CN113533407A - USPIO-MOF assembly and preparation method and application thereof - Google Patents
USPIO-MOF assembly and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a USPIO-MOF assembly and a preparation method and application thereof, wherein the assembly comprises a USPIO material combined with a first antigen or a first antibody and a MOF material combined with a second antibody or a second antigen corresponding to the first antigen or the first antibody, and the USPIO material and the MOF material are combined through antigen-antibody specificity to form the assembly. According to the assembly, the USPIO is assembled on the MOF surface, so that water molecules are prevented from entering the assembly, the apparent diffusion coefficient of the assembly is increased, and the transverse relaxation rate of the assembly is further improved, so that the sensitivity of the magnetic relaxation switch sensor is improved.
Description
Technical Field
The invention relates to the field of nano material science, in particular to a USPIO-MOF assembly and a preparation method and application thereof.
Background
In recent years, magnetic relaxation switch sensors based on the change of state of magnetic nanoparticles have received increasing attention in modern analysis. Magnetic relaxation switch sensors have been widely used to detect different targets, such as heavy metals, bacteria, pesticides, viruses, and antibiotics. The magnetic relaxation switch sensor has more immunity to detection of food samples than the currently existing detection modes because the magnetic relaxation switch sensor is uniform and light independent and the magnetic susceptibility of most food samples is negligible.
However, the conventional magnetic relaxation switch sensor is not adequate for analyzing the trace target due to its low sensitivity. To address these challenges, many efforts have been made in recent years. Researchers have increased the sensitivity of conventional magnetic relaxation switch sensors by integrating magnetic separation into the magnetic relaxation switch sensor to increase the sensitivity or by improving the amount of binding of magnetic nanoparticles to the surface of the magnetic relaxation switch sensor using signal amplification steps including streptavidin-biotin recognition, bio-orthogonal reactions or nanoparticles. Although higher sensitivity and better reproducibility have been achieved, it still fails to detect small molecules that require very high sensitivity. Therefore, it is very important to develop effective techniques to improve the sensitivity and stability of the magnetic relaxation switching sensor.
Disclosure of Invention
In order to solve the above technical problems in the prior art and to improve the sensitivity and stability of the magnetic relaxation switch sensor, an object of the present invention is to provide a USPIO-MOF assembly, which reduces the entrance of water molecules into the assembly, increases the apparent diffusion coefficient of the assembly, and further improves the transverse relaxation rate thereof by assembling the USPIO on the MOF surface, so as to improve the sensitivity of the magnetic relaxation switch sensor.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a USPIO-MOF assembly comprising a USPIO material bound to a first antigen or a first antibody and a MOF material bound to a second antibody or a second antigen corresponding to the first antigen or first antibody, the USPIO material and the MOF material forming an assembly by specific binding of the antigen antibodies.
In some embodiments, the method of making the USPIO material comprises the steps of:
mixing ferric acetylacetonate, 1, 2-hexadecanediol, oleic acid, oleylamine and phenyl ether and magnetically stirring under a nitrogen stream; then heating up, heating to reflux under a nitrogen blanket, and keeping for 30 min; and then removing a heat source to cool the obtained mixture to room temperature, adding ethanol into the mixture, precipitating, and centrifuging to obtain the USPIO material.
In some embodiments, the method of making the USPIO material comprises the steps of:
mixing ferric triacetylacetonate, 1, 2-hexadecanediol, oleic acid, oleylamine and phenyl ether and magnetically stirring under nitrogen flow, then heating to 200 ℃ and maintaining for 30min, then heating to reflux under nitrogen blanket and maintaining for 30min, removing heat source and cooling the obtained mixture to room temperature; and adding ethanol into the mixture to obtain a precipitate, and finally performing centrifugal separation to obtain the USPIO material.
In some embodiments, the MOF is MIL-101.
