CN108318461A - A kind of Sparfloxacin molecular engram-quantum dot mesoporous material and its preparation method and application - Google Patents
A kind of Sparfloxacin molecular engram-quantum dot mesoporous material and its preparation method and application Download PDFInfo
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- CN108318461A CN108318461A CN201711280661.4A CN201711280661A CN108318461A CN 108318461 A CN108318461 A CN 108318461A CN 201711280661 A CN201711280661 A CN 201711280661A CN 108318461 A CN108318461 A CN 108318461A
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- G01N21/64—Fluorescence; Phosphorescence
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Abstract
The present invention provides a kind of preparation method of Sparfloxacin molecular engram quantum dot mesoporous material and includes the following steps：First, by template molecule Sparfloxacin, 3 aminopropyl triethoxysilanes, propionic acid butylthiomethyl acetyloxypropyl trimethoxy silane, preact compound is formed；Then, by surfactant, crosslinking agent, the preact compound and L cysteine modified Mn doping ZnS quantum points, compound is formed；Finally, by compound template molecule Sparfloxacin and surfactant elute, obtain Sparfloxacin molecular engram quantum dot mesoporous material.The application of Sparfloxacin content, the application of Sparfloxacin content especially in detecting serum the present invention also provides a kind of Sparfloxacin molecular engram quantum dot mesoporous material prepared by above-mentioned preparation method and its in detecting sample.Preparation method step provided by the invention is simple；Prepared molecular engram quantum dot mesoporous material can quick, sensitive and specificity the Sparfloxacin detected in sample.
Description
Technical field
The invention belongs to molecular engram preparation fields, are related to a kind of molecular engram-quantum dot mesoporous material more particularly to one
Kind Sparfloxacin molecular engram-quantum dot mesoporous material and its preparation method and application.
Background technology
Sparfloxacin (Sparfloxacin, SPFX) be third generation Comprecin, be widely used in veterinary science and
Medical treatment of humans's respiratory system, urinary system and digestive system and skin soft-tissue infection etc., to gram positive bacteria, feminine gender
Bacterium, mycoplasma, mycobacteria etc. all have powerful antibacterial activity.But environmental pollution can be caused by being excessively used, and it is strong to jeopardize the mankind
Health.Currently, the method for detection Sparfloxacin includes mainly spectrophotometer method, electrochemical process, thin-layer chromatography hair, high-efficient liquid phase color
Spectrometry, liquid chromatography-mass spectrometry, capillary electrophoresis etc..But these methods are mostly complicated for operation, take time and effort.Therefore, it finds
A kind of inexpensive, easy quick, high sensitivity and selective method, which detect Sparfloxacin, to have great importance.
Molecularly imprinted polymer, as a kind of multifunctional polymer, development is swift and violent in recent years, and unique advantage is as selected
Property it is high, stability is good and preparation process simply etc. makes it show huge application value and potentiality in multiple fields.Fluorescence passes
Sense has apparent advantage, including high sensitivity in substance context of detection, easy to operate quick, and instrument cost is low etc..In recent years,
Many fluorescent nano particles such as semiconductor-quantum-point, carbon quantum dot and noble-metal nanoclusters etc., which are widely used, improves substance detection
Sensitivity.Wherein, semiconductor-quantum-point application is most, be mainly due to its special optical characteristics such as shine it is strong, have compared with
Wide excitation spectrum range and relatively narrow emission peak, anti-light bleaching and preparation are simply and bio-compatibility is good etc..And molecule prints
The advantages such as mark fluorescence sense is provided simultaneously with higher sensitivity, and fabulous selectivity and detection are simple and quick, are a kind of detections
The ideal transducer of substance in complex environment.
Mesoporous material is structurally ordered because of its large specific surface area, and uniformly adjustable and thermostabilization is good etc. distinctive for pore size
Advantage obtains higher concern in field of nanometer technology.As the carrier in molecular engram site, mesoporous material can accelerate trace
The speed of Molecular Adsorption and separation, and microsphere is combined with mesoporous material hole wall and is advantageously implemented its quickly identification and inspection
It surveys.Molecular engram fluorescence sense and mesoporous material combination will be given full play into its respective advantage, be one kind collect it is highly sensitive,
The novel sensing material of highly selective, high specific and many advantages such as fast and convenient.Currently, the research of this respect has had
A small amount of report, but be no ordered meso-porous structure mostly.
Therefore, a kind of incorporating quantum point, molecular engram and mesoporous silicon oxide are developed, and there is highly ordered mesosize pores knot
Structure, the molecular engram-quantum dot mesoporous material to Sparfloxacin with specific recognition, and for quick, sensitive and single-minded
Property detection sample in Sparfloxacin.
Invention content
The technical problem to be solved by the present invention is to deficiencies existing for the above-mentioned prior art, provide a kind of to taking charge of pa
Sha Xing has the preparation method of molecular engram-quantum dot mesoporous material of specific recognition, step simple；Prepared point
Sub- trace-quantum dot mesoporous material can quick, sensitive and specificity the Sparfloxacin detected in sample.
To achieve the goals above, the present invention uses technical solution below：
A kind of preparation method of Sparfloxacin molecular engram-quantum dot mesoporous material includes the following steps：
First, by template molecule Sparfloxacin, 3- aminopropyl triethoxysilanes and propionic acid butylthiomethyl acetoxyl group third
Base trimethoxy silane forms preact compound；
Then, ZnS amounts are adulterated by surfactant, crosslinking agent, the preact compound and L-cysteine modification Mn
It is sub-, form compound；
Finally, by compound template molecule Sparfloxacin and surfactant elute, obtain Sparfloxacin molecule print
Mark-quantum dot mesoporous material.
