CN113634240B - Fluorescent magnetic composite nanofiber, preparation method and application thereof - Google Patents
Fluorescent magnetic composite nanofiber, preparation method and application thereof Download PDFInfo
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- CN113634240B CN113634240B CN202110986387.2A CN202110986387A CN113634240B CN 113634240 B CN113634240 B CN 113634240B CN 202110986387 A CN202110986387 A CN 202110986387A CN 113634240 B CN113634240 B CN 113634240B
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses fluorescent magnetic composite nanofiber, and a preparation method and application thereof, and belongs to the technical field of nanofiber preparation. The fluorescent magnetic composite nanofiber is prepared by electrostatic spinning of phenylboronic acid modified magnetic nanoparticles and phenylboronic acid modified core-shell structure quantum dots in a spinning polymer solution. The fluorescent magnetic composite nanofiber has the double functions of magnetic separation and fluorescent tracing, and can be used for selectively identifying, separating, enriching and detecting glycoprotein.
Description
Technical Field
The invention belongs to the technical field of nanofiber preparation, and particularly relates to fluorescent magnetic composite nanofibers, a preparation method and application thereof.
Background
Quantum dots and magnetic nanoparticles have shown significant advantages in many fields, especially biomedical fields. However, the two functions are single, such as quantum dots for fluorescent labeling and magnetic particles for magnetic separation. If the two functions of separation and marking are dissolved into a whole to form fluorescent magnetic nano particles, the product can have double functions of magnetic separation and fluorescent tracing, the performance and application range of the fluorescent magnetic nano particles are far more than those of nano particles with single functions, the detection and separation on the level of biological molecules can be realized, and the imaging in multiple modes, namely fluorescent imaging, magnetic Resonance Imaging (MRI), laser confocal microscopic imaging and the like can be realized, so that the fluorescent magnetic nano particles have a wide application prospect.
Disclosure of Invention
The invention provides a fluorescent magnetic composite nanofiber which is prepared by electrostatic spinning of magnetic nanoparticles and quantum dots in a spinning polymer solution. Wherein, the surfaces of the magnetic nano particles and the quantum dots are modified by functionalization, mainly by phenylboronic acid. The quantum dot is modified by phenylboronic acid to form the quantum dot with the core-shell structure.
In the preparation process, interaction between phenylboronic acid and 1,2 or 1,3 o-hydroxyl structures in the high molecular polymer can introduce phenylboronic acid modified magnetic nano particles and quantum dots into a molecular chain of the high molecular polymer, and the fluorescent magnetic composite nano fibers are formed by self-assembly after electrostatic spinning.
The preparation method of the fluorescent magnetic composite nanofiber comprises the following steps:
dispersing the phenylboronic acid modified magnetic nano particles and phenylboronic acid modified core-shell structure quantum dots in a solvent, uniformly stirring, then pouring the mixture into a spinning polymer solution, and fully stirring to obtain an electrostatic spinning precursor solution; and carrying out electrostatic spinning on the electrostatic spinning precursor solution, and carrying out vacuum drying to obtain the fluorescent magnetic composite nanofiber.
In the preparation method of the fluorescent magnetic composite nanofiber, the mass concentration of the phenylboronic acid modified magnetic nanoparticle in the electrostatic spinning precursor solution is 0.1-5 wt%, and the mass concentration of the phenylboronic acid modified core-shell structure quantum dot in the electrostatic spinning precursor solution is 0.5-10 wt%.
In the preparation method of the fluorescent magnetic composite nanofiber, the solvent is one or more of water, ethanol, DMF, methanol, acetone, methylene dichloride and chloroform.
In the preparation method of the fluorescent magnetic composite nanofiber, the spinning polymer is a polymer containing an ortho-glycol bond and comprises one or more of polyethylene glycol, polyvinyl alcohol, sodium alginate and xanthan gum. The spinning polymer solution is a solution with a mass concentration of 3-15% formed by dissolving the polymer containing the ortho-glycol bond in a solvent; wherein the solvent is one or more of water, ethanol, DMF, methanol, acetone, dichloromethane and chloroform.
In the preparation method of the fluorescent magnetic composite nanofiber, the physical conditions of electrostatic spinning are as follows: the propelling speed of the propelling pump is 1-2 mL/h, the spinning voltage is 10-20 KV, the distance from the spinning port to the receiver is 10-25 cm, and the diameter of the spinning nozzle is 0.2-0.8 mm.
The magnetic nano particles modified by phenylboronic acid and the quantum dots with core-shell structures modified by phenylboronic acid are uniformly distributed on the surface of the fluorescent magnetic composite nano fiber prepared by the method in a monodisperse mode, wherein the particle size of the magnetic nano particles is 10-300 nm, and the particle size of the quantum dots is 2-10 nm.
The fluorescent magnetic composite nanofiber prepared by the method can be used for selectively identifying, separating, enriching and detecting glycoprotein; the selective identification and detection of glycoprotein is based on fluorescence quenching or fluorescence emission spectrum change of quantum dots in the fluorescent magnetic composite nanofiber, and is used as a signal for selectively identifying glycoprotein; the separation and enrichment of glycoprotein is realized by capturing and releasing glycoprotein molecules by fluorescent magnetic composite nanofibers.
The glycoprotein is selected from one of adenosine, chicken egg albumin, horseradish peroxidase, glycosylated hemoglobin and immunoglobulin G.
When the glycoprotein is detected, the fluorescent magnetic composite nanofiber can be prepared into a fluorescent probe so as to realize trace detection of the glycoprotein.
The preparation method of the phenylboronic acid modified magnetic nanoparticle comprises the following steps:
(1) Amination modification
Dissolving magnetic nano particles in a natural polymer solution, introducing nitrogen for deoxidation and ultrasound to form a uniformly dispersed magnetic particle polymer solution; adding a magnetic particle polymer solution as a water phase into a microemulsion system formed by a surfactant, a cosurfactant and an oil phase dropwise, emulsifying for 20-60 min, adding a cross-linking agent solution, adjusting the temperature of a reaction system to 30-50 ℃, reacting for 1-5 h, and alternately washing the obtained reaction product by absolute ethyl alcohol and petroleum ether to obtain amino modified magnetic nano particles;
(2) Phenylboronic acid modification
Dissolving the amination modified magnetic nano particles in PBS buffer solution, adding N-hydroxysuccinimide, and performing ultrasonic treatment for 10-20 min to form amination modified magnetic nano particle mixed solution; dissolving carboxyphenylboronic acid in PBS buffer solution, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (CAS: 25952-53-8), and performing ultrasonic treatment for 10-20 min to form a carboxyphenylboronic acid mixed solution; mixing the amination modified magnetic nanoparticle mixed solution with the carboxyphenylboronic acid mixed solution, oscillating at room temperature for reaction for 1-6 h, washing with distilled water, and centrifugally separating to obtain the phenylboronic acid modified magnetic nanoparticle.
