CN110026157B - Glutathione functionalized graphene oxide/gold nanorod composite material and preparation method and application thereof - Google Patents
Glutathione functionalized graphene oxide/gold nanorod composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a glutathione functionalized graphene oxide/gold nanorod composite material, a preparation method thereof and application thereof in ciprofloxacin adsorption separation. Gold nanorods are loaded on graphene oxide by a seed-mediated method, and finally, the graphene oxide/gold nanorod composite material is modified by reduced glutathione, so that the glutathione functionalized graphene oxide/gold nanorod composite material is successfully synthesized. The maximum adsorption capacity of the glutathione functionalized graphene oxide/gold nanorod composite material is higher than the reported adsorption capacity of graphene oxide, quantitative adsorption can be achieved in a short time, the adsorption performance is good, and the maximum adsorption capacity of ciprofloxacin in a solution is 476.2mg g‑1。
Description
Technical Field
The invention belongs to the technical field of antibiotic residue analysis, and particularly relates to a glutathione functionalized graphene oxide/gold nanorod composite material, a preparation method thereof and application thereof in ciprofloxacin adsorption separation.
Background
In recent years, the development of nano science and technology is rapid, more and more nano materials are continuously emerged, and the discovery and synthesis of carbon nano materials also arouse the research enthusiasm of researchers in the world. Researchers firstly prepare Graphene Oxide (GO) by chemically oxidizing and stripping graphite powder, compared with Graphene, the surface of a single carbon atomic layer of Graphene oxide has a large number of active oxygen-containing functional groups, so that the Graphene oxide has excellent hydrophilicity and dispersibility in water, and in addition, the Graphene oxide has a larger specific surface area, and the Graphene oxide becomes a high-performance adsorption material due to the two most considerable characteristics, and can be compounded with a plurality of materials to improve the adsorption effect.
Ciprofloxacin (Ciprofloxacin) is a chemically synthesized antibacterial agent widely used by people in recent years, has the advantages of wide antibacterial spectrum, high efficiency, low toxicity, long half-life period and the like, is a third-generation fluoroquinolone antibacterial agent which is most widely applied, is suitable for treating infectious diseases caused by various bacteria, and can effectively prevent and treat various infectious diseases of animals by adding a proper amount of Ciprofloxacin into feed of meat poultry in the breeding process. However, with the wide use of ciprofloxacin in food animals, the problem that ciprofloxacin medicaments are remained in the animal bodies is increasingly serious. The ciprofloxacin with high concentration can cause adverse reactions such as tachycardia, skin allergy, photosensitive dermatosis, gastrointestinal reaction and the like, and long-term low-dose ingestion can cause high concentration of drug residues in a body to cause accumulative poisoning and also can cause the problem of drug resistance. The development of modern analytical instruments is rapid, but the resolution, sensitivity and stability of the detection method are still to be further improved, so that it is of great importance to research a technology for quickly and effectively removing ciprofloxacin residues.
The Solid-phase extraction (SPE) technology is one of the most widely used sample pretreatment technologies, has the advantages of rapidness, low cost, simplicity in operation and the like, can remarkably reduce the dosage of a solvent, and is widely applied to detection of pesticide or veterinary drug residues in various food matrixes due to the characteristics of high efficiency, high selectivity, high automation and the like. The solid phase extraction technology mainly utilizes the difference of the distribution coefficients of a target compound and a matrix in an adsorbent in a tested sample, and uses a corresponding solvent for elution to separate the target compound from the matrix, namely, the target compound is separated, purified and enriched by utilizing the distribution between the solvent and the adsorbent, wherein the selection of the adsorbent is the most important factor influencing the extraction and enrichment efficiency and selectivity. GO is used as a new-generation carbon nano material, has a huge development prospect in the aspect of SPE technology due to good adsorption performance, is low in preparation cost and easy in raw material acquisition, but is difficult to disperse, is not beneficial to effective adsorption and elution of a sample to be detected and influences the adsorption efficiency, and the GO is easily agglomerated after being directly used as a solid phase extraction material for adsorption. Therefore, how to perform effective functional modification on GO is a technical problem which needs to be solved urgently to develop a novel adsorbent with high selectivity and high adsorption capacity.