Preferably, a kind of preparation method of Sparfloxacin molecular engram-quantum dot mesoporous material includes the following steps：
1) preact compound is prepared
Template molecule Sparfloxacin is dissolved in dimethyl formamide solution, 3- aminopropyl triethoxysilanes and third are added
Sour butylthiomethyl acetyloxypropyl trimethoxy silane is stirred to react 2 hours at ambient temperature, and it is compound that preact is made
Object；
2) compound is prepared
Surfactant is soluble in water, the sodium hydroxide solution of molar concentration 2.0M is added, solution ph is adjusted to 11,
Under conditions of temperature is 80 DEG C, the Mn of preact compound and L-cysteine modification made from crosslinking agent, step 1) is added
The ZnS quantum dot of doping, and react 6 hours, compound is made；
3) template molecule Sparfloxacin and surfactant are eluted
It waits for that compound made from step 2) is cooled to room temperature, centrifuges 10 minutes, go under conditions of rotating speed is 12000rpm
Fall supernatant, washed repeatedly with eluent, removes the template molecule Sparfloxacin and surfactant in compound, it is dry, it obtains
To Sparfloxacin molecular engram-quantum dot mesoporous material.
Preferably, the template molecule Sparfloxacin, 3- aminopropyl triethoxysilanes, propionic acid butylthiomethyl acetoxyl group
The molar ratio of propyl trimethoxy silicane is 1: 4: 4.Using two kinds of function monomer propionic acid butylthiomethyl acetyloxypropyl front threes
Oxysilane, 3- aminopropyl triethoxysilanes make the recognition group (amino or carboxyl) and template molecule department pa of function monomer
The group of Sha Xing fully acts on and is formed hydrogen bond, is conducive to the utilization rate and print identification effect that improve function monomer.
Preferably, molal volume ratio mol: L 1: 50.07 of the template molecule Sparfloxacin and dimethylformamide.
Preferably, the propionic acid butylthiomethyl acetyloxypropyl trimethoxy silane prepares gained by following steps：
3- mercaptopropionic acids and γ-(methacryloxypropyl) propyl trimethoxy silicane are dissolved in absolute ethyl alcohol, are added three
Solution ph is adjusted to 8 by ethylamine solution, under the conditions of temperature is 40 DEG C, is stirred to react 2 hours, propionic acid butylthiomethyl second is made
Acryloxypropylethoxysilane trimethoxy silane.
It is particularly preferred, the 3- mercaptopropionic acids, γ-(methacryloxypropyl) propyl trimethoxy silicanes and absolute ethyl alcohol
Volume ratio be 1: 2.85: 57.38.
Preferably, the molar ratio of the template molecule Sparfloxacin and L-cysteine modification Mn doping ZnS quantum points
1.21- 1.83。
Particularly preferred, the molar concentration that L-cysteine modifies Mn doping ZnS quantum points is 0.0201mol/L；It is described
Molal volume ratio mol: L 1: 60.37- of template molecule Sparfloxacin and L-cysteine modification Mn doping ZnS quantum points
90.55。
Preferably, the L-cysteine modification Mn doping ZnS quantum points prepare gained by following steps：
S1：By ZnSO4·7H2O、MnCl2·4H2O and L-cysteine are soluble in water, then molar concentration is added dropwise and is
The pH of mixed liquor is adjusted to 8-9 by 1M sodium hydroxide solutions；Logical nitrogen half an hour removes the oxygen dissolved in solution；
S2：By Na2S·9H2O is soluble in water, is then added dropwise to the mixed solution for having removed oxygen prepared by step S1
In, under conditions of being communicated with air, temperature is 50 DEG C, flow back 14 hours；
S3：Isopropanol is added, the L-cysteine modification purified after precipitation, centrifugation, separation, cleaning, resuspension
Mn doping ZnS quantum points.
It is particularly preferred, the ZnSO4·7H2O、MnCl2·4H2O and L-cysteine and Na2S·9H2The mass ratio of O
It is 1: 0.033: 0.839: 1.666.
Particularly preferred, in step S1 and step S2, the water is purified water.
It is particularly preferred, in step S1, ZnSO4·7H2Mass volume ratio g: ml 1: 173.37 of O and water.
It is particularly preferred, in step S2, Na2S·9H2Mass volume ratio g: ml 1: 20.81 of O and water.
Preferably, the surfactant is cetyl trimethylammonium bromide.
Particularly preferred, the molar ratio of the template molecule Sparfloxacin and cetyl trimethylammonium bromide is 1:
13.74。
Preferably, the crosslinking agent is selected from ethyl orthosilicate or methyl orthosilicate.
Particularly preferred, the crosslinking agent is ethyl orthosilicate.
Most preferably, molal volume ratio mol: L 1: 25.04 of the template molecule Sparfloxacin and ethyl orthosilicate.
Preferably, the eluant, eluent is the ethanol/water solution of 80% (v/v).
The present invention also provides a kind of Sparfloxacin molecular engram-quantum dot mesoporous materials, by above-mentioned Sparfloxacin molecule
What the preparation method of trace-quantum dot mesoporous material prepared.