In the preparation method of the phenylboronic acid modified magnetic nano particles, the Magnetic Nano Particles (MNPs) are at least one of superparamagnetic, paramagnetic or ferromagnetic metals, metal oxides or alloys. The metal is selected from Fe, co or Ni, and the metal oxide is selected from Fe 3 O 4 、Fe 2 O 3 、Co 3 O 4 Or MeFe 2 O 4 (Me＝Co、Mn, ni), the alloy is selected from Fe 2 Co、Ni 2 Fe. Neodymium iron boron or samarium cobalt. The magnetic nano particles can be obtained from commercial sources, and can also be prepared by methods such as precipitation method, hydrothermal method and the like.
In the preparation method of the phenylboronic acid modified magnetic nano particles, the natural polymer solution is selected from chitosan gel solution or carboxymethyl chitosan solution. Wherein, the chitosan gel solution is prepared by dispersing chitosan powder in 2-6% weak acid solution by ultrasonic, and the concentration of the formed chitosan gel solution is 0.002-0.02 g/mL; the carboxymethyl chitosan solution is prepared by dissolving carboxymethyl chitosan in distilled water to form carboxymethyl chitosan solution with the concentration of 0.005-0.05 g/mL. The weak acid is selected from one of acetic acid, formic acid, tartaric acid and citric acid.
In the preparation method of the phenylboronic acid modified magnetic nano particles, the surfactant is at least one selected from Span80, OP-10 and Triton X-114, the cosurfactant is ethanol or isopropanol, and the oil phase is one selected from paraffin oil, palm oil, n-hexane and cyclohexane.
In the preparation method of the phenylboronic acid modified magnetic nano particle, the mass percentage of the surfactant, the cosurfactant, the oil phase and the water phase is 5-40%, 20-90% and 2-10%.
In the preparation method of the phenylboronic acid modified magnetic nano particles, the cross-linking agent solution is an aqueous solution of the cross-linking agent, the mass concentration is 4-15%, and the cross-linking agent is selected from formaldehyde, glyoxal or glutaraldehyde.
In the preparation method of the phenylboronic acid modified magnetic nanoparticle, the PBS buffer solution is selected from PBS buffer solutions with the pH value of 6.0 and the concentration of 0.01-0.05 mol/L.
In the preparation method of the phenylboronic acid modified magnetic nanoparticle, the carboxyphenylboronic acid is selected from one or more of 2-carboxyphenylboronic acid, 3-carboxyphenylboronic acid, 4-carboxy-2-fluorobenzeneboronic acid, 4-carboxy-3-fluorobenzeneboronic acid, 4-carboxy-2-chlorobenzeneboronic acid, 4-carboxy-3-chlorobenzeneboronic acid, 5-carboxy-2-fluorobenzeneboronic acid, 5-carboxy-2-chlorobenzeneboronic acid, 3, 5-dicarboxyphenylboronic acid and 5-carboxy-2-hydroxymethylphenylboronic acid.
The preparation method of the phenylboronic acid modified core-shell structure quantum dot comprises the following steps:
and dissolving the II-VI group quantum dots, a metal source and phenylboronic acid in water, regulating the pH value to 8-11, setting the reaction temperature to 90-160 ℃, reacting for 1-8 hours, and washing and drying the reaction product to obtain the phenylboronic acid modified core-shell structure quantum dot.
In the preparation method of the phenylboronic acid modified core-shell structure quantum dot, the II-VI group quantum dot is ZnSe, cdSe, cdTe, cdS, zn X Cd 1-X Se、CdSe 1-X S X 、CdSe 1-X Te X CdSe/ZnSe, cdS/ZnSe, cdTe/ZnSe or CdTe/CdS, wherein X is more than 0 and less than 1. The II-VI group quantum dots can be obtained from commercial sources, and can also be prepared by a hydrothermal method, a solvothermal method, a coprecipitation method, a microemulsion method or a high-temperature thermal decomposition method and the like.
The quantum dot shell layer with the core-shell structure prepared by the method is M 1-y N y S, wherein M, N is at least one of Zn, cd, cu, mn, and 0 < y < 1.
In the preparation method of the phenylboronic acid modified core-shell structure quantum dot, the metal source is selected from nitrate, acetate or chlorate of Zn, cd, cu or Mn. Phenylboronic acid is a surface stabilizer selected from p-mercaptophenylboronic acid or m-mercaptophenylboronic acid.
In the preparation method of the phenylboronic acid modified core-shell structure quantum dot, the molar ratio of the II-VI group quantum dot to the metal source to the phenylboronic acid is 1:1.5-3:1-10.
In the preparation method of the phenylboronic acid modified core-shell structure quantum dot, the washing of the reaction product is performed in the following mode: washing with isopropanol, or alternatively with ethanol and water.
The beneficial effects of the invention are as follows:
(1) The fluorescent magnetic composite nanofiber has the advantages of controllable magnetic content, strong magnetic responsiveness, adjustable fluorescence, high light stability, controllable appearance and size of fluorescent materials and magnetic materials and the like.
(2) The preparation process is simple, the reaction condition is mild, the influence of a complicated synthesis process on the fluorescence performance of the quantum dots is avoided, and the stability of the functional material can be protected to the maximum extent.
(3) The fluorescent magnetic composite nanofiber has high porosity and high specific surface area, magnetic nanoparticles and quantum dots are uniformly distributed on the surface and inside of the nanofiber, and the magnetic performance and the fluorescent performance are more stable and durable.
(4) The fluorescent magnetic composite nanofiber can control the fluorescence performance, the magnetic performance and the content of the surface boric acid functional groups by adjusting the molecular weight of the spinning polymer, the content of the magnetic nano particles and the quantum dots, the feeding ratio and other modes.
(5) The fluorescent magnetic composite nanofiber can selectively identify, separate and enrich glycoprotein, and can realize regeneration through simple adjustment of the pH value of the solution, namely, the fluorescent magnetic composite nanofiber can realize recycling.