It is a second object of the present invention to provide a method for preparing a USPIO-MOF assembly according to any of the above embodiments, comprising the steps of:
s1, binding the USPIO material with a first antigen or a first antibody;
s2, binding the MOF material to the first antigen or a second antibody or a second antigen corresponding to the first antibody;
s3, binding the USPIO material bound to the first antigen or antibody and the MOF material bound to the second antibody or antigen corresponding to the first antigen or antibody by antigen-antibody specific binding to form an assembly.
In some embodiments, step S1 is specifically: mixing a PB solution (phosphate buffer solution), a first antigen or first antibody solution, an EDC solution (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride solution), an NHS solution (N-hydroxysuccinimide solution) and a USPIO solution, incubating, washing and then re-suspending to obtain the USPIO material combined with the first antigen or the first antibody.
More specifically, step S1 further includes a step of preparing a USPIO solution, specifically: mixing Fe (acac)3Mixing 1, 2-hexadecanediol, oleic acid, oleylamine and phenylate, magnetically stirring under nitrogen flow, heating to 200 ℃ for 30min, heating under nitrogen blanket to reflux, keeping for 30min, stopping heating, cooling the obtained mixture to room temperature, adding ethanol into the obtained mixture, precipitating, and centrifugally separating to obtain a black product, wherein the black product is USPIO material; dissolving the black product in ethane in the presence of oleic acid and oleylamine, centrifuging to remove undispersed residues, adding ethanol into the solution from which the residues are removed to obtain a precipitate, centrifuging to remove the solvent, dispersing the obtained precipitate in ethane to obtain a solution containing USPIO, and diluting the solution containing USPIO with toluene; DMSA (dimercaptodibutyrate) is dissolved in methanol to obtain a mixed solution, the mixed solution is added into a solution which is diluted by toluene and contains USPIO, and the solution is incubated for 24 hours at room temperature to obtain the USPIO solution.
In some embodiments, step S2 is specifically: and mixing the PB solution, the second antigen or second antibody solution, the EDC solution, the NHS solution and the MOF solution to obtain the MOF material combined with the second antibody or the second antigen.
More specifically, step S2 further includes a step of preparing a MOF solution, specifically: dissolving ferric chloride hexahydrate in ultrapure water to prepare solution A, dissolving 2-amino terephthalic acid in N, N' -dimethylformamide aqueous solution (volume ratio DMF: dH)2O1: 1) to prepare a solution B; adding N, N' -dimethylformamide and ultrapure water into a reaction vessel, uniformly mixing to obtain an initial solution, heating in a water bath, adding a part of solution A and a part of solution B into the initial solution at a certain speed respectively, reacting for 1h, and taking a first solution out of the reaction solution to obtain a first growth product; then produced in the first growthAnd taking the substance as an initial solution, adding a part of the solution A and a part of the solution B into the initial solution at certain speeds respectively, reacting for 1h to obtain a second growth product, sequentially growing until a sixth growth product is obtained, and washing the MOF solution for later use.
In some embodiments, step S3 is specifically: mixing and incubating a solution A containing USPIO material combined with a first antigen or a first antibody and a solution B containing MOF material combined with a second antibody or a second antigen to form the USPIO-MOF assembly.
The invention also aims to provide an application of the USPIO-MOF assembly in any embodiment or the USPIO-MOF assembly prepared by the preparation method in any embodiment as a magnetic relaxation switch sensor.
Further, the application is the application of the USPIO-MOF assembly in detecting bisphenol A.
Compared with the prior art, the beneficial effects of this application are as follows:
(1) according to the invention, a first antigen or a first antibody is combined with the USPIO material, a second antibody or a second antigen corresponding to the first antigen or the first antibody is combined with the MOF material, and the USPIO is assembled on the MOF surface by utilizing the specific combination of the antigen and the antibody, so that the entry of water molecules into the formed assembly is reduced, the apparent diffusion coefficient of the assembly is increased, and the transverse relaxation rate of the assembly is improved.
(2) The key point of the invention lies in synthesizing MOF material and USPIO nano particles, constructing a magnetic relaxation switch sensing system by utilizing the high water-holding performance of MOF and the excellent magnetic performance and other excellent characteristics of the USPIO nano particles, and establishing the linear relation between the concentration of a target object and the transverse relaxation time signal value.