Sparfloxacin content that the present invention also provides Sparfloxacin molecular engram-quantum dot mesoporous materials in detecting sample
Using the application of Sparfloxacin content especially in detecting serum.
Preferably, Sparfloxacin molecular engram-quantum dot mesoporous material detects the detector bar of Sparfloxacin content in sample
Part is respectively：PH is 7.0, and the response time is 30 minutes.
Beneficial effects of the present invention：
1, preparation method provided by the invention, reaction condition is mild, reaction speed is fast, yield is high, and the material of synthesis is easy
Elution, physicochemical properties are stablized, and are a kind of easy, efficient to prepare the Sparfloxacin for having specific recognition to Sparfloxacin
The preparation method of molecular engram-quantum dot mesoporous material.
2, present invention utilizes by the superior optical property of quantum dot, molecularly imprinted polymer it is highly selective and specific
And the high-specific surface area of mesoporous material is combined together, using L-cysteine modification Mn doping ZnS quantum points as signal element,
Using a kind of Sparfloxacin molecular engram with highly ordered mesosize pores structure-mesoporous material of quantum dot of one-step method hydrothermal synthesis
Material.
3, Sparfloxacin molecular engram-quantum dot mesoporous material of the invention has carried out the reality of the fluorescence titration to Sparfloxacin
It tests, it is 0.05-20.0 μ g/ml to obtain linear detection range, and linearly dependent coefficient 0.998 detects and is limited to 0.118 μ g/ml, specially
One property recognition factor is 2.55.
4, Sparfloxacin molecular engram-quantum dot mesoporous material of the present invention has carried out analog and has been done to Sparfloxacin detection
Disturb experiment, it was demonstrated that Sparfloxacin molecular engram-quantum dot mesoporous material of the present invention has preferable selectivity to Sparfloxacin.
5, Sparfloxacin molecular engram-quantum dot mesoporous material of the present invention is applied to the mark-on inspection of Sparfloxacin in serum
It surveys, the rate of recovery is in 88.8%-102%, and relative standard deviation is respectively less than 5%.These are the result shows that Sparfloxacin of the present invention point
Sub- trace-quantum dot mesoporous material has actually detected value and potentiality to Sparfloxacin.
Description of the drawings
Fig. 1 is the process flow chart of preparation method of the present invention；
Fig. 2 is MCM-41, the non-trace of molecule-quantum dot mesoporous material (MS-FNIPs), the compound (MS- before elution
FMIPs), the FT-IR phenograms of Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs after elution), wherein figure
2A is MCM-41, the non-trace of molecule-quantum dot mesoporous material (MS-FNIPs) and Sparfloxacin molecular engram-mesoporous material of quantum dot
Expect the FT-IR phenograms of (MS-FMIPs after elution), Fig. 2 B are compound (MS-FMIPs before elution), Sparfloxacin molecule
The FT-IR phenograms of trace-quantum dot mesoporous material (MS-FMIPs after elution)；
Fig. 3 is the XRD characterization figure of Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs)；
Fig. 4 is the thermal gravimetric analysis curve of MCM-41 and Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs)
Figure；
Fig. 5 is transmission electron microscope characterization (TEM) figure of Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs)；
Fig. 6 is scanning electron microscope characterization (SEM) figure of Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs)；
Fig. 7 is the nitrogen adsorption desorption curve figure of Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs)；
Fig. 8 is Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs) absorption dynamic curve figure；
Fig. 9 is the shadow that pH value measures Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs) Sparfloxacin
Ring test result figure；
Figure 10 is the Sparfloxacin that Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs) measures various concentration
Fluorescence spectrum；
Figure 11 is the fluorescence for the Sparfloxacin that the non-trace of molecule-quantum dot mesoporous material (MS-FNIPs) measures various concentration
Spectrum；
Figure 12 be Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs) fluorescence intensity and Sparfloxacin it is dense
The linear relationship chart of degree；
Figure 13 is the line of the fluorescence intensity and Sparfloxacin concentration of the non-trace of molecule-quantum dot mesoporous material (MS-FNIPs)
Sexual intercourse figure；
Figure 14 is that Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs) and the non-trace of molecule-quantum dot are situated between
Choice tests result figure of the Porous materials (MS-FNIPs) to Sparfloxacin and the like.
Specific implementation mode
As shown in Figure 1, the present invention provides a kind of preparation method of Sparfloxacin molecular engram-quantum dot mesoporous material includes
Following steps：First, by template molecule Sparfloxacin, 3- aminopropyl triethoxysilanes, propionic acid butylthiomethyl acetoxyl group third
Base trimethoxy silane forms preact compound；Then, by surfactant, crosslinking agent, the preact compound and L-
Cysteine modified Mn doping ZnS quantum points form compound；Finally, by the template molecule Sparfloxacin and table in compound
Face activating agent elution, obtains Sparfloxacin molecular engram-quantum dot mesoporous material.
The present invention also provides the Sparfloxacin prepared by above-mentioned preparation method molecular engram-quantum dot mesoporous material and
It detects the application of Sparfloxacin in sample.
Various test apparatuses and reagent are commercial goods in the embodiment of the present invention, are that can buy to obtain by commercial sources
.
Below by specific preferred embodiment combination preparation process test example, structural characterization test example, testing conditions experiment
Example and effete test embodiment are described further technical scheme of the present invention, but the present invention is not limited in embodiment below.