Drawings
FIG. 1 is a diagram of a process for forming and applying fluorescent magnetic composite nanofibers;
FIG. 2 is an SEM image of fluorescent magnetic composite nanofibers prepared in example 1;
FIG. 3 shows the fluorescence magnetic composite nanofiber in a magnetic material (phenylboronic acid modified magnetic Fe 3 O 4 Nanoparticles) saturation magnetization at different addition levels;
FIG. 4 is a graph showing the saturation magnetization of fluorescent magnetic composite nanofibers over time;
FIG. 5 is an SEM image of fluorescent magnetic composite nanofibers prepared in example 2;
FIG. 6 is an EDS spectrum of the fluorescent magnetic composite nanofiber prepared in example 2;
FIG. 7 is CoFe 2 O 4 XRD patterns of nano particles, cdTe@ZnS core-shell structure quantum dots and fluorescent magnetic composite nano fibers;
FIG. 8 shows fluorescence intensity of fluorescent magnetic composite nanofibers at different addition levels of fluorescent materials (phenylboronic acid modified CdTe@ZnS core-shell structured quantum dots);
FIG. 9 is a graph showing the change of fluorescence intensity of fluorescent magnetic composite nanofibers over time;
FIG. 10 is a graph showing adsorption amounts of different types of glycoproteins and non-glycoproteins by the fluorescent magnetic composite nanofibers prepared in example 1;
FIG. 11 shows the amount of adsorption of adenosine and deoxyadenosine by fluorescent magnetic composite nanofibers;
FIG. 12 is a graph showing the effect of different concentrations of adenosine solution on fluorescence properties of fluorescent magnetic composite nanofibers;
FIG. 13 is a graph showing the relationship between the concentration of adenosine and the fluorescence emission intensity.
Detailed Description
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated. The invention will be described in further detail below in connection with specific embodiments and with reference to the data. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1
The preparation method of the fluorescent magnetic composite nanofiber comprises the following steps:
(1) Preparation of phenylboronic acid modified magnetic Fe 3 O 4 Nanoparticles
(a) Amination modification
The chitosan powder was ultrasonically dispersed in 2% acetic acid solution to prepare 5mL of chitosan gel solution of 0.005 g/mL. 200mg of magnetic Fe is weighed 3 O 4 The nano particles are dissolved in the chitosan gel solution, nitrogen is introduced for deoxidation, and ultrasonic cleaning is performed by using an ultrasonic cleaner to form the uniformly dispersed magnetic particle chitosan gel solution. Adding a magnetic particle chitosan gel solution into a microemulsion system (80 g of paraffin oil, 80g of span80 g and 5g of ethanol) dropwise, emulsifying for 30min, adding 0.5mL of 5% glyoxal solution into the microemulsion system, adjusting the temperature of the reaction system to 30 ℃, reacting for 2h, and alternately washing the obtained reaction product with absolute ethyl alcohol and petroleum ether to obtain the amino modified magnetic Fe 3 O 4 And (3) nanoparticles.
(b) Phenylboronic acid modification
50mg of amination-modified magnetic Fe 3 O 4 Dissolving the nano particles in 10mL PBS buffer solution (pH is 6.0 and concentration is 0.01 mol/L), adding 0.05g N-hydroxysuccinimide, and performing ultrasonic treatment for 10min to form the amination modified magnetic Fe 3 O 4 Nanoparticle mixed solution. 80mg of 2-carboxyphenylboronic acid is dissolved in 5mL of PBS buffer solution (pH 6.0, concentration 0.01 mol/L), 0.05g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is added, and the mixture is sonicated for 20min to form a carboxyphenylboronic acid mixture. Magnetic Fe modified by amination 3 O 4 Mixing the nanoparticle mixed solution and the carboxyphenylboronic acid mixed solution, oscillating at room temperature for reaction for 3 hours, washing with distilled water, and centrifugally separating to obtain the phenylboronic acid modified magnetic Fe 3 O 4 And (3) nanoparticles.
(2) Preparation of phenylboronic acid modified core-shell structure quantum dot
Preparation of ZnSe Quantum dots by hydrothermal method, 0.92g Zinc acetate and 0.86g Na 2 SeO 3 And 4g PVP (with the molecular weight of 30000) is added into a mixed solution containing 98mL of ethylene glycol and 2mL of ethylenediamine, the mixed solution is obtained after uniform stirring, then the mixed solution is transferred into a reaction kettle to react for 10 hours at 180 ℃, and the reaction product is alternately washed by ethanol and water, so as to obtain the ZnSe quantum dot. Dissolving 0.72g of ZnSe quantum dot, 1.4g of copper nitrate and 1.54g of p-mercaptophenylboronic acid in 100mL of water, regulating the pH value of the solution to 10 by using a NaOH solution (1 mol/L), transferring the mixed solution into a reaction kettle, controlling the reaction temperature to 90 ℃, reacting for 2 hours, and alternately washing and drying the reaction product by using ethanol and water to obtain the ZnSe@CuS core-shell structure quantum dot powder modified by phenylboronic acid.
(3) Preparation of fluorescent magnetic composite nanofiber
1g of xanthan gum was dissolved in 19mL of water and stirred well to prepare a xanthan gum solution having a mass concentration of 5%. Magnetic Fe modified with 0.2g phenylboronic acid 3 O 4 The nano particles and 0.6g of ZnSe@CuS core-shell structure quantum dots modified by phenylboronic acid are respectively dispersed in 5mL of aqueous solution, and after being fully stirred, the aqueous solution is poured into a xanthan gum solution, and the aqueous solution is fully stirred, so that an electrostatic spinning precursor solution is obtained. Injector for sucking and fixing electrostatic spinning precursor solution on propelling pumpThe method comprises the steps of (1) carrying out electrostatic spinning, wherein the propelling speed of a propelling pump in the electrostatic spinning process is 1mL/h, the spinning voltage is set to be 15KV, the distance from a spinning port to a receiver is 15cm, and the diameter of a spinning nozzle is 0.5mm. And carrying out vacuum drying on the fiber obtained by electrostatic spinning to obtain the fluorescent magnetic composite nanofiber.
Fig. 1 illustrates the formation and application of fluorescent magnetic composite nanofibers.
Fig. 2 shows SEM photographs of the fluorescent magnetic composite nanofibers prepared in example 1. As can be seen from FIG. 2, tetrahedral Fe 3 O 4 The nano particles are uniformly attached to the surface and the inside of the nanofiber, the particle size is about 50nm, and meanwhile, the particle size of the ZnSe@CuS quantum dots is smaller and is not shown in an SEM photo.