(3) The MOF material is modified with a specific antibody on the surface, can specifically recognize a target, and the concentration of the target in a detection system can mediate the assembly efficiency of the functional material, so that the assembly efficiency is highest in the absence of the target, and is lower in the presence of the target; the specific principle is shown in fig. 2.
(4) The invention is different from other magnetic relaxation sensing systems, the MOF material and USPIO nano particles are selected as functional materials, and a method for detecting a target object through a nuclear magnetic resonance analysis imager is constructed, so that the simple, convenient, rapid, high-sensitivity and high-flux detection of the target object is realized.
Drawings
FIG. 1 shows bisphenol A concentration and T2A standard curve in between;
FIG. 2 is a schematic diagram of a magnetic relaxation switch sensor detecting a target;
in FIG. 3, a is an electron micrograph of MOF, b is a hydrated particle size plot of the MOF produced, c is a nitrogen adsorption and desorption curve of the MOF, d is an electron micrograph of USPIO, e is a hydrated particle size plot of the USPIO produced, and f is an M-H curve at 300K of USPIO;
in FIG. 4, a is an electron micrograph of MOF bound to an antibody, b is an electron micrograph of USPIO bound to an antigen, c is an electron micrograph of an MOF and USPIO assembly, d is a hydrated particle size plot, e is an apparent diffusion coefficient, and f is a transverse relaxation rate;
in fig. 5, a is the influence of USPIO concentration on the relaxation sensing system, b is the influence of antigen/antibody concentration on the relaxation sensing system, c is the influence of incubation time on the relaxation sensing system, and d is the influence of echo time on the relaxation sensing system;
FIG. 6 shows the effect of BPA, BADGE, 4-CP, 4-OP on a magnetic relaxation switch sensor.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
A USPIO-MOF assembly comprises USPIO material combined with a first antigen or a first antibody, MOF material combined with a second antibody or a second antigen, and the USPIO material is assembled on the surface of the MOF material by the specific combination of the first antigen and the second antibody or the first antibody and the second antibody to form the USPIO-MOF assembly.
The preparation method of the USPIO-MOF assembly comprises the following steps:
s1, binding the USPIO material with a first antigen or a first antibody;
s2, binding the MOF material to a second antibody or a second antigen;
s3, specifically binding the USPIO material bound to the first antigen or first antibody and the MOF material bound to the second antibody or second antigen through the antigen-antibody to form an assembly.
More specifically, the preparation method of the USPIO-MOF assembly of the present example comprises the following steps:
(1) preparation of MOF
0.4055g of ferric chloride hexahydrate is accurately weighed and dissolved in 100mL of ultrapure water to form solution A, 0.2720g of 2-aminoterephthalic acid is accurately weighed and dissolved in 100mL of N, N' -dimethylformamide aqueous solution (the volume ratio of DMF: dH2O is 1:1) to form solution B; adding 2.5mL of N, N' -dimethylformamide and 7.5mL of ultrapure water into a 50mL conical flask, uniformly mixing to obtain an initial solution, and heating in a water bath at 50 ℃; respectively adding 10mL of the solution A and 10mL of the solution B into 10mL of the initial solution at a constant speed by an injection pump at the flow rate of 30mL/h and 10mL/h, and reacting for 1 hour to obtain a first growth product; taking 20mL of the first growth product out of the reaction system, taking 10mL of the first growth product as a new initial solution, then respectively injecting 10mL of the solution A and 10mL of the solution B at constant speed through an injection pump at the flow rates of 30mL/h and 10mL/h, and reacting for 1 hour to obtain a second growth product; and sequentially growing to the sixth time to obtain a sixth growth product, so as to obtain an MIL-101 solution, and washing and storing for later use. And carrying out structural characterization and related detection on the prepared MIL-101, wherein the detection results are shown in a graph a, a graph b and a graph c of figure 3.