Embodiment 1：
(1) synthesis of propionic acid butylthiomethyl acetyloxypropyl trimethoxy silane (KH-3-MAP)
It is in the round-bottomed flask of 10ml, 87.14 microlitres of 3- mercaptopropionic acids (3-MAP) and 248.35 microlitres of silane is even
Connection agent γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570) is dissolved in the absolute ethyl alcohol of 5ml, then uses triethylamine
The pH of solution is adjusted to 8,2h is stirred to react under 40 DEG C of water bath condition, propionic acid butylthiomethyl acetyloxypropyl front three is made
Oxysilane (KH-3-MAP).Products therefrom is stored in spare under the conditions of 4 DEG C of refrigerator.
(2) synthesis of L-cysteine modification Mn doping ZnS quantum points (Mn: ZnS QDs)
S1：Weigh 0.1442g ZnSO respectively with assay balance4·7H2O, 0.0047g MnCl2·4H2O and 0.1210g
L-cysteine, and stirring makes it be dissolved in the ultra-pure water of 25ml, then it is 1M hydrogen-oxygens that the molar concentration of Fresh, which is added dropwise,
Change sodium solution and the pH of mixed liquor is adjusted to 8-9；Logical nitrogen half an hour removes the oxygen dissolved in solution.
S2：It weighs in the balance and takes 0.2402g Na2S·9H2O is simultaneously dissolved in the ultra-pure water of 5ml, is then leaked using constant pressure addition
Bucket is added dropwise in the above-mentioned mixed solution for having removed oxygen；50 DEG C of reflux obtain for 14 hours under conditions of being communicated with air
Mn doping ZnS quantum points (Mn: the ZnS QDs) solution modified to transparent L-cysteine；
S3：Isometric isopropanol is added into quantum dot solution obtained, by precipitation, centrifugation, separation, cleaning, again
The L-cysteine modification purified after outstanding Mn doping ZnS quantum points (Mn: ZnS QDs) solution (prepared Mn:
The molar concentration of ZnS QDs solution is 0.0201mol/L), and be kept in dark place spare under the conditions of 4 DEG C.Solid sample can be
Vacuum drying obtains at room temperature.
(3) Sparfloxacin molecular engram-quantum dot mesoporous material is prepared
1) preact compound is prepared
It weighs template molecule Sparfloxacin 13mg to be dissolved in the dimethyl formamide solution of 2ml, 40 microlitres is added thereto
3- aminopropyl triethoxysilanes (APTES) and propionic acid butylthiomethyl acetyloxypropyl trimethoxy silane (KH-3-
MAP), at ambient temperature, magnetic agitation is reacted 2 hours, and preact compound is made；
2) compound is prepared
The cetyl trimethylammonium bromide (CTAB) for weighing 0.2g is dissolved in the ultra-pure water of 100ml, is added thereto
The sodium hydroxide solution of 0.7ml molar concentrations 2.0M, 11 are adjusted to by solution ph；80 DEG C will be heated to after solution mixing, successively
With constant pressure funnel the ethyl orthosilicate (TEOS) of 1ml, step 1) is added dropwise made from preact compound and 2-3ml
The ZnS quantum dot (Mn: ZnS QDs) of the Mn doping of L-cysteine modification, and react 6 hours, compound is made；
3) template molecule Sparfloxacin and surfactant are eluted
It waits for that compound made from step 2) is cooled to room temperature, centrifuges 10 minutes, go under conditions of rotating speed is 12000rpm
Fall supernatant, washed repeatedly with the ethanol/water solution of 80% (v/v), removes the template molecule Sparfloxacin and ten in compound
Six alkyl trimethyl ammonium bromides (CTAB)；Product is put into vacuum drying chamber, it is dry under conditions of temperature is 40 DEG C, it obtains
Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs).
Structural characterization test example 1：FT-IR is characterized
MCM-41, the non-trace of molecule-quantum dot mesoporous material (MS-FNIPs), the compound (MS before elution are detected respectively
- FMIPs), the FT-IR of Sparfloxacin molecular engram-quantum dot mesoporous material MS-FMIPs (MS-FMIPs after elution) characterization
The preparation method of the non-trace of molecule-quantum dot mesoporous material (MS-FNIPs) and Sparfloxacin molecular engram-quantum
The preparation method of point mesoporous material (MS-FMIPs) is identical, does not add template molecule Sparfloxacin only.
The preparation method of MCM-41：The cetyl trimethylammonium bromide (CTAB) for weighing 0.2g is dissolved in the ultrapure of 100ml
In water, the sodium hydroxide solution of 0.7ml molar concentrations 2.0M is added thereto, solution ph is adjusted to 11；After solution mixing
It is heated to 80 DEG C.Then the ethyl orthosilicate (TEOS) of 1ml is added dropwise with constant pressure funnel successively and reacts 6 hours；Instead
After answering, solution is cooled to room temperature, is centrifuged 10 minutes under conditions of rotating speed is 12000rpm, removes supernatant, is used
The ethanol/water solution of 80% (v/v) is washed repeatedly, removes template molecule Sparfloxacin and cetyl trimethyl in compound
Ammonium bromide (CTAB)；Product is put into vacuum drying chamber, it is dry under conditions of temperature is 40 DEG C, solid sample is obtained, i.e.,
For MCM-41.
