CN108318461B - Sparfloxacin molecular imprinting-quantum dot mesoporous material and preparation method and application thereof - Google Patents
Sparfloxacin molecular imprinting-quantum dot mesoporous material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a sparfloxacin molecular imprinting-quantum dot mesoporous material, which comprises the following steps: firstly, forming a pre-acting compound by template molecules of sparfloxacin, 3-aminopropyltriethoxysilane and propionic acid sulfenyl methyl acetoxy propyl trimethoxysilane; then, modifying Mn doped ZnS quantum dots by a surfactant, a cross-linking agent, the pre-acting compound and L-cysteine to form a compound; and finally, eluting the template molecule sparfloxacin and the surfactant in the compound to obtain the sparfloxacin molecular imprinting-quantum dot mesoporous material. The invention also provides the sparfloxacin molecular imprinting-quantum dot mesoporous material prepared by the preparation method and application thereof in detecting the content of sparfloxacin in a sample, in particular to application in detecting the content of sparfloxacin in serum. The preparation method provided by the invention has simple steps; the prepared molecular imprinting-quantum dot mesoporous material can quickly, sensitively and specifically detect the sparfloxacin in a sample.
Description
Technical Field
The invention belongs to the field of molecular imprinting preparation, relates to a molecular imprinting-quantum dot mesoporous material, and particularly relates to a sparfloxacin molecular imprinting-quantum dot mesoporous material as well as a preparation method and application thereof.
Background
Sparfloxacin (SPFX) is a third-generation quinolone antibacterial agent, is widely used in veterinary and human medicine for treating respiratory, urinary and digestive system and skin soft tissue infections, and has strong antibacterial activity against gram-positive bacteria, gram-negative bacteria, mycoplasma, mycobacteria, and the like. But excessive use causes environmental pollution and endangers human health. At present, methods for detecting sparfloxacin mainly comprise a spectrophotometer method, an electrochemical method, a thin-layer chromatography method, a high performance liquid chromatography method, a liquid chromatography-mass spectrometry method, a capillary electrophoresis method and the like. However, most of these methods are complicated, time-consuming and labor-consuming. Therefore, the method for detecting the sparfloxacin, which has the advantages of low cost, simplicity, rapidness, high sensitivity and selectivity, has important significance.
The molecular imprinting polymer, as a multifunctional polymer, has rapid development in recent years, and has great application value and potential in multiple fields due to unique advantages such as high selectivity, good stability, simple preparation process and the like. Fluorescence sensing has obvious advantages in substance detection, including high sensitivity, simple and rapid operation, low instrument cost, etc. In recent years, many fluorescent nanoparticles such as semiconductor quantum dots, carbon quantum dots, noble metal nanoclusters, and the like have been used in large quantities to improve the sensitivity of substance detection. Among them, the semiconductor quantum dots are most used mainly due to their special optical characteristics such as luminous intensity, broad excitation spectrum range and narrow emission peak, anti-photobleaching, simple preparation and good biocompatibility. The molecular imprinting fluorescence sensing has the advantages of high sensitivity, excellent selectivity, simplicity and rapidness in detection and the like, and is an ideal sensor for detecting substances in complex environments.
The mesoporous material has the specific advantages of large specific surface area, ordered structure, uniform and adjustable pore size, good thermal stability and the like, and has higher attention in the field of nanotechnology. As a carrier of the molecular imprinting sites, the mesoporous material can accelerate the adsorption and separation speed of the imprinted molecules, and the imprinted molecules are combined with the pore wall of the mesoporous material, so that the rapid recognition and detection of the imprinted molecules can be realized. The advantages of the molecular imprinting fluorescence sensor and the mesoporous material are fully exerted by combining, and the molecular imprinting fluorescence sensor is a novel sensing material integrating a plurality of advantages of high sensitivity, high selectivity, high specificity, rapidness, simplicity and the like. At present, few studies on this aspect have been reported, but most of them are disordered mesoporous structures.
Therefore, the molecular imprinting-quantum dot mesoporous material which combines quantum dots, molecular imprinting and mesoporous silica, has a highly ordered mesoporous structure and has specific recognition on the sparfloxacin is developed and is used for quickly, sensitively and specifically detecting the sparfloxacin in a sample.
Disclosure of Invention
Aiming at the defects in the prior art, the technical problem to be solved by the invention is to provide a preparation method of a molecular imprinting-quantum dot mesoporous material with specific recognition on sparfloxacin, which has simple steps; the prepared molecular imprinting-quantum dot mesoporous material can quickly, sensitively and specifically detect the sparfloxacin in a sample.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the sparfloxacin molecular imprinting-quantum dot mesoporous material comprises the following steps:
firstly, forming a pre-acting compound by template molecules of sparfloxacin, 3-aminopropyltriethoxysilane and propionic acid sulfenyl methyl acetoxy propyl trimethoxysilane;
then, modifying Mn doped ZnS quantum dots by a surfactant, a cross-linking agent, the pre-acting compound and L-cysteine to form a compound;
and finally, eluting the template molecule sparfloxacin and the surfactant in the compound to obtain the sparfloxacin molecular imprinting-quantum dot mesoporous material.