In recent years, studies on Gold Nanorods (GNRs) have been increasing, and studies on applications of the gold nanorods after functionalization have been attracting attention. The gold nanorods have high electron density, catalytic action and dielectric property, can be combined with various biological macromolecules, cannot influence the biological activity of the gold nanorods, reduces the use of various activating agents, and is green and environment-friendly. A large number of oxygen-containing groups exist on the surface of the graphene oxide, and can provide reactive sites for nucleation, growth and loading of the gold nanorod. The combination of GNRs and GO has the potential to simultaneously take advantage of these two materials, on the one hand improving the dispersion properties of graphene oxide and on the other hand enhancing synergistic properties such as catalytic, magnetic, electrical and optical activities. In addition, the sulfydryl and the gold nanorods have strong affinity and are easy to form Au-S bonds, so that sulfydryl compounds can be modified on the surfaces of the gold nanorods, GO can indirectly modify the sulfydryl compounds through the action of connecting arms of the gold nanorods, and more binding sites are provided for detected target compounds
Disclosure of Invention
The technical problem to be solved is as follows: the invention aims to solve the technical problems that graphene oxide is easy to agglomerate and difficult to disperse after being adsorbed as a solid-phase extraction material and is not beneficial to effective adsorption and elution of a sample to be detected, and provides a glutathione functionalized graphene oxide/gold nanorod composite material (GO/GNRs-GSH), which is obtained by loading gold nanorods on graphene oxide and modifying the surfaces of the gold nanorods by utilizing mercapto groups contained in glutathione, and the composite material is used as a novel adsorbent for solid-phase extraction and can be used for adsorbing and separating ciprofloxacin in a solution to perform trace analysis.
The technical scheme is as follows: the glutathione functionalized graphene oxide/gold nanorod composite material takes graphene oxide as a carrier and loads gold nanorods, the surface of each gold nanorod is modified with glutathione, and the gold nanorods are connected with the glutathione through sulfydryl.
The preparation method of the glutathione functionalized graphene oxide/gold nanorod composite material comprises the following steps:
step 1, adding oxidized graphene into water, and performing ultrasonic dispersion to obtain oxidized graphene dispersion liquid;
step 2, HAuCl4·4H2Mixing the O solution and CTAB solution, adding NaBH4Incubating the solution at 25 deg.C for 30min to obtain seed solution;
step 3, mixing CTAB solution and HAuCl4·4H2Mixing the O solution, adding AgNO3Preparing a growth solution by using the solution and an ascorbic acid solution;
step 4, adding the graphene oxide dispersion liquid into the growth solution, adding the seed solution, carrying out heat preservation reaction at the temperature of 25-28 ℃ for 10-12h, purifying the reaction solution by using deionized water through centrifugation, washing by using ethanol, and drying to obtain graphene oxide/gold nanorods;
and 5, adding the graphene oxide/gold nanorods into water, performing ultrasonic dispersion, adding reduced glutathione into the dispersion liquid under the stirring condition, stirring and reacting for 2-4h at 25-28 ℃, centrifuging the product, washing with water and ethanol in sequence, and drying to obtain the glutathione functionalized graphene oxide/gold nanorod composite material.
Further, the volume ratio of the graphene oxide dispersion liquid to the seed solution in the step 4 is 20:1, and the concentration of the graphene oxide dispersion liquid is 50mg mL-1。
Further, in the step 5, the mass ratio of the graphene oxide/gold nanorod composite material to the glutathione is 3.5.
Further, in the step 5, the drying condition is 40-60 ℃ for 10-16 h.
The glutathione functionalized graphene oxide/gold nanorod composite material is applied to ciprofloxacin adsorption separation.
Further, the glutathione functionalized graphene oxide/gold nanorod adsorbent is directly added into a sample solution containing ciprofloxacin, and after static adsorption, centrifugal separation is carried out, so that the method is obtained.
Has the advantages that:
1. the method combines the advantages of the graphene oxide and the gold nanorods, and solves the technical problems that the graphene oxide is easy to agglomerate and difficult to disperse after being adsorbed as a solid phase extraction material, and is not beneficial to effective adsorption and elution of a sample to be detected.