Test method：The 100mg potassium bromide of drying and MCM-41, MS-FNIPs, the embodiment of the present invention of 1mg are weighed respectively
The Sparfloxacin molecule print that 1 step 2) prepares the compound (MS-FMIPs before elution) of gained, prepared by the embodiment of the present invention 1
Mark-quantum dot mesoporous material MS-FMIPs (MS-FMIPs after elution) is mixed uniformly simultaneously in dry agate mortar
It is ground into fine powder, is put into the infrared transformation instrument of Fourier and is scanned after tabletting, obtain infrared spectrogram (Fig. 2).Pass through analysis
The characteristic absorption peak of the functional groups such as carbonyl, silica silicon key, silicon oxygen bond, silica hydrogen bond is characterized.
Fig. 2A is the infrared spectrogram (FT-IR phenograms) of the MS-FMIPs after MCM-41, MS-FNIPs and elution, figure
2B is the infrared spectrogram (FT-IR phenograms) of the MS-FMIPs and the MS-FMIPs after elution before elution.It can be with from Fig. 2A
Find out, 1085cm-1, 951cm-1And 800cm-1Absorption peak at three is the characteristic peak of the main component silica-base material of mesoporous material.
Absorption peak at 1700 in MS-FMIPs after MS-FNIPs and elution represents the stretching vibration absworption peak of C=0, shows function
Monomer has successfully taken part in the skeleton synthesis of mesoporous material.As can be seen from Figure 2B, the MS-FMIP of preparation is before elution
2924cm-1And 2854cm-1There are apparent C-H stretching vibration absworption peaks at place, and this absorption peak at two disappears after elution
, show that CTAB has been removed totally.
Structural characterization test example 2：X-ray diffraction characterizes (XRD)
Detect the XRD characterization of Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs).
Test method：Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs) solid prepared by Example 1
Sample, grind into powder, and be placed on dedicated glass plate, sweep measuring in instrument is put into after pressing.Measurement result is tested, is seen
Fig. 3.
From figure 3, it can be seen that three apparent characteristic peaks, respectively represent (100), (110) and (200) three crystal faces,
Small angle XRD's the result shows that MS-FMIPs have high-sequential MCM-41 meso-hole structure.
Structural characterization test example 3：Thermogravimetric analysis characterizes (TGA)
Detect the thermogravimetric analysis characterization of MCM-41 and Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs).
Sparfloxacin molecular engram-quantum dot of the MCM-41 and the preparation of embodiment 1 that weigh 2-3mg respectively with balance are mesoporous
Material (MS-FMIPs), and be carefully added into dedicated crucible, it is measured after instrument parameter is set.Measurement result is shown in figure
4。
This it appears that the weight-loss ratio of MS-FMIPs is much larger than MCM-41 from Fig. 4, it is primarily due in MS-FMIPs
It is decomposed after molecularly imprinted polymer is heated.This result shows that molecularly imprinted polymer successful synthesis.
Structural characterization test example 4：Transmission electron microscope characterizes (TEM)
Detect the transmission electron microscope characterization of Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs).
Test method：The Sparfloxacin molecular engram prepared in Example 1-quantum dot mesoporous material (MS-FMIPs) is molten
Solution in water, is uniformly dispersed using ultrasound, and a small amount of solution is then therefrom drawn with micropipette rifle, and to drop in transmission electron microscope special
Copper mesh surface is placed on drying in 40 DEG C of baking oven and for 24 hours, then copper mesh is put into instrument and is observed.Test result is shown in Fig. 5.
Wherein, Fig. 5 A, Fig. 5 B are the transmission electron microscope phenograms of MS-FMIPs.
To find out as can be seen from Fig. 5, Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs) is in microspheroidal,
Grain size distribution is uniform, and diameter is in 100nm or so.
Structural characterization test example 5：Scanning electron microscope characterizes (SEM)
Detect the scanning electron microscope characterization of Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs).
Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs) solid sample prepared by Example 1 is equal
It is even to be layered on the gold plaque for posting double faced adhesive tape, it is then placed in the pattern that sample is observed in scanning electron microscope instrument.Test result is shown in Fig. 6.
Fig. 6 A, Fig. 6 B, Fig. 6 C and Fig. 6 D are the scanning electron microscope phenogram of MS-FMIPs.
From fig. 6, it can be seen that the hexagon duct structural arrangement of MS-FMIPs is closely regular, have apparent order mesoporous
Structure, it is consistent with the result of front XRD characterization.
Structural characterization test example 6：Ammonia gas absorption desorption characterization
Nitrogen adsorption desorption experiment is carried out to Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs).Nitrogen
Adsorption/desorption experiment can be used for measuring surface area, aperture and the Kong Rong of mesoporous material.
Test method：Sparfloxacin molecular engram prepared by embodiment 1-quantum dot mesoporous material (MS-FMIPs) is solid
Body sample is put into vacuum drying chamber drying after a certain period of time, quickly weigh 0.1g and by paper groove it is careful pour into dry profession
Guan Zhong is then placed in nitrogen adsorption instrument and tests.Test result is shown in Fig. 7.