Preferably, the preparation method of the sparfloxacin molecular imprinting-quantum dot mesoporous material comprises the following steps:
1) preparation of Pre-action complexes
Dissolving template molecule sparfloxacin into a dimethylformamide solution, adding 3-aminopropyltriethoxysilane and propionic sulfenyl methyl acetoxy propyl trimethoxysilane, and stirring and reacting for 2 hours at room temperature to obtain a pre-acting compound;
2) preparation of the composite
Dissolving a surfactant in water, adding a sodium hydroxide solution with the molar concentration of 2.0M, adjusting the pH value of the solution to 11, adding a cross-linking agent, the pre-acting compound prepared in the step 1) and Mn-doped ZnS quantum dots modified by L-cysteine at the temperature of 80 ℃, and reacting for 6 hours to prepare a compound;
3) elution template molecule sparfloxacin and surfactant
And (3) cooling the compound prepared in the step 2) to room temperature, centrifuging for 10 minutes at the rotating speed of 12000rpm, removing the supernatant, repeatedly washing with eluent, removing template molecules of sparfloxacin and a surfactant in the compound, and drying to obtain the sparfloxacin molecular imprinting-quantum dot mesoporous material.
Preferably, the mole ratio of the template molecule sparfloxacin, 3-aminopropyltriethoxysilane and thiomethyl acetoxy propyl trimethoxysilane is 1: 4. Two functional monomers, namely, thiomethylacetoxypropyltrimethoxysilane and 3-aminopropyltriethoxysilane, are adopted, so that an identification group (amino or carboxyl) of the functional monomer and a group of a template molecule sparfloxacin fully act and form a hydrogen bond, and the utilization rate of the functional monomer and the imprinting identification effect are improved.
Preferably, the mol volume ratio L of the template molecule sparfloxacin to the dimethylformamide is 1: 50.07.
Preferably, the thiomethylacetoxypropyltrimethoxysilane propionate is prepared by the following steps:
dissolving 3-mercaptopropionic acid and gamma- (methacryloyloxy) propyl trimethoxy silane in absolute ethyl alcohol, adding triethylamine solution, adjusting the pH value of the solution to 8, and stirring and reacting for 2 hours at the temperature of 40 ℃ to prepare the propionic acid sulfenyl methyl acetoxy propyl trimethoxy silane.
Particularly preferably, the volume ratio of the 3-mercaptopropionic acid, the gamma- (methacryloyloxy) propyltrimethoxysilane and the absolute ethyl alcohol is 1: 2.85: 57.38.
Preferably, the mole ratio of the template molecule sparfloxacin to the L-cysteine modified Mn doped ZnS quantum dot is 1.21-1.83.
Particularly preferably, the molar concentration of the L-cysteine modified Mn doped ZnS quantum dots is 0.0201 mol/L; the mol volume ratio of the template molecule sparfloxacin to the L-cysteine modified Mn doped ZnS quantum dot is 1: 60.37-90.55.
Preferably, the L-cysteine modified Mn doped ZnS quantum dot is prepared by the following steps:
s1: ZnSO is added4·7H2O、MnCl2·4H2Dissolving O and L-cysteine in water, and then dropwise adding a sodium hydroxide solution with the molar concentration of 1M to adjust the pH of the mixed solution to 8-9; introducing nitrogen for half an hour to remove oxygen dissolved in the solution;
s2: mixing Na2S·9H2Dissolving O in water, then dropwise adding the dissolved O into the mixed solution which is prepared in the step S1 and is subjected to oxygen removal, and refluxing for 14 hours under the conditions of air communication and 50 ℃;
s3: adding isopropanol, and obtaining the purified L-cysteine modified Mn doped ZnS quantum dot after precipitation, centrifugation, separation, cleaning and resuspension.
Particularly preferably, the ZnSO4·7H2O、MnCl2·4H2O and, L-cysteine and Na2S·9H2The mass ratio of O is 1: 0.033: 0.839: 1.666.
Particularly preferably, in step S1 and step S2, the water is purified water.
Particularly preferably, ZnSO in step S14·7H2The mass volume ratio g to ml of O and water is 1: 173.37.
Particularly preferably, in step S2, Na2S·9H2The mass volume ratio g to ml of O and water is 1: 20.81.
Preferably, the surfactant is cetyltrimethylammonium bromide.
Particularly preferably, the mole ratio of the template molecules of sparfloxacin and hexadecyl trimethyl ammonium bromide is 1: 13.74.
Preferably, the cross-linking agent is selected from ethyl orthosilicate or methyl orthosilicate.
Particularly preferably, the cross-linking agent is tetraethoxysilane.
Most preferably, the mol volume ratio L of the template molecule sparfloxacin to the tetraethoxysilane is 1: 25.04.
Preferably, the eluent is an 80% (v/v) ethanol/water solution.
The invention also provides a sparfloxacin molecular imprinting-quantum dot mesoporous material, which is prepared by the preparation method of the sparfloxacin molecular imprinting-quantum dot mesoporous material.
The invention also provides application of the sparfloxacin molecular imprinting-quantum dot mesoporous material in detecting the content of sparfloxacin in a sample, in particular application in detecting the content of sparfloxacin in serum.
Preferably, the detection conditions for detecting the content of the sparfloxacin in the sample by using the sparfloxacin molecular imprinting-quantum dot mesoporous material are respectively as follows: the pH was 7.0 and the response time was 30 minutes.