FIG. 3 shows fluorescent magnetic composite nanofibers in a magnetic material (phenylboronic acid modified magnetic Fe 3 O 4 Nanoparticles) saturation magnetization at different addition levels. Wherein, the fluorescent magnetic composite nano-fiber represented by curve a and curve c is different from the preparation process of example 1 in that the phenylboronic acid modified magnetic Fe 3 O 4 The amount of the added nanoparticles was varied, the amount of the magnetic material added in curve b (representing the fluorescent magnetic composite nanofiber prepared in example 1) was 0.2g, the amount of the magnetic material added in curve a was 0.15g, and the amount of the magnetic material added in curve c was 0.3g. As can be seen from FIG. 3, when the addition amounts of the magnetic materials are 0.15g, 0.2g and 0.3g, respectively, the saturation magnetization of the prepared fluorescent magnetic composite nanofiber is 59.5emu/g, 64.8emu/g and 73.8emu/g, respectively; therefore, the fluorescent magnetic composite nanofiber has the advantages of strong magnetic response and controllable magnetic content.
Fig. 4 shows the saturation magnetization of fluorescent magnetic composite nanofibers as a function of time. As can be seen from fig. 4, the fluorescent magnetic composite nanofiber prepared in example 1 can maintain an initial saturation magnetization of 95% after being placed for one month, and exhibits excellent magnetic property stability.
Example 2
The preparation method of the fluorescent magnetic composite nanofiber comprises the following steps:
(1) Preparation of phenylboronic acid modified magnetic CoFe 2 O 4 Nanoparticles
(a) Amination modification
Carboxymethyl chitosan powder is dispersed in water solution by ultrasonic to prepare 5mL of carboxymethyl chitosan gel solution with the concentration of 0.01 g/mL. 300mg of magnetic CoFe was weighed out 2 O 4 The nano particles are dissolved in the carboxymethyl chitosan gel solution, nitrogen is introduced for deoxidation, and ultrasonic cleaning is performed by using an ultrasonic cleaner, so that the uniformly dispersed magnetic particle carboxymethyl chitosan gel solution is formed. Adding a magnetic particle carboxymethyl chitosan gel solution into a microemulsion system (85 g of paraffin oil, 80g of span and 5g of ethanol) dropwise, emulsifying for 30min, adding 2mL of glutaraldehyde solution with the concentration of 10% into the microemulsion system, adjusting the temperature of the reaction system to 40 ℃, reacting for 3h, and alternately washing the obtained reaction product with absolute ethanol and petroleum ether to obtain the amino modified magnetic CoFe 2 O 4 And (3) nanoparticles.
(b) Phenylboronic acid modification
150mg of amination-modified magnetic CoFe 2 O 4 Dissolving the nano particles in 10mL PBS buffer solution (pH is 6.0 and concentration is 0.02 mol/L), adding 0.1-g N-hydroxysuccinimide, and performing ultrasonic treatment for 10min to form the amination modified magnetic CoFe 2 O 4 Nanoparticle mixed solution. 120mg of 4-carboxyphenylboronic acid is dissolved in 5mL of PBS buffer solution (pH 6.0, concentration 0.02 mol/L), 0.1g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (CAS: 25952-53-8) is added, and the mixture is sonicated for 15min to form a carboxyphenylboronic acid mixture solution. Magnetic CoFe modified by amination 2 O 4 Mixing the nanoparticle mixed solution and the carboxyphenylboronic acid mixed solution, oscillating at room temperature for reaction for 4 hours, washing with distilled water, and centrifugally separating to obtain the phenylboronic acid modified magnetic CoFe 2 O 4 And (3) nanoparticles.
(2) Preparation of phenylboronic acid modified core-shell structure quantum dot
0.86g of cadmium acetate and 1.1g of Na 2 TeO 3 And 5g PVP (molecular weight 30000) were added to a mixed solution containing 98mL of ethylene glycol and 2mL of ethylenediamine, and stirredAnd (3) uniformly obtaining a mixed solution, transferring the mixed solution into a reaction kettle to react for 10 hours at 180 ℃, and alternately washing a reaction product by ethanol and water to obtain the CdTe quantum dot. 1.2g of CdTe quantum dot, 1.8g of zinc acetate and 2.2g of m-mercaptophenylboric acid are dissolved in 100mL of water solution, the pH value of the solution is adjusted to 11 through NaOH solution (1 mol/L), the mixed solution is transferred into a reaction kettle, the reaction temperature is controlled to be 90 ℃, the reaction is carried out for 4 hours, and the phenylboric acid modified CdTe@ZnS core-shell structure quantum dot powder is obtained after the alternate cleaning and drying of ethanol and water.
(3) Preparation of fluorescent magnetic composite nanofiber
2g of polyvinyl alcohol was dissolved in 18mL of water, and the solution was stirred well to prepare a 10% polyvinyl alcohol solution. 0.3g of phenylboronic acid modified magnetic CoFe 2 O 4 The nanoparticle and 1g of phenylboronic acid modified CdTe@ZnS core-shell structure quantum dot are respectively dispersed in 5mL of aqueous solution, and are poured into polyvinyl alcohol solution after being fully stirred, and electrostatic spinning precursor solution is obtained. Sucking the electrostatic spinning precursor solution into an injector fixed on a propulsion pump for electrostatic spinning, wherein the propulsion speed of the propulsion pump in the electrostatic spinning process is 1.5mL/h, the spinning voltage is set to be 18KV, the distance from a spinning port to a receiver is 18cm, and the diameter of a spinning nozzle is 0.6mm. And carrying out vacuum drying on the fiber obtained by electrostatic spinning to obtain the fluorescent magnetic composite nanofiber.
Fig. 5 shows SEM photographs of the fluorescent magnetic composite nanofibers prepared in example 2. As can be seen from FIG. 5, spherical CoFe 2 O 4 The particles are uniformly attached to the surface and the inside of the nanofiber, and the particle size is about 300nm, and meanwhile, the particle size of the CdTe@ZnS quantum dots is smaller and is not shown in an SEM photograph. Fe in comparative example 1 3 O 4 The morphology can be known, and the morphology and the size of the magnetic material in the final fluorescent magnetic composite nanofiber can be realized by controlling the type and morphology of the added magnetic material.