As shown in fig. 7, nitrogen adsorption-desorption isotherm of MS-FMIPs is a kind of IV types curve, belong to mesoporous material allusion quotation
Nitrogen adsorption-desorption isotherm of type.The ratio of this material is calculated according to Bamauer-Enunett-Teller (BET) method
Surface area is 1115.2m2g-1, Kong Rongwei 1.13cm3g-1, these are the result shows that MS-FMIPs has larger specific surface area and hole
Hold, is very beneficial for the adsorption process again of a large amount of distributions and template molecule of imprinted sites.It can from graph of pore diameter distribution
Go out, aperture peak type is distributed Relatively centralized and sharp, is concentrated mainly between 2.9-3.4nm, according to Barrett-Joyner-
The average pore size that Halenda (BJH) method handles to obtain this material is 3.1nm.These are the result shows that aperture in MS-FMIPs
Be distributed it is uniform, and have high-sequential.
Testing conditions test example 1：Equilibrium adsorption dynamic test
Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs) and the non-trace of molecule-quantum dot mesoporous material
(MS-FNIPs) tests the adsorption dynamics adsorption kinetics of Sparfloxacin.
Test method：
Take respectively MS-FMIPs solution prepared by a certain amount of Sparfloxacin standard solution and 1mg/ml embodiments 1 in
In 40ml conical flasks, volume is mended to 40ml with the pH phosphate buffers for being 6.0, is made into the department of final concentration of 5.00 μ g/ml
Pa sand star standard solution.Parameter setting by sepectrophotofluorometer F-4600 is：Excitation wavelength is 365nm, and scanning range is
400-700nm, grating slit are 10.0nm, excitation voltage 400V.Successively 0,2,5,10,15,20,25,30,40,
50, the fluorescent value of a solution is surveyed when 60min, each sample parallel determination 3 times is averaged.MS-FNIPs also uses identical
Method measure different time fluorescence intensity, explore two kinds of compounds adsorption dynamics adsorption kinetics.Test result is shown in Fig. 8.
As can be seen from Figure 8, molten after the Sparfloxacin of final concentration of 5.0 μ g/ml being added in MS-FNIPs solution
Liquid fluorescence intensity gradually weakens, and reaches balance after 5 minutes or so.And same amount of Sparfloxacin is added to MS-FMIPs
After in solution, solution fluorescence intensity be also in the trend weakened, but unlike solution fluorescence quenching amplitude bigger, and in length
Up to 30 minutes or so, rear ability fluorescence intensity holding was stablized constant.These the result shows that MS-FNIPs equilibrium adsorption ratio MS-
FMIPs is faster.It is primarily due to MS-FNIPs and lacks specificity, rely primarily on physical absorption, and exist in MS-FMIPs very much
Specific imprinted cavity extends the action time with Sparfloxacin, and enhances MS-FMIPs to the affine of Sparfloxacin
Adsorption capacity.
Testing conditions test example 2：PH measures MS-FMIPs the influence of Sparfloxacin
Under the conditions of different pH, functional group's existence form of binding site is different in imprinted polymer, imprinted polymer
Binding performance is also different.To improve the binding performance of imprinted polymer, different pH conditions are explored to Sparfloxacin molecular engram-
The influence that quantum dot mesoporous material (MS-FMIPs) measures Sparfloxacin is very important.
Test method：The buffer solution that pH=5.0 and pH=5.5 is prepared with citric acid and sodium citrate, with one hydrogen of phosphoric acid
Sodium and disodium hydrogen phosphate prepare the buffer solution of pH=6.0, pH=6.5, pH=7.0, pH=7.5 and pH=8.0, buffer solution
Concentration is 0.01mol/L.Then it takes respectively prepared by a certain amount of Sparfloxacin standard solution and 1mg/ml embodiments 1
MS-FMIPs solution mends each volume to 4ml in 4ml EP pipes, with the buffer solution of different pH, is made into final concentration of 5.00 μ
The Sparfloxacin standard solution of g/ml.30min is stored at room temperature after shaking up.By the parameter setting of sepectrophotofluorometer F-4600
For：Excitation wavelength is 365nm, and scanning range 450-600nm, grating slit is 10.0nm, excitation voltage 400V.It measures
The fluorescence intensity of different samples, each sample parallel determination 3 times, is averaged.The non-trace of molecule-quantum dot mesoporous material
(MS-FNIPs) influence that pH measures MS-FNIPs Sparfloxacin is also measured using identical method.Test result is shown in Fig. 9.
From fig. 9, it can be seen that with the increase of pH value of solution, imprinting factor first increases and reduces afterwards, reaches most in pH=6.0
Big value.When pH is in 5.0-6.0, the amino of Sparfloxacin is easy to happen protonation, reduces MS-FMIPs to Sparfloxacin
Binding ability.When pH is in 6.0-8.0, function monomer propionic acid butylthiomethyl acetyloxypropyl trimethoxy silane (KH-3-
MAP carboxyl) is dissolved in generation deprotonation, and binding ability is caused to weaken.It is non-specific meanwhile in the solution of slightly slant acidity
Absorption weakens.Therefore, there is this phenomenon of imprinting factor maximum in pH=6.0.
Effete test embodiment 1：Influence of the Sparfloxacin of various concentration to MS-FMIPs fluorescent quenchings
In order to assess Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs) and the non-trace-quantum dot of molecule
Mesoporous material (MS-FNIPs) measures MS-FMIPs and MS- respectively to the different recognition capabilities of Sparfloxacin using titration
Fluorescence responses of the FNIPs to the Sparfloxacin of various concentration.