The invention has the beneficial effects that:
1. the preparation method provided by the invention has the advantages of mild reaction conditions, high reaction speed, high yield, easy elution of the synthesized material and stable physicochemical properties, and is a simple, convenient and efficient preparation method for the sparfloxacin molecular imprinting-quantum dot mesoporous material with specific recognition on the sparfloxacin.
2. The invention combines the excellent optical performance of quantum dots, the high selectivity and specificity of a molecularly imprinted polymer and the high specific surface area of a mesoporous material, takes the Mn-doped ZnS quantum dots modified by L-cysteine as a signal element, and adopts a one-step method to hydrothermally synthesize the sparfloxacin molecularly imprinted-quantum dot mesoporous material with a highly ordered mesoporous structure.
3. The sparfloxacin molecular imprinting-quantum dot mesoporous material is used for carrying out a fluorescence titration experiment on sparfloxacin, and the linear detection range is 0.05-20.0 mu g/ml, the linear correlation coefficient is 0.998, the detection limit is 0.118 mu g/ml, and the specific recognition factor is 2.55.
4. The interference test of the analog on the detection of the sparfloxacin is carried out on the sparfloxacin molecular imprinting-quantum dot mesoporous material, and the sparfloxacin molecular imprinting-quantum dot mesoporous material has better selectivity on the sparfloxacin.
5. The sparfloxacin molecular imprinting-quantum dot mesoporous material is applied to labeling detection of sparfloxacin in serum, the recovery rate is 88.8-102%, and the relative standard deviation is less than 5%. The results show that the sparfloxacin molecular imprinting-quantum dot mesoporous material has actual detection value and potential on sparfloxacin.
Drawings
FIG. 1 is a process flow diagram of the preparation process according to the invention;
FIG. 2 is a FT-IR characterization diagram of MCM-41, a molecular non-imprinting-quantum dot mesoporous material (MS-FNIPs), a compound (MS-FMIPs before elution), and a sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs after elution), wherein FIG. 2A is the FT-IR characterization diagram of the MCM-41, the molecular non-imprinting-quantum dot mesoporous material (MS-FNIPs) and the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs after elution), and FIG. 2B is the FT-IR characterization diagram of the compound (MS-FMIPs before elution), the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs after elution);
FIG. 3 is an XRD characterization diagram of a sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs);
FIG. 4 is a thermogravimetric analysis graph of MCM-41 and sparfloxacin molecular imprinting-quantum dot mesoporous materials (MS-FMIPs);
FIG. 5 is a Transmission Electron Microscope (TEM) representation of a sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs);
FIG. 6 is a Scanning Electron Microscope (SEM) image of a sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs);
FIG. 7 is a nitrogen adsorption and desorption curve diagram of a sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs);
FIG. 8 is a graph of adsorption power of a sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs);
FIG. 9 is a graph of the test results of the effect of pH value on the determination of sparfloxacin by sparfloxacin molecular imprinting-quantum dot mesoporous materials (MS-FMIPs);
FIG. 10 is fluorescence spectra of sparfloxacin with different concentrations measured by sparfloxacin molecular imprinting-quantum dot mesoporous materials (MS-FMIPs);
FIG. 11 is fluorescence spectra of the molecular non-imprinting-quantum dot mesoporous material (MS-FNIPs) for measuring sparfloxacin with different concentrations;
FIG. 12 is a linear relationship graph of the fluorescence intensity of the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs) and the sparfloxacin concentration;
FIG. 13 is a linear relationship graph of fluorescence intensity of a molecular non-imprinting-quantum dot mesoporous material (MS-FNIPs) and sparfloxacin concentration;
FIG. 14 is a diagram of the results of the selectivity tests of sparfloxacin molecular imprinting-quantum dot mesoporous materials (MS-FMIPs) and molecular non-imprinting-quantum dot mesoporous materials (MS-FNIPs) on sparfloxacin and analogues thereof.
Detailed Description
As shown in figure 1, the preparation method of the sparfloxacin molecular imprinting-quantum dot mesoporous material provided by the invention comprises the following steps: firstly, forming a pre-acting compound by template molecules of sparfloxacin, 3-aminopropyltriethoxysilane and propionic acid sulfenyl methyl acetoxy propyl trimethoxysilane; then, modifying Mn doped ZnS quantum dots by a surfactant, a cross-linking agent, the pre-acting compound and L-cysteine to form a compound; and finally, eluting the template molecule sparfloxacin and the surfactant in the compound to obtain the sparfloxacin molecular imprinting-quantum dot mesoporous material.
The invention also provides the sparfloxacin molecular imprinting-quantum dot mesoporous material prepared by the preparation method and application of the sparfloxacin molecular imprinting-quantum dot mesoporous material in detection of sparfloxacin in a sample.
In the examples of the present invention, the various test instruments and reagents were commercially available and commercially available.
The technical solution of the present invention is further described below by using specific preferred embodiments in combination with preparation process test examples, structure characterization test examples, detection condition test examples, and effect test examples, but the present invention is not limited to the following embodiments.
Example 1:
synthesis of (mono) thiomethylacetoxypropyltrimethoxysilane propionate (KH-3-MAP)
In a 10ml round bottom flask, 87.14. mu.l of 3-mercaptopropionic acid (3-MAP) and 248.35. mu.l of the silane coupling agent gamma- (methacryloyloxy) propyl trimethoxysilane (KH-570) were dissolved in 5ml of absolute ethanol, then the pH of the solution was adjusted to 8 with triethylamine, and the reaction was stirred for 2 hours under the water bath condition at 40 ℃ to prepare thiomethylacetoxypropyltrimethoxysilane (KH-3-MAP). The product was stored in a refrigerator at 4 ℃ until use.