(2) Preparation of USPIO
2mmol of Fe (acac)310mmol of 1, 2-hexadecanediol, 6mmol of oleic acid, 6mmol of oleylamine and 20mL of phenyl ether were mixed and magnetically stirred under a nitrogen stream to give a mixture which was heated to 200 ℃ for 30min and then heated under a nitrogen blanket to reflux (265 ℃) for 30min to give a dark brown mixture; removing the heat source to cool the dark brown mixture to room temperature; then adding 40mL of ethanol into the black-brown mixture, precipitating a black product, and carrying out centrifugal separation to obtain a product USPIO; dissolving the obtained black product in hexane, centrifuging at 6000rpm for 10min, removing undispersed residue, and collecting supernatant to obtain USPIO ethane solution, and storing for use;
the obtained USPIO is subjected to structural characterization and related detection, and the detection results are shown in a d diagram, an e diagram and a f diagram of FIG. 3.
Precipitating USPIO ethane solution with ethanol, centrifuging at 6000rpm for 10min, removing solvent, and dispersing in hexane to obtain solution A; adding 2mL of ethanol solution into 2mL of solution A to precipitate USPIO, centrifuging to remove supernatant, and adding 5mL of toluene solution into the obtained precipitate to obtain solution B; the mixture was added to solution B, and the solution was incubated at room temperature for 24 hours, and then centrifuged to remove the supernatant, and stored for use.
(3) Preparation of USPIO-MOF assemblies
Covalent coupling is used as a coupling method to couple antibodies/antigens on the surfaces of MOF and USPIO, and the method specifically comprises the following steps: adding 0.72mL of 10mM PB solution (pH 7.4), 2mL of 1 microgram/mL antibody solution, 0.2mL of 10mg/mL EDC solution, 0.08mL of 10mg/mL NHS solution and 10mL of 0.5mg/mL MIL-101 solution into a 10mL centrifuge tube in sequence, shaking uniformly, incubating at 4 ℃ for 12h, washing with ultrapure water and then suspending to obtain the functionalized MOF (namely the MOF bound with the antibody), and storing at 4 ℃ for later use;
adding 0.72mL of PB (pH 7.4) with the concentration of 10mM, 2mL of antigen solution with the concentration of 1 mug/mL, 0.2mL of EDC solution with the concentration of 10mg/mL, 0.08mL of NHS solution with the concentration of 10mg/mL and 2mL of USPIO solution with the concentration of 0.2mg/mL into a 10mL centrifuge tube in sequence, shaking uniformly, incubating for 12h at 4 ℃, washing with ultrapure water and then resuspending to obtain functionalized USPIO (namely USPIO combined with antigen), and storing for later use at 4 ℃;
adding 0.15mL of functionalized USPIO solution and 0.15mL of functionalized MOF solution into a 2mL centrifuge tube, and placing the centrifuge tube on a shaking table at room temperature for incubation for 1h to obtain the USPIO-MOF assembly. The obtained USPIO-MOF assembly is subjected to structure characterization and related performance detection, and the detection result is shown in figure 4.
(4) Optimization of relaxation sensing system conditions based on USPIO-MOF assembly
The influence of USPIO concentration, antigen/antibody concentration, incubation time and echo time on a relaxation sensing system is respectively inspected, a proper relaxation sensing system is selected,
the specific method comprises the following steps:
the influence of the concentration of USPIO on a relaxation sensing system is examined: under the conditions of MOF concentration of 0.05mg/mL, antigen/antibody concentration of 1 mug/mL, incubation time of 60min and echo time of 2ms, the response intensity of a relaxation sensing system formed by adding USPIO with different concentrations (0.06, 0.08, 0.10, 0.12 and 0.14mg/mL) is respectively measured;
investigating the influence of different antigen/antibody concentrations on a relaxation sensing system: under the conditions of MOF concentration of 0.05mg/mL, incubation time of 60min and echo time of 2ms, respectively adding the response intensity of a relaxation sensing system consisting of antigens/antibodies with different concentrations (0.2, 0.4, 0.6, 0.8 and 1.0 mu g/mL);
investigating the influence of different incubation times on a relaxation sensing system: respectively incubating for different times (10 min, 30min, 50 min, 70 min, 90 min and 110min) under the conditions of MOF concentration of 0.05mg/mL, antibody/antigen concentration of 0.4 mug/mL and echo time of 2.0ms, and relaxing corresponding strength of a sensing system;
investigating the influence of different echo times on a relaxation sensing system: different echo times (0.5, 1, 1.5, 2 and 2.5ms) were selected at a MOF concentration of 0.05mg/mL, an antibody/antigen concentration of 0.4. mu.g/mL and an incubation time of 60 min.