Test method：Weigh with scale the Sparfloxacin of 1.0mg, is dissolved in the ultra-pure water of 1ml, and department's pa of 1mg/ml is made
Husky star standard solution, and it is put in 4 DEG C of preservations of refrigerator.A certain amount of Sparfloxacin standard solution and 1mg/ml embodiments 1 are taken respectively
Volume is mended to 4ml with the pH phosphate buffers for being 6.0 in 4ml EP pipes, is made into end by prepared MS-FMIPs solution
Concentration is respectively the standard solution of 0.50,1.00,2.00,5.00,10.00,15.00,20.00 μ g/ml.By fluorescence spectrophotometry
Meter F-4600 parameter setting be：Excitation wavelength is 365nm, and scanning range 400-700nm, grating slit is 10.0nm,
Excitation voltage is 400V.Each sample parallel determination 3 times, is averaged.The non-trace of molecule-quantum dot mesoporous material (MS-
FNIPs it) is operated using with above-mentioned identical method.MS-FMIPs tests the fluorescence response of the Sparfloxacin of various concentration
The result is shown in Figure 10；MS-FNIPs is shown in Figure 11 to the fluorescence response test result of the Sparfloxacin of various concentration.
From Figure 10,11 as can be seen that when range of the Sparfloxacin concentration in 0.5-20.0 μ g/ml, MS-FMIPs and
The fluorescence intensity of MS-FNIPs increases with its concentration and is weakened, and the fluorescent quenching amplitude bigger of MS-FMIPs.
Meanwhile being mapped according to Stern-Volmer formula, the standard curve that can be detected：
F0/F-1=Ksv [Cq]
Wherein F0 is the fluorescence intensity of original MS-FMIPs solution, and F is under each Sparfloxacin solution concentration corresponds to
Fluorescence intensity.Figure 12 is the linear relationship chart of the fluorescence intensity and Sparfloxacin concentration of MS-FMIPs, and Figure 13 is MS-FNIPs
Fluorescence intensity and Sparfloxacin concentration linear relationship chart.
As shown in Figure 12,13, MS-FMIPs and MS-FNIPs is presented the Sparfloxacin of place concentration range good
Linear relationship, relative coefficient are 0.998.
The ratio between slope of standard curve Ksv obtained by MS-FMIPs and MS-FNIPs(MS-FMIPs)/Ksv(MS-FNIPs)As trace
The factor (IF), can be used to the imprinting effect for weighing imprinted polymer.According to slope K sv(MS-FMIPs)/Ksv(MSFNIPs)Calculate trace
The factor is 2.55, illustrates that MS-FMIPs has preferable specific recognition ability to Sparfloxacin.In addition, using 3 σ/
Ksv(MS-FMIPs)The detection line for finding out this method is 0.118 μ g/ml, and wherein σ is the standard deviation of instrument blank signal.
Effete test embodiment 2：Analog measures MS-FMIPs the influence of Sparfloxacin
The selectivity of Sparfloxacin is known in order to explore Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs)
Other ability selects Sparfloxacin, Norfloxacin, Ciprofloxacin, gatifloxacin and Clinafloxacin as analogue in experiment,
And it is studied under identical molar concentration.
Test method：Take respectively a certain amount of Sparfloxacin, Norfloxacin, Ciprofloxacin, gatifloxacin, Clinafloxacin and
MS-FMIPs solution prepared by 1mg/ml embodiments 1 is mended volume with the pH phosphate buffers for being 6.0 in 4ml EP pipes
To 4ml, the molar concentration for being made into template and analog is 15.4umol/L (being equal to a concentration of 5.00 μ g/ml of Sparfloxacin)
Solution.After being stored at room temperature 30min, its fluorescence intensity is measured respectively, and each sample parallel determination 3 times is averaged.The non-print of molecule
Mark-quantum dot mesoporous material (MS-FNIPs) also measures analog using identical method and measures Sparfloxacin to MS-FNIPs
It influences.Test result is shown in Figure 14.
As shown in figure 14, it can be seen that compared to analogue, fluorescent quenching efficiency of the Sparfloxacin to MS-FMIPs
Maximum, and (F0/F-1)MS-FMIPs/(F0/F-1)MS-FNIPsRatio is up to 2.48, and efficiency is quenched relatively in analogue
It is low, (F0/F-1)MS-FMIPs/(F0/F-1)MS-FNIPsRatio is respectively：Norfloxacin is 1.29, and Ciprofloxacin 1.50 adds and replaces
Sha Xing is 1.35 and Clinafloxacin is 1.27.These the result shows that MS-FMIPs to Sparfloxacin have preferable selectivity and
Specific recognition capability.Reason is mainly to exist in MS-FMIPs and the specific trace of Sparfloxacin space size complementation sky
Cave, and MS-FNIPs lacks specificity, relies only on physical absorption identification.
Effete test embodiment 3：Actual sample detects
In order to verify the practicality that Sparfloxacin molecular engram-quantum dot mesoporous material (MS-FMIPs) detects Sparfloxacin
Property, recovery testu is carried out using human serum.
Test method：Blood serum sample is provided by Hospital's healthy premenopausal volunteers of South China Normal University, and ice is put in after fetching
- 20 DEG C of case freezes.Sample is placed on slowly vibrating dissolving under 37 DEG C of water bath conditions using preceding.Because department is not detected in blood serum sample
Pa sand star, therefore use recovery testu.Blood serum sample is diluted with water 20 times when use, and a series of differences are added thereto
The Sparfloxacin solution and the MS-FMIPs solution prepared by the 1mg/ml embodiment of the present invention 1 of concentration stand 30min after mixing,
Then supernatant is removed with the rotating speed of 5000rpm centrifugation 10min, MS-FMIPs is resuspended in the phosphate that isometric pH is 6.0
Fluorescence measurement is carried out in buffer solution.Mean value is taken after each sample parallel determination 3 times.Test result is shown in Table 1.