(II) synthesis of Mn-doped ZnS quantum dots (Mn: ZnS QDs) modified by L-cysteine
S1: 0.1442g of ZnSO was weighed out separately with an analytical balance4·7H2O，0.0047g MnCl2·4H2O and 0.1210 gL-cysteine, and stirring to dissolve the mixture in 25ml of ultrapure water, and then dropwise adding a freshly prepared sodium hydroxide solution with the molar concentration of 1M to adjust the pH of the mixed solution to 8-9; and introducing nitrogen for half an hour to remove dissolved oxygen in the solution.
S2: 0.2402g of Na are weighed by a balance2S·9H2O and dissolved in 5ml of ultrapure water, thenThen dropwise adding the mixed solution into the mixed solution after the oxygen removal by using a constant-pressure dropping funnel; refluxing for 14 hours at 50 ℃ under the condition of communicating with air to obtain a transparent L-cysteine modified Mn doped ZnS quantum dot (Mn: ZnS QDs) solution;
s3: adding isopropanol with the same volume into the prepared quantum dot solution, precipitating, centrifuging, separating, cleaning and resuspending to obtain a purified L-cysteine modified Mn doped ZnS quantum dot (Mn: ZnS QDs) solution (the molar concentration of the prepared Mn: ZnS QDs solution is 0.0201mol/L), and keeping away from light at 4 ℃ for later use. Solid samples can be obtained by vacuum drying at room temperature.
(III) preparing the sparfloxacin molecular engram-quantum dot mesoporous material
1) Preparation of Pre-action complexes
Weighing 13mg of template molecule sparfloxacin, dissolving the template molecule sparfloxacin in 2ml of dimethylformamide solution, adding 40 microliter of 3-Aminopropyltriethoxysilane (APTES) and thiomethyl acetoxy propyl trimethoxysilane (KH-3-MAP), magnetically stirring at room temperature, and reacting for 2 hours to obtain a pre-acting compound;
2) preparation of the composite
0.2g of cetyltrimethylammonium bromide (CTAB) was weighed out and dissolved in 100ml of ultrapure water, 0.7ml of 2.0M sodium hydroxide solution was added thereto in molar concentration, and the pH of the solution was adjusted to 11; uniformly mixing the solution, heating to 80 ℃, dropwise adding 1ml of Tetraethoxysilane (TEOS), the pre-acting compound prepared in the step 1) and 2-3ml of L-cysteine modified Mn-doped ZnS quantum dots (Mn: ZnS QDs) by using a constant-pressure dropping funnel in sequence, and reacting for 6 hours to prepare a compound;
3) elution template molecule sparfloxacin and surfactant
Cooling the compound prepared in the step 2) to room temperature, centrifuging for 10 minutes at the rotating speed of 12000rpm, removing supernatant, repeatedly washing with 80% (v/v) ethanol/water solution, and removing template molecules sparfloxacin and Cetyl Trimethyl Ammonium Bromide (CTAB) in the compound; and (3) putting the product into a vacuum drying oven, and drying at the temperature of 40 ℃ to obtain the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs).
Structural characterization test example 1:FT-IR characterization
Respectively detecting FT-IR characterization of MCM-41, molecular non-imprinting-quantum dot mesoporous materials (MS-FNIPs), compounds (MS-FMIPs before elution) and sparfloxacin molecular imprinting-quantum dot mesoporous materials MS-FMIPs (MS-FMIPs after elution)
The preparation method of the molecular non-imprinting-quantum dot mesoporous material (MS-FNIPs) is the same as that of the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs), except that the template molecule sparfloxacin is not added.
The preparation method of MCM-41 comprises the following steps: 0.2g of cetyltrimethylammonium bromide (CTAB) was weighed out and dissolved in 100ml of ultrapure water, 0.7ml of 2.0M sodium hydroxide solution was added thereto in molar concentration, and the pH of the solution was adjusted to 11; the solution was mixed well and heated to 80 ℃. Then, 1ml of Tetraethoxysilane (TEOS) is added dropwise in sequence by using a constant-pressure dropping funnel and reacted for 6 hours; after the reaction is finished, cooling the solution to room temperature, centrifuging for 10 minutes under the condition that the rotating speed is 12000rpm, removing supernate, repeatedly washing with 80% (v/v) ethanol/water solution, and removing template molecules sparfloxacin and hexadecyl trimethyl ammonium bromide (CTAB) in the compound; and (3) putting the product into a vacuum drying oven, and drying at the temperature of 40 ℃ to obtain a solid sample, namely MCM-41.
The test method comprises the following steps: the dried 100mg of potassium bromide, 1mg of MCM-41 and MS-FNIPs which are dried and the compound (MS-FMIPs before elution) prepared in the step 2) of the embodiment 1 of the invention and the sparfloxacin molecular imprinting-quantum dot mesoporous material MS-FMIPs (MS-FMIPs after elution) prepared in the embodiment 1 of the invention are respectively weighed, uniformly mixed in a dry agate mortar and ground into fine powder, and the fine powder is tableted and placed in a Fourier infrared converter for scanning to obtain an infrared spectrogram (figure 2). The characterization is carried out by analyzing the characteristic absorption peaks of functional groups such as carbonyl, silicon-oxygen-silicon bonds, silicon-oxygen hydrogen bonds and the like.