The optimized result is shown in fig. 5, when the USPIO concentration in the relaxation sensing system is 0.08mg/mL, the antigen/antibody concentration is 0.4 mug/mL, the incubation time is 90 minutes, and the echo time of the NMR analyzer (nuclear magnetic resonance) is 1ms, the relaxation sensing system is optimal.
It should be noted that, in the assembly, the position having a response to the analyzer is the USPIO, the change of the USPIO concentration in the relaxation sensing system has a large influence on the system, and the MOF mainly has the function of changing the diffusion of water molecules around the USPIO without generating a relaxation signal, and only needs a proper concentration ratio of MOF to USPIO, so the MOF concentration does not need to be taken into consideration for optimization.
Example 2
Bisphenol a was detected using the USPIO-MOF assembly prepared in example 1 as a magnetic relaxation switching sensor.
Bisphenol a (BPA) is an important raw material that is widely used in the production of baby bottles, dental fillings and liners for food cans. The residues of BPA in food products are mainly derived from food raw materials and food packaging materials. A number of researchers have shown that BPA is considered to be an endocrine disrupting chemical, and studies have found that BPA may cause diseases of the reproductive system, including neurological and behavioral changes in infants and children, diabetes, hyperactivity, obesity, and various cancers such as breast, prostate, and testicular cancers. The limit value of BPA is regulated to be 0.01mg/L in the sanitary Standard for Drinking Water GB5749-2006 in China, and the specific migration quantity or the maximum residual quantity of BPA in coating, plastic and adhesive is not more than 0.6mg/kg according to the sanitary Standard for use of additives for food containers and packaging materials GB 9685 one 2008. We constructed a magnetic relaxation switch sensor based on USPIO and MOF for detection of BPA.
(1) Establishment of BPA Standard Curve
Taking 150 mu L of each of the antibody functionalized MOF and the antigen functionalized USPIO, respectively adding 300 mu L of bisphenol A standard solution (5pg/mL, 10pg/mL, 20pg/mL, 50pg/mL, 100pg/mL, 200pg/mL, 500pg/mL, 1000pg/mL) with different concentrations, mixing and shaking uniformly, incubating at room temperature for 60min, balancing for 2min, and performing T at room temperature by using an NMR imaging analyzer NMI 20-CA2Relaxation timeAnd detecting to obtain a standard curve shown in figure 1.
(2) Specificity analysis
4-Cinnamaldehyde (4-CP), 4-octylphenol (4-OP) and bisphenol A glycidyl ether (BDAGE) were used as analogs following the same procedure as for BPA to study the specificity of nMRS for detecting BPA. The concentration of these analogues was 500pg/mL, the concentration of BPA was 100pg/mL, and the results are shown in FIG. 6, which illustrates that the USPIO-MOF assembly prepared in example 1 has a specific recognition function for BPA.
(3) Actual sample detection
Dissolving 5mg of BPA in 5mL of methanol to prepare 1mg/mL of BPA stock solution; thereafter, the concentration of the BPA stock solution was further diluted with ultrapure water to prepare working solutions of 50pg/mL, 100pg/mL and 200pg/mL, respectively, for the tests. To test BPA levels in canned orange and Yibao water, two brands of food were purchased from local retail stores: canned oranges (i.e., canned food, from Linjia shop, http:// www.leasunfood.com /) and Yibao water (i.e., mineral water, from Huarun Yibao, https:// www.crbeverage.com /). Collecting liquid part of food sample from canned orange and Yibao water samples, taking 300 μ L of canned orange and Yibao water each time, and performing T-test using 0.5T Nuclear Magnetic Resonance (NMR) instrument2Measuring, at least three tests are carried out for each measurement; next, the food samples were spiked into known levels of BPA solution and tested for recovery. 50pg/mL, 100pg/mL and 200pg/mL BPA solutions were added to orange cans and Yibao water and the average T measured2The values are substituted into the dose response equation for the sensor. To calculate the recovery (R) of the spiked, the following formula was used:
% R ═ ((a-B)/S) × 100; where A is the post-calibration sensor response, B is the pre-calibration sensor response, and S is the post-calibration sensor response peak.