Fig. 6 shows EDS spectra of fluorescent magnetic composite nanofibers. As can be seen from FIG. 6, the elements such as C, co, fe, cd, te, S and Zn appearing in the energy spectrum preliminarily prove CoFe 2 O 4 And cdte@zns have been successfully embedded in nanofiber matrices.
FIG. 7 shows CoFe 2 O 4 XRD patterns of nano particles, cdTe@ZnS core-shell structure quantum dots and fluorescent magnetic composite nano fibers. As can be seen from fig. 7, all diffraction peaks from cdte@zns QDs demonstrate that the synthesized quantum dots have a good cubic sphalerite structure. CoFe 2 O 4 Description of the main characteristic peaks of synthesized CoFe 2 O 4 The crystals have a cubic spinel structure. For fluorescent magnetic composite nano-fiber, diffraction peak and CoFe 2 O 4 Good matching with the derivative peak of CdTe@ZnS appears, indicating the presence of both components, thereby confirming CoFe 2 O 4 And cdte@zns have been successfully modified at the surface of nanofibers.
Fig. 8 shows fluorescence intensity of fluorescent magnetic composite nanofibers at different addition levels of fluorescent materials (phenylboronic acid modified cdte@zns core-shell structured quantum dots). The preparation process of the fluorescent magnetic composite nanofiber represented by the curve a and the curve c is different from that of the fluorescent magnetic composite nanofiber represented by the example 2 in that the addition amount of the quantum dot in the phenylboronic acid modified CdTe@ZnS core-shell structure is different, the addition amount of the quantum dot in the curve b (representing the fluorescent magnetic composite nanofiber prepared by the example 2) is 1g, the addition amount of the quantum dot in the curve a is 0.6g, and the addition amount of the quantum dot in the curve c is 1.3g. As can be seen from fig. 8, when the addition amounts of the fluorescent materials are 0.6g, 1g, and 1.3g, respectively, the fluorescent intensities of the fluorescent magnetic composite nanofibers are 401, 480, and 607, respectively; therefore, the fluorescent magnetic composite nanofiber has the advantage of adjustable fluorescence.
Fig. 9 shows the fluorescence intensity profile of fluorescent magnetic composite nanofibers over time. As can be seen from fig. 9, the fluorescent magnetic composite nanofiber prepared in example 2 can also maintain an initial fluorescence intensity of 95% after being placed for one month, and exhibits excellent fluorescence stability.
Example 3
The preparation method of the fluorescent magnetic composite nanofiber comprises the following steps:
(1) Preparation of phenylboronic acid modified magnetic Co 3 O 4 Nanoparticles
(a) Amination modification
Carboxymethyl chitosan powder is dispersed in water solution by ultrasonic to prepare 5mL of carboxymethyl chitosan gel solution with the concentration of 0.05 g/mL. 500mg of magnetic Co was weighed 3 O 4 The nano particles are dissolved in the carboxymethyl chitosan gel solution, nitrogen is introduced for deoxidation, and ultrasonic cleaning is performed by using an ultrasonic cleaner, so that the uniformly dispersed magnetic particle carboxymethyl chitosan gel solution is formed. Adding a magnetic particle carboxymethyl chitosan gel solution into a microemulsion system (80 g of paraffin oil, 80g of span and 10g of ethanol) dropwise, emulsifying for 60min, adding 3mL of formaldehyde solution with concentration of 15% into the microemulsion system, adjusting the temperature of a reaction system to 50 ℃, reacting for 5h, and alternately washing the obtained reaction product with absolute ethyl alcohol and petroleum ether to obtain amino modified magnetic Co 3 O 4 And (3) nanoparticles.
(b) Phenylboronic acid modification
200mg of amination-modified magnetic Co 3 O 4 Dissolving the nano particles in 10mL PBS buffer solution (pH is 6.0 and concentration is 0.04 mol/L), adding 0.3g N-hydroxysuccinimide, and performing ultrasonic treatment for 10min to form the amination modified magnetic Co 3 O 4 Nanoparticle mixed solution. 200g of 5-carboxy-2-chlorobenzoic acid was dissolved in 5mL of PBS buffer (pH 6.0, concentration 0.04 mol/L), and 0.3g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and sonicated for 15min to form a carboxyphenylboronic acid mixed solution. Magnetic Co modified by amination 3 O 4 Mixing the nanoparticle mixed solution and the carboxyphenylboronic acid mixed solution, oscillating at room temperature for reaction for 6 hours, washing with distilled water, and centrifugally separating to obtain the phenylboronic acid modified magnetic Co 3 O 4 And (3) nanoparticles.
(2) Preparation of phenylboronic acid modified core-shell structure quantum dot
0.36g NaBH 4 And 0.24g Se powder is dissolved in 10mL distilled water, and magnetically stirred under the protection of nitrogen to generate NaHSe solution; the reaction process is carried out in an oxygen-free environment, nitrogen is firstly introduced into the reaction for a period of time, and the whole reaction process is carried out in a nitrogen atmosphere. When the black Se powder gradually disappears, the reaction solution gradually changes from black to colorless or pale red,the solution formed at this time is NaHSe solution.
0.3g of zinc acetate, 0.41g of cadmium acetate and 1.48g of Glutathione (GSH) were dissolved in 60mL of distilled water, magnetically stirred, and the pH value of the solution was adjusted to 12 to obtain a Zn precursor solution. Transferring the prepared Zn precursor solution and NaHSe solution into a reaction bottle, refluxing in an oil bath at 90 ℃ for 1.5 hours, stopping heating, immediately placing into a refrigerator freezing chamber for cooling, and then taking out to obtain the ZnSe quantum dot colloid solution. The quantum dots prepared by washing the mixed solution of absolute ethyl alcohol and isopropanol can be centrifugally separated to obtain pure Zn 0.4 Cd 0.6 Se QDs。
0.4g of Zn 0.4 Cd 0.6 Dissolving Se quantum dots, 1.2g of manganese acetate and 1.15g of m-mercaptophenylboronic acid in 100mL of water, regulating the pH value of the solution to 11 through NaOH solution (1 mol/L), transferring the mixed solution into a reaction kettle, controlling the reaction temperature to 120 ℃, reacting for 5h, and alternately washing and drying the reaction product by isopropanol and water to obtain the phenylboronic acid modified Zn 0.4 Cd 0.6 Se@MnS core-shell structure quantum dots.