FIG. 2A is an infrared spectrum (FT-IR spectrum) of MCM-41, MS-FNIPs and MS-FMIPs after elution, and FIG. 2B is an infrared spectrum (FT-IR spectrum) of MS-FMIPs before elution and MS-FMIPs after elution. As can be seen from FIG. 2A, 1085cm-1，951cm-1And 800cm-1The absorption peaks at three positions are characteristic peaks of silicon-based materials which are main components of the mesoporous materials. The absorption peak at 1700 positions in MS-FNIPs and eluted MS-FMIPs represents a stretching vibration absorption peak with C being 0, and the functional monomer is shown to successfully participate in the skeleton synthesis of the mesoporous material. As can be seen from FIG. 2B, the prepared MS-FMIP was 2924cm before elution-1And 2854cm-1There was a clear C-H stretching vibration absorption peak, and the two absorption peaks disappeared after elution, indicating that CTAB had been removed cleanly.
Structural characterization test example 2:characterization by X-ray diffraction (XRD)
And (3) detecting XRD representation of the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs).
The test method comprises the following steps: taking a solid sample of the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs) prepared in the example 1, grinding the solid sample into powder, placing the powder on a special glass plate, flattening the powder, and then placing the powder into an instrument for scanning and measuring. The results of the test are shown in FIG. 3.
As can be seen from FIG. 3, three distinct characteristic peaks, representing three crystal planes (100), (110) and (200), respectively, are shown, and the results of small-angle XRD show that MS-FMIPs have a highly ordered mesoporous structure of MCM-41.
Structural characterization test example 3:thermogravimetric characterization (TGA)
Detecting the thermogravimetric analysis representation of MCM-41 and sparfloxacin molecular engram-quantum dot mesoporous materials (MS-FMIPs).
2-3mg of MCM-41 and the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs) prepared in example 1 were weighed by a balance, and carefully added into a special crucible, and the measurement was performed after setting the instrument parameters. The results of the measurements are shown in FIG. 4.
It is evident from FIG. 4 that the weight loss of MS-FMIPs is much greater than that of MCM-41, mainly because the molecularly imprinted polymer in MS-FMIPs is decomposed by heating. This result indicates successful synthesis of molecularly imprinted polymers.
Structural characterization test example 4:transmission Electron microscopy characterization (TEM)
And detecting the transmission electron microscope representation of the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs).
The test method comprises the following steps: dissolving the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs) prepared in the embodiment 1 in water, uniformly dispersing the sparfloxacin molecular imprinting-quantum dot mesoporous material by using ultrasound, then sucking a small amount of solution from the sparfloxacin molecular imprinting-quantum dot mesoporous material by using a micro-pipette, dripping the solution on the surface of a copper mesh special for a transmission electron microscope, drying the copper mesh in an oven at the temperature of 40 ℃ for 24 hours, and then putting the copper mesh into an instrument for observation. The test results are shown in FIG. 5. Wherein, FIG. 5A and FIG. 5B are the transmission electron microscope characterization images of MS-FMIPs.
As can be seen from FIG. 5, the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs) is microspherical, has uniform particle size distribution and has a diameter of about 100 nm.
Structural characterization test example 5:scanning Electron microscopy characterization (SEM)
And detecting the scanning electron microscope representation of the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs).
The sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs) solid sample prepared in the embodiment 1 is uniformly paved on a gold sheet pasted with double faced adhesive tape, and then the gold sheet is placed into a scanning electron microscope instrument to observe the appearance of the sample. The test results are shown in FIG. 6. FIG. 6A, FIG. 6B, FIG. 6C and FIG. 6D are all the characterization images of MS-FMIPs by scanning electron microscope.
As can be seen from FIG. 6, the hexagonal pore structures of the MS-FMIPs are arranged closely and regularly, have obvious ordered mesoporous structures, and are consistent with the results of the previous XRD characterization.
Structural characterization test example 6:characterization of ammonia adsorption and desorption
And (3) carrying out a nitrogen adsorption and desorption test on the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs). The nitrogen adsorption and desorption test can be used for measuring the surface area, the pore diameter and the pore volume of the mesoporous material.
The test method comprises the following steps: after a solid sample of the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs) prepared in example 1 is placed in a vacuum drying oven to be dried for a certain time, 0.1g of the solid sample is quickly weighed and carefully poured into a dry professional tube by means of a paper groove, and then the solid sample is placed in a nitrogen adsorption instrument to be tested. The test results are shown in FIG. 7.
As shown in FIG. 7, the nitrogen adsorption-desorption isotherm of MS-FMIPs is a type IV curve, and belongs to the nitrogen adsorption-desorption isotherm typical of mesoporous materials. The specific surface area of the material was calculated to be 1115.2m according to the Bamauer-Enunett-Teller (BET) method2g-1Pore volume of 1.13cm3g-1These results indicate that MS-FMIPs have large specific surface area and pore volume, and are very beneficial to mass distribution of the imprinted sites and the re-adsorption process of the template molecules. As can be seen from the pore size distribution, the pore size peak profile is relatively concentrated and sharp, mainly concentrated between 2.9-3.4nm, and the average pore size of the material obtained by treatment according to the Barrett-Joyner-Halenda (BJH) method is 3.1 nm. These results indicate that the pore size distribution in MS-FMIPs is uniform and highly ordered.