1 MS-FMIPs of table tests the rate of recovery of Sparfloxacin in serum
As can be seen from the table, the Sparfloxacin of final concentration of 1.0,2.0,4.0 μ g/ml is added separately to blood serum sample
In, the gained rate of recovery is respectively 93.2%, 88.8% and 102%, and relative standard deviation is respectively 3.2%, 4.5% and 4.0%,
Respectively less than 5%.These are the result shows that this method has preferable effect for the detection of Sparfloxacin in actual sample.
The above described is only a preferred embodiment of the present invention, limitation in any form not is done to the present invention, therefore
All contents without departing from technical solution of the present invention, it is made to the above embodiment according to the technical essence of the invention any simply to repair
Change, equivalent variations and modification, in the range of still falling within technical solution of the present invention.
Claims (10)
1. a kind of preparation method of Sparfloxacin molecular engram-quantum dot mesoporous material, which is characterized in that include the following steps：
First, by template molecule Sparfloxacin, 3- aminopropyl triethoxysilanes and propionic acid butylthiomethyl acetyloxypropyl three
Methoxy silane forms preact compound；
Then, Mn doping ZnS quantum points are modified by surfactant, crosslinking agent, the preact compound and L-cysteine,
Form compound；
Finally, by compound template molecule Sparfloxacin and surfactant elute, obtain Sparfloxacin molecular engram-amount
Son point mesoporous material.
2. preparation method according to claim 1, which is characterized in that include the following steps：
1) preact compound is prepared
Template molecule Sparfloxacin is dissolved in dimethyl formamide solution, 3- aminopropyl triethoxysilanes and propionic acid sulphur is added
Ylmethyl acetamide oxygroup propyl trimethoxy silicane is stirred to react 2 hours at ambient temperature, and preact compound is made；
2) compound is prepared
Surfactant is soluble in water, the sodium hydroxide solution of molar concentration 2.0M is added, solution ph is adjusted to 11, in temperature
Under conditions of degree is 80 DEG C, the Mn doping of preact compound made from crosslinking agent, step 1) and L-cysteine modification is added
ZnS quantum dot, and react 6 hours, be made compound；
3) template molecule Sparfloxacin and surfactant are eluted
Wait for that compound made from step 2) is cooled to room temperature, rotating speed be 12000rpm under conditions of centrifuge 10 minutes, remove on
Clear liquid is washed repeatedly with eluent, removes template molecule Sparfloxacin and surfactant in compound, dry, is taken charge of
Pa sand star molecular engram-quantum dot mesoporous material.
3. preparation method according to claim 1 or 2, it is characterised in that：The template molecule Sparfloxacin, 3- aminopropyls
Triethoxysilane, propionic acid butylthiomethyl acetyloxypropyl trimethoxy silane molar ratio be 1: 4: 4.
4. preparation method according to claim 1 or 2, which is characterized in that the propionic acid butylthiomethyl acetyloxypropyl
Trimethoxy silane prepares gained by following steps：
3- mercaptopropionic acids and γ-(methacryloxypropyl) propyl trimethoxy silicane are dissolved in absolute ethyl alcohol, triethylamine is added
Solution ph is adjusted to 8 by solution, under the conditions of temperature is 40 DEG C, is stirred to react 2 hours, propionic acid butylthiomethyl acetyl oxygen is made
Base propyl trimethoxy silicane.
5. preparation method according to claim 1 or 2, which is characterized in that the L-cysteine modification Mn adulterates ZnS amounts
Son point prepares gained by following steps：
S1：By ZnSO4·7H2O、MnCl2·4H2O and L-cysteine are soluble in water, then sodium hydroxide solution is added dropwise will mix
The pH for closing liquid is adjusted to 8-9；Logical nitrogen half an hour removes the oxygen dissolved in solution；
S2：By Na2S.9H2O is soluble in water, is then added dropwise in the mixed solution for having removed oxygen prepared by step S1, with
Under conditions of air communicates, temperature is 50 DEG C, flow back 14 hours；
S3：Isopropanol is added, the L-cysteine modification Mn purified after precipitation, centrifugation, separation, cleaning, resuspension mixes
Miscellaneous ZnS quantum dot.
6. preparation method according to claim 1 or 2, it is characterised in that：The surfactant is cetyl front three
Base ammonium bromide.
7. preparation method according to claim 1 or 2, it is characterised in that：The crosslinking agent is selected from ethyl orthosilicate or just
Methyl silicate.
8. preparation method according to claim 2, it is characterised in that：The eluant, eluent is that the ethanol/water of 80% (v/v) is molten
Liquid.
9. a kind of Sparfloxacin molecular engram-quantum dot mesoporous material, it is characterised in that：Sparfloxacin molecular engram-the amount
Son point mesoporous material is Sparfloxacin molecular engram-quantum dot mesoporous material according to any one of claim 1-8
Preparation method prepare.
10. the Sparfloxacin content in detecting sample of Sparfloxacin molecular engram-quantum dot mesoporous material described in claim 9
Application.
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