(3) Preparation of fluorescent magnetic composite nanofiber
3.2g of sodium alginate was dissolved in 18mL of water and stirred well to prepare a sodium alginate solution having a concentration of 15%. Magnetic Co modified with 0.1g phenylboronic acid 3 O 4 Nanoparticle and 0.4g phenylboronic acid modified Zn 0.4 Cd 0.6 And respectively dispersing Se@MnS core-shell structure quantum dots in 5mL of aqueous solution, fully stirring, pouring into sodium alginate solution, and fully stirring to obtain electrostatic spinning precursor solution. Sucking the electrostatic spinning precursor solution into an injector fixed on a propulsion pump for electrostatic spinning, wherein the propulsion speed of the propulsion pump is 2mL/h in the electrostatic spinning process, the spinning voltage is set to be 20KV, the distance from a spinning port to a receiver is 20cm, and the diameter of a spinning nozzle is 0.8mm. And carrying out vacuum drying on the fiber obtained by electrostatic spinning to obtain the fluorescent magnetic composite nanofiber.
Glycoprotein enrichment and isolation assay
Test example 1
Adenosine (glycoprotein), chicken ovalbumin solution (glycoprotein), human serum protein (non-glycoprotein) and deoxyadenosine solution (non-glycoprotein) were diluted to gradient concentrations with 0.1mol/L, ph=8.5 PBS buffer, respectively: 0.1mg/mL, 0.2mg/mL, 0.3mg/mL, 0.4mg/mL, 0.5mg/mL, 0.6mg/mL, 0.7mg/mL, 0.8mg/mL, 0.9mg/mL, 1.0mg/mL, and the adsorption amounts of the fluorescent magnetic composite nanofibers to glycoproteins and non-glycoproteins under different concentration gradients were tested. The test procedure was as follows:
glycoprotein and non-glycoprotein under each concentration gradient were placed in test tubes, respectively, with 5mL of each. To each test tube was added 5mg of the fluorescent magnetic composite nanofiber prepared in example 1, and the test tube was continuously shaken on a shaker at room temperature for 3 hours, and it was confirmed that adsorption equilibrium was reached. Then, the composite nanofiber is adsorbed on the wall of a test tube by using a magnet, the supernatant is removed, 2mL of PBS buffer solution (with the concentration of 0.1mol/L and the pH value of 8.5) is added as a cleaning solution, the composite nanofiber is redispersed, the adsorption and cleaning operation is repeated for 3 times, finally, the composite nanofiber is dispersed in 2mL of acetic acid solution with the concentration of 0.1mol/L, the vibration is carried out on an oscillator for 1h, the desorption of the adsorbed protein is realized, and finally, the magnet is used for adsorbing the composite nanofiber on the wall of the test tube, and the desorbed solution is collected. And (5) carrying out absorbance test on the desorbed solution by an ultraviolet-visible spectrophotometer, and calculating the adsorption quantity.
Experiments show that the repeated use of the fluorescent magnetic composite nanofiber can be realized by adjusting the pH value of the solution, namely the pH value, and the adsorption amount of the fluorescent magnetic composite nanofiber to different types of glycoproteins and non-glycoproteins is shown in fig. 10. As shown in FIG. 10, the maximum adsorption amount of the fluorescent magnetic composite nanofiber to adenosine is 420mg/g, the maximum adsorption amount to chicken ovalbumin is 370mg/g, and the adsorption amounts to human serum albumin and deoxyadenosine are 52mg/g and 24.5mg/g respectively, which shows that the fluorescent magnetic composite nanofiber prepared by the invention has good specific adsorption to glycoprotein.
Test example 2
5mg of the fluorescent magnetic composite nanofiber prepared in example 2 was added to a test tube, and then 5mL of a mixed solution of adenosine and deoxyadenosine (PBS buffer solution having an adenosine and deoxyadenosine content of 1mg, a solvent of 0.1mol/L, pH=8.5) was added, and the test tube was continuously shaken on a shaker at room temperature for 3 hours, to confirm that adsorption equilibrium was reached. Then, the composite nanofiber is adsorbed on the wall of a test tube by using a magnet, the supernatant is removed, 2mL of PBS buffer solution (with the concentration of 0.1mol/L and the pH value of 8.5) is added as a cleaning solution, the composite nanofiber is redispersed, the adsorption and cleaning operation is repeated for 3 times, finally, the composite nanofiber is dispersed in 2mL of acetic acid solution with the concentration of 0.1mol/L, the vibration is carried out on an oscillator for 1 hour, the desorption of the adsorbed protein is realized, and finally, the magnet is used for adsorbing the composite nanofiber on the wall of the test tube, and the desorbed solution is collected. And (5) carrying out absorbance test on the desorbed solution by an ultraviolet-visible spectrophotometer, and calculating the adsorption quantity.
FIG. 11 shows the amount of adsorption of adenosine and deoxyadenosine by fluorescent magnetic composite nanofibers. As can be seen from FIG. 11, when adenosine and deoxyadenosine are in the mixed solution, the adsorption amounts of the fluorescent magnetic composite nanofiber to two proteins are 128mg/g and 25mg/g respectively because adenosine becomes a non-glycoprotein after deoxyadenosine, so that the fluorescent magnetic composite nanofiber has good specific recognition and adsorption capacity to adenosine (glycoprotein).
Glycoprotein assay
Adenosine solutions were formulated with a concentration gradient of 0.1mol/L, ph=8.5 in PBS buffer as follows: 0X 10 - 6 mol/L、3×10 -6 mol/L、5×10 -6 mol/L、10×10 -6 mol/L、15×10 -6 mol/L、20×10 -6 mol/L、25×10 -6 mol/L、30×10 -6 mol/L、35×10 -6 mol/L、40×10 -6 mol/L、50×10 -6 And (3) testing the influence of the adenosine solution on the fluorescence performance of the fluorescent magnetic composite nanofiber under each concentration gradient by mol/L. The test procedure was as follows:
taking 11 test tubes, adding 5mg of the fluorescent magnetic composite nanofiber prepared in the example 3 and 1.9mL of PBS buffer solution (with the concentration of 0.01mol/L and the pH=8), then adding the adenosine solution under each concentration gradient into the 11 test tubes respectively, and carrying out oscillation reaction for 20min to determine the fluorescent intensity of the fluorescent magnetic composite nanofiber.