2. The maximum adsorption capacity of the glutathione functionalized graphene oxide/gold nanorod composite material is higher than the reported adsorption capacity of graphene oxide, quantitative adsorption can be achieved in a short time, the adsorption performance is good, and the maximum adsorption capacity of ciprofloxacin in a solution is 476.2mg g-1。
Drawings
FIG. 1 is the graph of the effect of GO/GNRs-GSH on ciprofloxacin adsorption at different acidity for example 3;
FIG. 2 is the adsorption effect curve of GO/GNRs-GSH with different mass on ciprofloxacin in example 4;
FIG. 3 is the graph of the effect of GO/GNRs-GSH on ciprofloxacin adsorption at different adsorption times in example 5;
FIG. 4 is the adsorption performance of GO/GNRs-GSH on ciprofloxacin under different ion interferences in example 6;
FIG. 5 is the adsorption capacity curve of GO/GNRs-GSH versus ciprofloxacin in example 7;
FIG. 6 is a linear model of the Langmuir adsorption isotherm of GO/GNRs-GSH on ciprofloxacin in example 7;
FIG. 7 is a graph showing the effect of different ratios of potassium dihydrogen phosphate to methanol on the elution efficiency of ciprofloxacin in example 8;
FIG. 8 is the effect of monopotassium phosphate-methanol at different pH values on ciprofloxacin elution efficiency in example 8.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments in order to better understand the present invention. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Preparation of glutathione functionalized graphene oxide/gold nanorod composite material (GO/GNRs-GSH)
The preparation method comprises the following steps:
step 1, adding 1.0g of graphene oxide into 20mL of water in advance, and performing ultrasonic dispersion for 2 hours to obtain a graphene oxide dispersion liquid for later use.
Step 2, HAuCl4·4H2O(0.50mmol L-15.0mL) with CTAB (0.20mol L)-110.0mL) was mixed and freshly prepared ice-cold NaBH was added4(0.01mol L-1600. mu.L) and incubated at 25 ℃ for 30min to prepare a seed solution.
Step 3, CTAB (0.02mol L)-150mL) and HAuCl4·4H2O(24mmol L-13.12mL) was mixed and AgNO was added3(4.0mmol L-12.8mL) and ascorbic acid (0.08mol L)-11.25mL) to prepare a growth solution.
Step 4, 20mL of graphene oxide dispersion (50mg mL)-1) Introduced into the growth solution. Finally, 1mL of the seed solution was added to the growth solution and maintained at 28 ℃ overnight. And purifying the final solution by using deionized water through three times of centrifugation, washing by using ethanol, and drying to obtain the graphene oxide/gold nanorods.
And 5, adding 80mg of the graphene oxide/gold nanorod into 60mL of water, and performing ultrasonic dispersion for 2 hours to obtain a graphene oxide-gold nanorod dispersion liquid. The dispersion was stirred in a water bath at 25 ℃ and 23.01mg of reduced glutathione was added and stirring was continued for 2 h. And centrifuging the product, washing with water and ethanol in sequence, and drying at 50 ℃ for 12h to obtain a solid product, namely the glutathione functionalized graphene oxide/gold nanorod composite material (GO/GNRs-GSH).
The FT-IR technology is used for characterizing each material, and whether the graphene oxide/gold nanorods and the reduced glutathione modified graphene oxide/-gold nanorods are successfully prepared or not is verified. The results show that: 3000-2850 cm-1Has a C-H stretching vibration peak at 1371cm-1Has bending vibration peak of methyl at 1465cm-1Bending vibration with methylene radicalsAnd (4) a peak indicating that the gold nanorods are successfully loaded on the graphene oxide. 2400cm-1And a characteristic peak of sulfydryl exists nearby, which indicates that reduced glutathione is successfully modified on the graphene oxide/gold nanorods.
According to the method, gold nanorods are loaded on graphene oxide by a seed-mediated method, and finally, the graphene oxide/gold nanorod composite material is modified by reduced glutathione, so that the graphene oxide-gold nanorod composite material with functionalized glutathione is successfully synthesized.
Example 2
Static adsorption experiment
Preparation (3.0, 4.0, 5.0, 6.0, 7.0, 8.0 mg/L)-1) The absorbance A values of the samples are sequentially measured by a series of ciprofloxacin standard solutions with different concentrations, and the obtained curve y is 0.0961x-0.0036, and R2 is 0.9985, so that the linear relation between the concentration of the ciprofloxacin standard solution and the absorbance is good.
In the subsequent experiments, the adsorption rate calculation formula is as follows:
adsorption rate (%) - (c)0–ce)/c0×100％
In the formula, c0And ceRepresents the concentration of ciprofloxacin solution at the onset of adsorption and at equilibrium of adsorption.