Test conditions test example 1:equilibrium adsorption kinetics test
And (3) carrying out adsorption kinetic test on the sparfloxacin by using sparfloxacin molecular imprinting-quantum dot mesoporous materials (MS-FMIPs) and molecular non-imprinting-quantum dot mesoporous materials (MS-FNIPs).
The test method comprises the following steps:
a certain amount of sparfloxacin standard solution and 1mg/ml of the MS-FMIPs solution prepared in the example 1 are respectively put into a 40ml conical flask, and the volume of the solution is supplemented to 40ml by using a phosphate buffer solution with the pH value of 6.0 to prepare the sparfloxacin standard solution with the final concentration of 5.00 mu g/ml. The parameters of the spectrofluorometer F-4600 were set to: the excitation wavelength is 365nm, the scanning range is 400-700nm, the grating slits are all 10.0nm, and the excitation voltage is 400V. The fluorescence values of the solutions were measured at 0, 2, 5, 10, 15, 20, 25, 30, 40, 50, 60min in sequence, 3 replicates per sample and the mean value was taken. MS-FNIPs also measure fluorescence intensity at different times by the same method, and explore the adsorption kinetics of the two compounds. The test results are shown in FIG. 8.
As can be seen from FIG. 8, when sparfloxacin was added to the MS-FNIPs solution at a final concentration of 5.0. mu.g/ml, the fluorescence intensity of the solution gradually decreased and reached equilibrium after about 5 minutes. After the same amount of sparfloxacin is added into the MS-FMIPs solution, the fluorescence intensity of the solution also tends to be weakened, but the difference is that the fluorescence quenching amplitude of the solution is larger, and the fluorescence intensity is kept stable and unchanged after about 30 minutes. These results indicate that equilibrium adsorption of MS-FNIPs is faster than that of MS-FMIPs. Mainly because MS-FNIPs lack specificity and mainly depend on physical adsorption, and a plurality of specific imprinting holes exist in MS-FMIPs, the action time of the MS-FMIPs and the sparfloxacin is prolonged, and the affinity adsorption capacity of the MS-FMIPs to the sparfloxacin is enhanced.
Test conditions test example 2:effect of pH on MS-FMIPs determination of sparfloxacin
Under different pH conditions, the functional groups of the binding sites in the imprinted polymers exist in different forms, and the binding performance of the imprinted polymers is different. In order to improve the binding performance of the imprinted polymer, the influence of exploring different pH conditions on the determination of the sparfloxacin by the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs) is very important.
The test method comprises the following steps: the buffer solution with pH 5.0 and pH 5.5 was prepared from citric acid and sodium citrate, and the buffer solution with pH 6.0, pH 6.5, pH 7.0, pH 7.5 and pH 8.0 was prepared from sodium monohydrogen phosphate and disodium hydrogen phosphate, and the concentration of the buffer solution was 0.01 mol/L. Then a certain amount of sparfloxacin standard solution and 1mg/ml of the MS-FMIPs solution prepared in the example 1 are respectively taken to be put in a 4ml EP tube, and the volume is supplemented to 4ml by buffer solutions with different pH values to prepare the sparfloxacin standard solution with the final concentration of 5.00 mu g/ml. Shaking, and standing at room temperature for 30 min. The parameters of the spectrofluorometer F-4600 were set to: the excitation wavelength is 365nm, the scanning range is 450-600nm, the grating slits are 10.0nm, and the excitation voltage is 400V. The fluorescence intensity of different samples was measured, 3 replicates of each sample were taken and averaged. The influence of pH on MS-FNIPs to determine the sparfloxacin by using the molecular non-imprinting-quantum dot mesoporous material (MS-FNIPs) is also determined by using the same method. The test results are shown in FIG. 9.
As can be seen from fig. 9, the blotting factor increased and then decreased with increasing pH of the solution, reaching a maximum at pH 6.0. When the pH value is 5.0-6.0, the amino group of the sparfloxacin is easy to protonate, and the binding capacity of the MS-FMIPs to the sparfloxacin is weakened. At pH 6.0-8.0, the carboxyl group of the functional monomer thiomethylacetoxypropyltrimethoxysilane (KH-3-MAP) is dissolved and deprotonated, resulting in reduced binding capacity. Meanwhile, in slightly acidic solutions, nonspecific adsorption is reduced. Therefore, the phenomenon that the blotting factor is maximized at pH 6.0 occurs.
Effect test example 1: effect of varying concentrations of sparfloxacin on fluorescence quenching of MS-FMIPs
In order to evaluate different recognition capabilities of the sparfloxacin molecular imprinting-quantum dot mesoporous materials (MS-FMIPs) and the molecular non-imprinting-quantum dot mesoporous materials (MS-FNIPs) on the sparfloxacin, the fluorescence responses of the MS-FMIPs and the MS-FNIPs on the sparfloxacin with different concentrations are respectively measured by adopting a titration method.