FIG. 12 shows the effect of different concentrations of adenosine solution on fluorescence properties of fluorescent magnetic composite nanofibers. As can be seen from FIG. 12, the fluorescence peak intensity of the fluorescent magnetic composite nanofiber gradually decreases with increasing concentration of the adenosine solution, and the intervals between the different peaks are approximately equal, and at the same time, the effect of adenosine on the fluorescence performance of the fluorescent magnetic composite nanofiber is mainly due to the competitive binding effect, zn when adenosine is added to the solution containing the composite fiber 0.4 Cd 0.6 The phenylboronic acid modified on the surface of the Se@MnS core-shell structure quantum dot is easy to combine with an adjacent glycol bond on the surface of adenosine, so that stripping of ligand molecules on the surface of the quantum dot and change of the surface state of the quantum dot are caused, and fluorescence of the quantum dot is quenched. Therefore, based on the fluorescence signal change (fluorescence quenching) of the fluorescent magnetic composite nanofiber, the fluorescent magnetic composite nanofiber can be prepared into a fluorescent probe so as to realize trace detection of adenosine.
FIG. 13 shows the relationship between the adenosine concentration and the fluorescence emission intensity. As can be seen from fig. 13, there is a certain linear relationship between the change in fluorescence peak intensity of the fluorescent magnetic composite nanofiber and the change in concentration of adenosine. Thus, trace amounts of adenosine in solutions can be quantitatively detected by this relationship. The relationship between the fluorescence peak intensity change of the fluorescent magnetic composite nanofiber and the concentration of adenosine accords with the Stern-Volmer equation, namely F 0 /F＝1+K sv C Adenosine concentration F in the formula 0 And F is the fluorescence peak intensity of the sample after the adenosine solution is added and C is the fluorescence peak intensity of the sample after the adenosine solution is not added Adenosine concentration Represents the concentration of the adenosine solution, K sv Represents the Stern-Volmer quenching constant. When the concentration of the adenosine is in the range of 1-50 mu mol/L, a good linear relation exists between the relative fluorescence intensity of the fluorescent magnetic composite nanofiber and the concentration of the adenosine solution, and F takes the concentration of the adenosine solution as an abscissa 0 with/F being the ordinate, a linear regression equation F is obtained 0 /F＝0.075C Adenosine concentration +0.76, the correlation coefficient of linear fitting is 0.994, and the detection limit (3σ) of the fluorescent magnetic composite nanofiber on the adenosine solution is 1.5X10 according to the equation 3σ/K -7 mol/L (n=11), where 3σ is the standard deviation of the blank measurement (n=11), K isThe sensitivity of the slope is calibrated.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (5)
1. The preparation method of the fluorescent magnetic composite nanofiber is characterized by comprising the following steps:
dispersing the phenylboronic acid modified magnetic nano particles and phenylboronic acid modified core-shell structure quantum dots in a solvent, uniformly stirring, then pouring the mixture into a spinning polymer solution, and fully stirring to obtain an electrostatic spinning precursor solution; carrying out electrostatic spinning on the electrostatic spinning precursor solution, and carrying out vacuum drying to obtain fluorescent magnetic composite nano fibers;
the phenylboronic acid modified magnetic nanoparticle is prepared by the following method:
dissolving the amination modified magnetic nano particles in PBS buffer solution, adding N-hydroxysuccinimide, and performing ultrasonic treatment for 10-20 min to form amination modified magnetic nano particle mixed solution; dissolving carboxyphenylboronic acid in PBS buffer solution, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and performing ultrasonic treatment for 10-20 min to form a carboxyphenylboronic acid mixed solution; mixing the amination modified magnetic nanoparticle mixed solution with the carboxyphenylboronic acid mixed solution, oscillating at room temperature for reaction for 1-6 h, washing with distilled water, and centrifugally separating to obtain phenylboronic acid modified magnetic nanoparticles;
the amination modified magnetic nanoparticle is prepared by the following method:
dissolving magnetic nano particles in a natural polymer solution, introducing nitrogen for deoxidation and ultrasound to form a uniformly dispersed magnetic particle polymer solution; adding a magnetic particle polymer solution as a water phase into a microemulsion system formed by a surfactant, a cosurfactant and an oil phase dropwise, emulsifying for 20-60 min, adding a cross-linking agent solution, adjusting the temperature of a reaction system to 30-50 ℃, reacting for 1-5 h, and alternately washing the obtained reaction product by absolute ethyl alcohol and petroleum ether to obtain amino modified magnetic nano particles;
the magnetic nano particles are at least one of superparamagnetic, paramagnetic or ferromagnetic metals, metal oxides or alloys; the natural polymer solution is a chitosan gel solution or a carboxymethyl chitosan solution; the surfactant is at least one of Span80, OP-10 and TritonX-114; the cosurfactant is ethanol or isopropanol; the oil phase is one of paraffin oil, palm oil, n-hexane and cyclohexane; the cross-linking agent solution is aqueous solution of formaldehyde, glyoxal or glutaraldehyde;
the phenylboronic acid modified core-shell structure quantum dot is prepared by the following method:
dissolving II-VI group quantum dots, a metal source and phenylboronic acid in water, regulating the pH value to 8-11, transferring to a reaction kettle, setting the reaction temperature to 90-160 ℃, reacting for 1-8 hours, washing and drying the reaction product to obtain phenylboronic acid modified core-shell structure quantum dots; the quantum dot shell layer with the core-shell structure prepared by the method is M 1-y N y S, wherein M, N is at least one of Zn, cd, cu, mn, and 0 < y < 1;
the mass concentration of the phenylboronic acid modified magnetic nano particles in the electrostatic spinning precursor solution is 0.1-5 wt%, and the mass concentration of the phenylboronic acid modified core-shell structure quantum dots in the electrostatic spinning precursor solution is 0.5-10 wt%; the solvent is one or more of water, ethanol, DMF, methanol, acetone, methylene dichloride and chloroform; the spinning polymer solution is a solution of a polymer containing an ortho-glycol bond; the physical conditions of the electrostatic spinning are as follows: the propelling speed of the propelling pump is 1-2 mL/h, the spinning voltage is 10-20 KV, the distance from the spinning port to the receiver is 10-25 cm, and the diameter of the spinning nozzle is 0.2-0.8 mm.
2. The method for preparing fluorescent magnetic composite nanofibers according to claim 1, wherein the carboxyphenylboronic acid is one or more of 2-carboxyphenylboronic acid, 3-carboxyphenylboronic acid, 4-carboxy-2-fluorobenzeneboronic acid, 4-carboxy-3-fluorobenzeneboronic acid, 4-carboxy-2-chlorobenzeneboronic acid, 4-carboxy-3-chlorobenzeneboronic acid, 5-carboxy-2-fluorobenzeneboronic acid, 5-carboxy-2-chlorobenzeneboronic acid, 3, 5-dicarboxyphenylboronic acid and 5-carboxy-2-hydroxymethylphenylboronic acid.