Example 3
Adsorbing effect of GO/GNRs-GSH adsorbent on ciprofloxacin under different acidity
A series of ciprofloxacin standard solutions (5.0mg L) with different pH values (2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0 and 10.0) are prepared-1) Accurately weighing a plurality of 10.0mg GO/GNRs-GSH in 25mL conical bottles, respectively adding the GO/GNRs-GSH into ciprofloxacin standard solutions with different pH values, fully mixing the materials uniformly, putting the materials into a water bath constant temperature oscillator, and oscillating the materials for 30 min. The experimental result is shown in figure 1, the pH value is within the range of 2.0-6.0, and the adsorption efficiency of GO/GNRs-GSH on ciprofloxacin is increased along with the increase of the pH value; quantitative adsorption can be achieved at pH 7.0: (>95%); when the pH value of the solution is 7.0-10.0, the GO/GNRs-GSH can quantitatively adsorb ciprofloxacin.
Example 4
Adsorption effect of GO/GNRs-GSH with different masses on ciprofloxacin
Precisely weighing GO/GNRs-GSH with different masses (2.0, 5.0, 10.0, 15.0, 20.0, 30.0mg) respectively, adding into an erlenmeyer flask, and preparing a portion of ciprofloxacin standard solution (5mg L) with pH of 7.0-1) And respectively adding 10mL of the mixture into each conical flask, and after fully and uniformly mixing, oscillating for 30 min. As shown in the experiment of figure 2, when the mass of the adsorbent is below 10.0mg, the adsorption efficiency of GO/GNRs-GSH to ciprofloxacin is in an increasing trend along with the mass of the adsorbent, when the mass of the adsorbent is equal to 10.0mg, the GO/GNRs-GSH achieves quantitative adsorption to ciprofloxacin, and when the mass of the adsorbent is 10.0-30.0mg, the quantitative adsorption is achieved.
Example 5
Adsorption effect of different adsorption time on ciprofloxacin
A series of 5mg L pH 7.0 formulations-1The ciprofloxacin standard solution is prepared by respectively adding 10.0mg of GO/GNRs-GSH into each centrifugal tube containing 10.0mL of standard solution, fully and uniformly mixing, putting into a water bath constant temperature oscillator, and respectively oscillating for 2min, 5min, 10min, 15min, 20min, 25min, 30min and 40 min. As a result, as shown in FIG. 3, the adsorption rate increased with the increase of the adsorption time in the first 5min, and quantitative adsorption was achieved at 5 min.
Example 6
Influence of ion interference on adsorption Performance
Preparing a series of Na-containing compositions with different concentrations+、K+、Ca2+、Mg2+、Cu2+、Cd2+、Cr3+Ciprofloxacin standard solution (pH 7.0,5.0mg L)-1) 10.0mL of the mixture is respectively added into conical bottles containing 10.0mg of GO/GNRs-GSH, and the mixture is put into a water bath constant temperature oscillator for full oscillation after being uniformly mixed. The results of the experiment are shown in FIG. 4, from which it can be seen that Na is present at a certain concentration+、K+、Ca2+、Mg2+、Cu2+、Cd2+、Cr3+Has little influence on the adsorption of ciprofloxacin.
Example 7
Maximum adsorption capacity of GO/GNRs-GSH adsorbent for ciprofloxacin
Preparing a series of different concentrations (150.0, 200.0, 250.0, 300.0, 350.0mg L)-1) The ciprofloxacin standard solution is prepared by respectively taking 10.0mL of ciprofloxacin standard solution, putting the ciprofloxacin standard solution into a conical flask containing 10.0mg of GO/GNRs-GSH after fully and uniformly mixing, and oscillating for 2 hours to reach adsorption balance.
According to equilibrium adsorption capacity (q)e) Calculates each qeThe value:
qe＝(c0-ce)V/m
in the formula, qeIn mg g-1,c0And ceThe concentration of the solution in mg L is expressed as the initial adsorption and equilibrium adsorption-1(ii) a V is the volume of the solution in mL; m is the mass of the adsorbent, the unit is mg, the experimental result is shown in figure 5, the amount of ciprofloxacin adsorbed by the adsorbent is continuously increased along with the increase of the concentration of ciprofloxacin standard solution, the linear relation is good, the GO/GNRs-GSH has good affinity to ciprofloxacin, and the investigation of the potential maximum adsorption capacity of the GO/GNRs-GSH to ciprofloxacin has important significance.