The test method comprises the following steps: 1.0mg of sparfloxacin weighed by Tianping is dissolved in 1ml of ultrapure water to prepare 1mg/ml of sparfloxacin standard solution, and the sparfloxacin standard solution is stored in a refrigerator at 4 ℃. A certain amount of sparfloxacin standard solution and 1mg/ml of the MS-FMIPs solution prepared in example 1 are respectively put into a 4ml EP tube, the volume of the solution is supplemented to 4ml by a phosphate buffer solution with the pH value of 6.0, and standard solutions with the final concentrations of 0.50, 1.00, 2.00, 5.00, 10.00, 15.00 and 20.00 mu g/ml are prepared. The parameters of the spectrofluorometer F-4600 were set to: the excitation wavelength is 365nm, the scanning range is 400-700nm, the grating slits are all 10.0nm, and the excitation voltage is 400V. Each sample was assayed in 3 replicates and averaged. The molecular non-imprinting-quantum dot mesoporous material (MS-FNIPs) is operated by the same method as the above method. The results of the fluorescence response test of MS-FMIPs to sparfloxacin at different concentrations are shown in FIG. 10; the results of the fluorescence response test of MS-FNIPs to sparfloxacin at different concentrations are shown in FIG. 11.
As can be seen from FIGS. 10 and 11, when the concentration of sparfloxacin is in the range of 0.5-20.0. mu.g/ml, the fluorescence intensity of both MS-FMIPs and MS-FNIPs decreases with the increase of the concentration, and the fluorescence quenching amplitude of MS-FMIPs is larger.
Meanwhile, drawing according to a Stern-Volmer formula to obtain a standard curve of detection:
F0/F-1＝Ksv[Cq]
wherein F0 is the fluorescence intensity of the original MS-FMIPs solution, and F is the fluorescence intensity corresponding to each concentration of sparfloxacin solution. FIG. 12 is a linear relationship graph of fluorescence intensity of MS-FMIPs and sparfloxacin concentration, and FIG. 13 is a linear relationship graph of fluorescence intensity of MS-FNIPs and sparfloxacin concentration.
As shown in FIGS. 12 and 13, the MS-FMIPs and the MS-FNIPs have good linear relation to the sparfloxacin in the concentration range, and the correlation coefficient is 0.998.
The ratio Ksv of the slopes of the standard curves obtained by MS-FMIPs and MS-FNIPs(MS-FMIPs)/Ksv(MS-FNIPs)Namely the Imprinting Factor (IF), can be used for measuring the imprinting effect of the imprinted polymer. According to the slope Ksv(MS-FMIPs)/Ksv(MSFNIPs)The imprinting factor is calculated to be 2.55, which indicates that the MS-FMIPs has better specificity recognition capability on the sparfloxacin. Furthermore, using 3 σ/Ksv(MS-FMIPs)The test line for this method was found to be 0.118. mu.g/ml, where σ is the standard deviation of the instrument blank signal.
Effect test example 2: effect of analogue on MS-FMIPs determination of sparfloxacin
In order to explore the selective recognition capability of the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs) on the sparfloxacin, norfloxacin, ciprofloxacin, gatifloxacin and clinafloxacin are selected as structural analogues in experiments and are researched under the same molar concentration.
The test method comprises the following steps: a certain amount of sparfloxacin, norfloxacin, ciprofloxacin, gatifloxacin, clinafloxacin and 1mg/ml of the MS-FMIPs solution prepared in example 1 were respectively taken out of a 4ml EP tube, and the volume was made up to 4ml with a phosphate buffer solution having a pH of 6.0 to prepare a solution in which the molar concentrations of the template and the analogue were 15.4umol/L (equal to the sparfloxacin concentration of 5.00. mu.g/ml). Standing at room temperature for 30min, respectively measuring the fluorescence intensity, and measuring each sample for 3 times in parallel, and taking an average value. The influence of the analogue on the determination of the sparfloxacin by the MS-FNIPs is also determined by adopting the same method for the molecular non-imprinting-quantum dot mesoporous material (MS-FNIPs). The test results are shown in FIG. 14.
As shown in FIG. 14, it can be seen that sparfloxacin pairs compare to the structural analogsMS-FMIPs showed the greatest efficiency of fluorescence quenching and (F0/F-1)MS-FMIPs/(F0/F-1)MS-FNIPsThe ratio is at most 2.48, but the quenching efficiency of the structural analogue is relatively low, (F0/F-1)MS-FMIPs/(F0/F-1)MS-FNIPsThe ratios are respectively: norfloxacin 1.29, ciprofloxacin 1.50, gatifloxacin 1.35 and clinafloxacin 1.27. These results indicate that MS-FMIPs have better selective and specific recognition capability on sparfloxacin. The reason is mainly that specific imprinting cavities which are complementary with the spafloxacin in spatial size exist in the MS-FMIPs, and the MS-FNIPs lack specificity and only depend on physical adsorption identification.
Effect test example 3: actual sample detection
In order to verify the practicability of detecting the sparfloxacin by using the sparfloxacin molecular imprinting-quantum dot mesoporous material (MS-FMIPs), a labeling recovery experiment is carried out by using human serum.
