-4200.
8. The method of claim 7, wherein the mass ratio of oxidized single-walled carbon nanohorns, modifier, and water is 1: 18-22: 3800-4000.
9. The method according to claim 5, wherein the activation time in step (1) is 0.8-1.2 h; and/or the heating reaction temperature in the step (2) is 78-82 ℃, and the heating reaction time is 4-6 h.
10. The method of claim 9, wherein the heating reaction is performed as a reflux reaction.
11. The method of claim 5, wherein the conditions of sonication in step (3) include: the ultrasonic time is 0.5-1.5 h; and/or, the temperature during ultrasonic treatment is 25-40 ℃; and/or the ultrasonic frequency is 40-60 kHZ;
and/or, wherein the mixing conditions of the oxidized single-walled carbon nanohorn and the water comprise: the mixing mode is ultrasonic mixing, and the ultrasonic frequency is 40-60 kHZ; and/or the mixing time is 0.5-1.5 h; and/or, the mixing temperature is 25-40 ℃;
and/or wherein the centrifugation conditions comprise: the centrifugation speed is 8000-15000rpm/min, and the centrifugation time is 10-20 min.
12. Use of the modified oxidized single-walled carbon nanohorns of any one of claims 1 to 4 for adsorbing antibiotics.
13. The use of claim 12, wherein the amount of adsorbed antibiotic per mg of modified oxidized single-wall carbon nanohorn is 0.9-1.1 mg.
14. A method for adsorbing antibiotics, comprising the step of mixing the modified oxidized single-walled carbon nanohorns according to any one of claims 1 to 4 with an antibiotic-containing solution.
15. The method for adsorbing antibiotics of claim 14, wherein the mass concentration of the modified oxidized single-walled carbon nanohorn in the mixed solution is 0.3-0.4mg/m L.
16. The method for adsorbing antibiotics of claim 14, wherein the mixing temperature is 10-55 ℃.
17. The method for adsorbing antibiotics according to claim 14, wherein the mixed solution has a pH of 5 to 9.
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