Langmuir adsorption isotherms were used to fit the GO/GNRs-GSH adsorption data for ciprofloxacin as shown in the equation:
Ce/qe＝Ce/Q+1/Qb
drawing by taking Ce as independent variable and Ce/qe as variable to obtain a straight line, wherein the slope is 1/Q, and the intercept is 1/QbAs shown in fig. 6, a linear equation y is obtained, where R is 0.0021x +0.02142The results confirm the validity of the Langmuir model of this process, 0.9891. Calculating the maximum adsorption capacity of GO/GNRs-GSH to ciprofloxacin in the solution from the slope of the straight line to obtain 476.2mg g-1。
Example 8
Elution conditions
A series of 5mg L pH 7.0 formulations-1The ciprofloxacin standard solution is prepared by respectively adding 10.0mg of GO/GNRs-GSH into each centrifugal tube containing 10.0mL of standard solution, fully mixing uniformly, and then respectively oscillating for 1h to respectively enableQuantitative adsorption is achieved, supernatant is removed through centrifugation, the absorbance A value is measured under the wavelength of 276nm, and precipitates in a centrifuge tube are used for an elution experiment.
Preparing a series of potassium dihydrogen phosphate-methanol eluents with pH of 2 in different proportions (80:20,70:30,60:40,50:50,60:30), respectively adding the eluates into centrifuge tubes after elution, uniformly mixing, putting the eluates into a water bath constant temperature oscillator for shaking for 1 hour, fully eluting, filtering, taking supernate, measuring the absorbance A value, and calculating the elution efficiency, wherein the experimental result is shown in figure 7, and the result shows that the better the elution efficiency is when the proportion of the potassium dihydrogen phosphate-methanol is closer to 1: 1.
Preparing a series of potassium dihydrogen phosphate-methanol (50:50) eluents with different pH values (2.0,1.5 and 1.0), respectively adding the eluates into centrifuge tubes after elution, uniformly mixing, putting the eluates into a water bath constant temperature oscillator for shaking for 1 hour, filtering after full elution, taking supernate to measure the absorbance A value, and calculating the elution efficiency, wherein the experimental result is shown in figure 8, and the result shows that the elution effect of the potassium dihydrogen phosphate-methanol (50:50) on ciprofloxacin is better and better along with the increase of the acidity of the eluates. When the pH value is 2, the potassium dihydrogen phosphate-methanol (50:50) has the best elution effect on the ciprofloxacin, and the elution efficiency reaches 70-80%.
Claims (2)
1. The application of the glutathione functionalized graphene oxide/gold nanorod composite material in ciprofloxacin adsorption separation,
the glutathione functionalized graphene oxide/gold nanorod composite material takes graphene oxide as a carrier, loads gold nanorods, modifies glutathione on the surfaces of the gold nanorods, and is connected with the glutathione through sulfydryl;
the glutathione functionalized graphene oxide/gold nanorod composite material is prepared by the following steps:
step 1, adding oxidized graphene into water, and performing ultrasonic dispersion to obtain oxidized graphene dispersion liquid;
step 2, HAuCl4·4H2Mixing the O solution and CTAB solution, adding NaBH4Incubating the solution to obtain a seed solution;
step 3, mixing CTAB solution withHAuCl4·4H2Mixing the O solution, adding AgNO3Preparing a growth solution by using the solution and an ascorbic acid solution;
step 4, adding the graphene oxide dispersion liquid into the growth solution, adding the seed solution, carrying out heat preservation reaction at the temperature of 25-28 ℃ for 10-12h, purifying the reaction solution by using deionized water through centrifugation, washing by using ethanol, and drying to obtain graphene oxide/gold nanorods;
step 5, adding graphene oxide/gold nanorods into water, performing ultrasonic dispersion, adding reduced glutathione into the dispersion liquid under the stirring condition, stirring and reacting for 2-4h at 25-28 ℃, centrifuging the product, washing with water and ethanol in sequence, and drying to obtain a glutathione functionalized graphene oxide/gold nanorod composite material;
in the step 4, the volume ratio of the graphene oxide dispersion liquid to the seed solution is 20:1, and the concentration of the graphene oxide dispersion liquid is 50mg mL-1 ；
In the step 5, the mass ratio of the graphene oxide/gold nanorods to the glutathione is 3.5, and the drying condition is that the graphene oxide/gold nanorods are dried for 10-16h at 40-60 ℃.
2. Use according to claim 1, characterized in that: the method specifically comprises the steps of directly adding the glutathione functionalized graphene oxide/gold nanorod composite material into a sample solution containing ciprofloxacin, and after static adsorption, performing centrifugal separation to complete the adsorption separation of the ciprofloxacin.
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