The test method comprises the following steps: the serum samples were provided by healthy volunteers at school hospitals of the university of south china, and were stored in a refrigerator at-20 ℃. Before use, the sample is placed in a water bath at 37 ℃ and slowly shaken to dissolve. Since no sparfloxacin was detected in the serum samples, a spiking recovery experiment was used. When in use, a serum sample is diluted by 20 times by water, a series of sparfloxacin solutions with different concentrations and a series of MS-FMIPs solutions of 1mg/ml prepared in the invention example 1 are added into the serum sample, the mixture is uniformly mixed and then stands for 30min, then the mixture is centrifuged at 5000rpm for 10min to remove supernatant, and the MS-FMIPs is resuspended in phosphate buffer solution with the same volume and the pH value of 6.0 for fluorescence measurement. Each sample was taken as a mean after 3 replicates. The test results are shown in Table 1.
TABLE 1 MS-FMIPs recovery of sparfloxacin in serum experiment
As can be seen from the table, when sparfloxacin was added to the serum samples at final concentrations of 1.0, 2.0, 4.0. mu.g/ml, the recoveries were 93.2%, 88.8%, and 102%, respectively, and the relative standard deviations were 3.2%, 4.5%, and 4.0%, respectively, each less than 5%. These results indicate that the method has a good effect on the detection of sparfloxacin in actual samples.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention will still fall within the scope of the technical solution of the present invention without departing from the content of the technical solution of the present invention.
Claims (10)
1. A preparation method of a sparfloxacin molecular imprinting-quantum dot mesoporous material is characterized by comprising the following steps:
firstly, forming a pre-acting compound by template molecules of sparfloxacin, 3-aminopropyltriethoxysilane and propionic acid sulfenyl methyl acetoxy propyl trimethoxysilane;
then, modifying Mn doped ZnS quantum dots by a surfactant, a cross-linking agent, the pre-acting compound and L-cysteine to form a compound;
finally, eluting the template molecule sparfloxacin and a surfactant in the compound to obtain the sparfloxacin molecular imprinting-quantum dot mesoporous material;
the structural formula of the propionic acid sulfenyl methyl acetoxyl propyl trimethoxy silane is as follows:
2. the method of claim 1, comprising the steps of:
1) preparation of Pre-action complexes
Dissolving template molecule sparfloxacin into a dimethylformamide solution, adding 3-aminopropyltriethoxysilane and propionic sulfenyl methyl acetoxy propyl trimethoxysilane, and stirring and reacting for 2 hours at room temperature to obtain a pre-acting compound;
2) preparation of the composite
Dissolving a surfactant in water, adding a sodium hydroxide solution with the molar concentration of 2.0M, adjusting the pH value of the solution to 11, adding a cross-linking agent, the pre-acting compound prepared in the step 1) and Mn-doped ZnS quantum dots modified by L-cysteine at the temperature of 80 ℃, and reacting for 6 hours to prepare a compound;
3) elution template molecule sparfloxacin and surfactant
And (3) cooling the compound prepared in the step 2) to room temperature, centrifuging for 10 minutes at the rotating speed of 12000rpm, removing the supernatant, repeatedly washing with eluent, removing template molecules of sparfloxacin and a surfactant in the compound, and drying to obtain the sparfloxacin molecular imprinting-quantum dot mesoporous material.
3. The production method according to claim 1 or 2, characterized in that: the mole ratio of the template molecule sparfloxacin, 3-aminopropyltriethoxysilane and propionic acid sulfenyl methyl acetoxy propyl trimethoxysilane is 1:4: 4.
4. The method according to claim 1 or 2, wherein the thiomethylacetoxypropyltrimethoxysilane is prepared by:
dissolving 3-mercaptopropionic acid and gamma- (methacryloyloxy) propyl trimethoxy silane in absolute ethyl alcohol, adding triethylamine solution, adjusting the pH value of the solution to 8, and stirring and reacting for 2 hours at the temperature of 40 ℃ to prepare the propionic acid sulfenyl methyl acetoxy propyl trimethoxy silane.
5. The preparation method according to claim 1 or 2, wherein the L-cysteine modified Mn doped ZnS quantum dot is prepared by the following steps:
s1: ZnSO is added4˙7H2O、MnCl2˙4H2Dissolving O and L-cysteine in water, and then dropwise adding a sodium hydroxide solution to adjust the pH of the mixed solution to 8-9; introducing nitrogen for half an hour to remove oxygen dissolved in the solution;
s2: mixing Na2S.9H2Dissolving the O in the water, and dissolving the O in the water,then dropwise adding the mixture into the mixed solution which is prepared in the step S1 and is subjected to oxygen removal, and refluxing for 14 hours under the conditions that the mixture is communicated with air and the temperature is 50 ℃;
s3: adding isopropanol, and obtaining the purified L-cysteine modified Mn doped ZnS quantum dot after precipitation, centrifugation, separation, cleaning and resuspension.
6. The production method according to claim 1 or 2, characterized in that: the surfactant is cetyl trimethyl ammonium bromide.
7. The production method according to claim 1 or 2, characterized in that: the cross-linking agent is selected from ethyl orthosilicate or methyl orthosilicate.
8. The method of claim 2, wherein: the eluent was an 80% (v/v) ethanol/water solution.
9. A sparfloxacin molecular imprinting-quantum dot mesoporous material is characterized in that: the sparfloxacin molecular imprinting-quantum dot mesoporous material is prepared by the preparation method of the sparfloxacin molecular imprinting-quantum dot mesoporous material according to any one of claims 1 to 8.
10. The application of the sparfloxacin molecular imprinting-quantum dot mesoporous material of claim 9 in detecting the content of sparfloxacin in a sample.
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