The results are shown in table 1:
TABLE 1 results of detection of BPA in actual samples
In addition to the above embodiments, in which the MOF material is bound to an antibody and the USPIO material is bound to an antigen, the USPIO-MOF assembly can be obtained by binding the MOF material to an antigen and binding the USPIO material to an antibody corresponding to the antigen, and the obtained assembly has corresponding functions.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A USPIO-MOF assembly comprising a USPIO material bound to a first antigen or a first antibody and a MOF material bound to a second antibody or a second antigen corresponding to the first antigen or first antibody, wherein the USPIO material and the MOF material form the assembly by specific binding of the antigen to the antibody.
2. The USPIO-MOF assembly according to claim 1, wherein the USPIO material is prepared by a process comprising the steps of:
mixing ferric acetylacetonate, 1, 2-hexadecanediol, oleic acid, oleylamine and phenyl ether and magnetically stirring under a nitrogen stream; then heating up, heating to reflux under a nitrogen blanket, and keeping for 30 min; and then removing a heat source to cool the obtained mixture to room temperature, adding ethanol into the mixture, precipitating, and centrifuging to obtain the USPIO material.
3. The USPIO-MOF assembly according to claim 2, characterized in that the USPIO material preparation method comprises the following steps:
mixing ferric triacetylacetonate, 1, 2-hexadecanediol, oleic acid, oleylamine and phenyl ether and magnetically stirring under nitrogen flow, then heating to 200 ℃ and maintaining for 30min, then heating to reflux under nitrogen blanket and maintaining for 30min, removing heat source and cooling the obtained mixture to room temperature; and adding ethanol into the mixture to obtain a precipitate, and finally performing centrifugal separation to obtain the USPIO material.
4. The USPIO-MOF assembly of claim 1, wherein the MOF is MIL-101.
5. A preparation method of a USPIO-MOF assembly is characterized by comprising the following steps:
s1, binding the USPIO material with a first antigen or a first antibody;
s2, binding the MOF material to the first antigen or a second antibody or a second antigen corresponding to the first antibody;
s3, binding the USPIO material bound to the first antigen or antibody and the MOF material bound to the second antibody or antigen corresponding to the first antigen or antibody by antigen-antibody specific binding to form an assembly.
6. The method for preparing a USPIO-MOF assembly according to claim 5, wherein step S1 is specifically: mixing the PB solution, the first antigen or first antibody solution, the EDC solution, the NHS solution and the USPIO solution, incubating, washing and then resuspending to obtain the USPIO material combined with the first antigen or the first antibody.
7. The method for preparing a USPIO-MOF assembly according to claim 5, wherein step S2 is specifically: and mixing the PB solution, the second antigen or second antibody solution, the EDC solution, the NHS solution and the MOF solution to obtain the MOF material combined with the second antibody or the second antigen.
8. The method for preparing a USPIO-MOF assembly according to claim 5, wherein step S3 is specifically: mixing and incubating a solution A containing USPIO material combined with a first antigen or a first antibody and a solution B containing MOF material combined with a second antibody or a second antigen to form the USPIO-MOF assembly.
9. Use of a USPIO-MOF assembly according to any of claims 1 to 4 or a USPIO-MOF assembly made by a method of manufacture according to any of claims 5 to 8 as a magnetic relaxation switch sensor.
10. Use according to claim 9, wherein the USPIO-MOF assembly is used for the detection of bisphenol A.
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