3. The method for preparing fluorescent magnetic composite nano-fiber according to claim 1, wherein the group II-VI quantum dots are ZnSe, cdSe, cdTe, cdS, zn X Cd 1-X Se、CdSe 1-X S X 、CdSe 1-X Te X CdSe/ZnSe, cdS/ZnSe, cdTe/ZnSe or CdTe/CdS, wherein X is more than 0 and less than 1;
the metal source is nitrate, acetate or chlorate of Zn, cd, cu or Mn; the phenylboronic acid is p-mercaptophenylboronic acid or m-mercaptophenylboronic acid; the molar ratio of the II-VI group quantum dots to the metal source to the phenylboronic acid is 1:1.5-3:1-10; the reaction product is washed with isopropanol or alternatively with ethanol and water.
4. A fluorescent magnetic composite nanofiber prepared by the method of any one of claims 1 to 3.
5. Use of a fluorescent magnetic composite nanofiber according to claim 4 for detecting, isolating or enriching glycoproteins.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684005A (en) * | 2008-09-28 | 2010-03-31 | 复旦大学 | Nano magnetic material of surface modified boric acid base group, preparation method and application thereof |
| CN102120168A (en) * | 2010-12-07 | 2011-07-13 | 复旦大学 | Multifunctional core-shell structure fluorescent coding magnetic microspheres and preparation method thereof |
| CN102877150A (en) * | 2012-10-25 | 2013-01-16 | 黑龙江东方学院 | Method for preparing cadmium telluride/ferroferric oxide magnetic fluorescent fiber through in-situ method |
| CN103525405A (en) * | 2013-10-21 | 2014-01-22 | 北京理工大学 | Magnetic fluorescent difunctional nano material based on natural polymer and preparation method thereof |
| CN104745193A (en) * | 2015-02-13 | 2015-07-01 | 中南大学 | Fluorescent magnetic nano composite material and preparation method thereof |
| CN105462590A (en) * | 2015-11-30 | 2016-04-06 | 江苏大学 | Boric acid quantum dot ratio fluorescent probe and preparation method and application thereof |
| CN106366182A (en) * | 2016-08-29 | 2017-02-01 | 四川大学 | PH-responsive type magnetic composite nanosphere as well as preparation method and application thereof |
| CN106693909A (en) * | 2017-01-19 | 2017-05-24 | 江苏大学 | Phenylboronic acid modified magnetic nanoparticle, and preparation method and application thereof |
| CN110161243A (en) * | 2018-02-13 | 2019-08-23 | 北京化工大学 | A kind of nano artificial antibody inhibition and preparation method thereof for tumor markers real time imagery in living cells |
| CN110731961A (en) * | 2014-10-14 | 2020-01-31 | 芝加哥大学 | Metal organic framework, pharmaceutical preparation and use thereof in preparing medicament |
| WO2021056137A1 (en) * | 2019-09-23 | 2021-04-01 | 国家纳米科学中心 | Chiral plasmon nanostructure and use thereof in circularly polarized luminescence system |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001087354A2 (en) * | 2000-05-17 | 2001-11-22 | Bristol-Myers Squibb Pharma Company | Use of small molecule radioligands for diagnostic imaging |
| WO2008138184A1 (en) * | 2007-05-14 | 2008-11-20 | Shanghai Hengrui Pharmaceutical Co.Ltd. | Derivatives of pyrroloazacycles, the method of making them and the use thereof as inhibitors of protein kinases |
| CN110082328A (en) * | 2019-05-05 | 2019-08-02 | 江南大学 | A kind of carbon quantum dot-molecular engram fluorescent sensor material and its preparation method and application detecting chloramphenicol |
-
2021
- 2021-08-26 CN CN202110986387.2A patent/CN113634240B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684005A (en) * | 2008-09-28 | 2010-03-31 | 复旦大学 | Nano magnetic material of surface modified boric acid base group, preparation method and application thereof |
| CN102120168A (en) * | 2010-12-07 | 2011-07-13 | 复旦大学 | Multifunctional core-shell structure fluorescent coding magnetic microspheres and preparation method thereof |
| CN102877150A (en) * | 2012-10-25 | 2013-01-16 | 黑龙江东方学院 | Method for preparing cadmium telluride/ferroferric oxide magnetic fluorescent fiber through in-situ method |
| CN103525405A (en) * | 2013-10-21 | 2014-01-22 | 北京理工大学 | Magnetic fluorescent difunctional nano material based on natural polymer and preparation method thereof |
| CN110731961A (en) * | 2014-10-14 | 2020-01-31 | 芝加哥大学 | Metal organic framework, pharmaceutical preparation and use thereof in preparing medicament |
| CN104745193A (en) * | 2015-02-13 | 2015-07-01 | 中南大学 | Fluorescent magnetic nano composite material and preparation method thereof |
| CN105462590A (en) * | 2015-11-30 | 2016-04-06 | 江苏大学 | Boric acid quantum dot ratio fluorescent probe and preparation method and application thereof |
| CN106366182A (en) * | 2016-08-29 | 2017-02-01 | 四川大学 | PH-responsive type magnetic composite nanosphere as well as preparation method and application thereof |
| CN106693909A (en) * | 2017-01-19 | 2017-05-24 | 江苏大学 | Phenylboronic acid modified magnetic nanoparticle, and preparation method and application thereof |
| CN110161243A (en) * | 2018-02-13 | 2019-08-23 | 北京化工大学 | A kind of nano artificial antibody inhibition and preparation method thereof for tumor markers real time imagery in living cells |
| WO2021056137A1 (en) * | 2019-09-23 | 2021-04-01 | 国家纳米科学中心 | Chiral plasmon nanostructure and use thereof in circularly polarized luminescence system |
Non-Patent Citations (2)
| Title |
|---|
| Hines M A, and Sionnest G P..Synthesis and Characterization of Strongly Luminescing ZnS-Capped CdSe Nanocrystals.《J. Phys. Chem.》.1996,全文. * |
| 黄孟琼 ; 王秀玲 ; 刘勇健 ; .双官能Fe_3O_4/CdSe/CdS荧光磁性复合物的制备和表征.化学学报.2010,(第16期),全文. * |
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