CN109718745B - Bernoulli type magnetic imprinting nanosheet and preparation method and application thereof - Google Patents
Bernoulli type magnetic imprinting nanosheet and preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003463 adsorbent Substances 0.000 claims abstract description 39
- 229920000344 molecularly imprinted polymer Polymers 0.000 claims abstract description 19
- ASETVIOYPLTWFT-IVZWLZJFSA-N 1-[(2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-5-(2-methoxyethenyl)pyrimidine-2,4-dione Chemical compound COC=CC=1C(NC(N([C@H]2C[C@H](O)[C@@H](CO)O2)C=1)=O)=O ASETVIOYPLTWFT-IVZWLZJFSA-N 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000000274 adsorptive effect Effects 0.000 claims abstract 2
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- OLXZPDWKRNYJJZ-UHFFFAOYSA-N 5-(6-aminopurin-9-yl)-2-(hydroxymethyl)oxolan-3-ol Chemical compound C1=NC=2C(N)=NC=NC=2N1C1CC(O)C(CO)O1 OLXZPDWKRNYJJZ-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 17
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
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- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 7
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- 238000000034 method Methods 0.000 claims description 7
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 7
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 8
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 8
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- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 5
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- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 description 4
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- CKTSBUTUHBMZGZ-SHYZEUOFSA-N 2'‐deoxycytidine Chemical compound O=C1N=C(N)C=CN1[C@@H]1O[C@H](CO)[C@@H](O)C1 CKTSBUTUHBMZGZ-SHYZEUOFSA-N 0.000 description 3
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- YKBGVTZYEHREMT-KVQBGUIXSA-N 2'-deoxyguanosine Chemical compound C1=NC=2C(=O)NC(N)=NC=2N1[C@H]1C[C@H](O)[C@@H](CO)O1 YKBGVTZYEHREMT-KVQBGUIXSA-N 0.000 description 2
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a Bernoulli type magnetic molecularly imprinted nanosheet and a preparation method and application thereof, and belongs to the technical field of functional materials. According to the invention, Janus hollow microspheres are prepared by a sol-gel method, and are subjected to ultrasonic crushing to obtain Janus nanosheets with one surface containing amino and the other surface containing chlorine; then, surface chlorine element is used as an initiator of atom transfer radical polymerization, dA is used as a template molecule, 5- (2-methoxyvinyl) -2' -deoxyuridine is used as a functional monomer, and dA molecularly imprinted polymer is grafted on the hydrophobic surface of the Janus nanosheet; then through the bonding action between amino and carboxyl, Fe coated with oleic acid3O4The particles are combined on the hydrophilic surface of Janus, a Janus type magnetic molecularly imprinted nanosheet adsorbent is prepared, and the obtained material is used for adsorptive separation of dA. The imprinting adsorption material constructed by the invention has the advantages of good selectivity, large adsorption capacity on the target object dA and quick separation.
Description
Technical Field
The invention relates to a Bernoulli type magnetic molecularly imprinted nanosheet and a preparation method and application thereof, and belongs to the technical field of functional materials.
Background
2' -deoxyadenosine (dA) is one of purine nucleosides having excellent physiological activity, and is an important material for gene medicine and genetic engineering research. In addition, dA has good physiological activity and is a well-recognized intermediate of many antiviral, antitumor and anti-AIDS drugs, so that dA has extremely wide demand in the market. At present, the common dA can be obtained by a synthesis method, a crystallization method and an adsorption method, but the synthesis method has more by-products and low product concentration; the crystallization method has high energy consumption and slow generation rate; the adsorption method has the advantages of high extraction rate and easy continuous operation on trace dA in the product, but the selectivity, adsorption capacity and mass transfer rate of common adsorbents still need to be further improved. Therefore, it is very important to study a novel adsorbent and use it for obtaining dA with high purity, based on the characteristics of dA molecular structure, starting from the interaction between dA and the adsorbent adsorption site.
Molecularly Imprinted Polymers (MIPs), commonly referred to as synthetic antibody mimetics, enable specific molecular recognition of target molecules. Compared with natural antibodies, MIPs are more stable, easily meet the requirements of wide application and are low in price. Surface imprinted polymers (SMIPs) are polymeric adsorbents that build molecular imprinted recognition sites on the surface of matrix materials, and exhibit high binding capacity, fast mass transfer, and fast binding kinetics. Heretofore, various silicon-based materials are often used as matrix materials for preparing SMIPs, and the silicon-based matrix is mostly in a spherical or tubular structure, such as silica, zeolite, kaolin, molecular sieve, halloysite nanotube, and the like. The nano-sheets have higher specific surface area and have differentiated directionality due to higher aspect ratio, so that multiple functions can be realized to act on the same nano-sheet matrix.
The composite imprinted polymers prepared by using superparamagnetic particles as a matrix are Magnetic Molecularly Imprinted Polymers (MMIPs). MMIPs can simultaneously realize the identification of target objects and the magnetic response quick separation of the adsorbent, and effectively avoid the separation of materials from mother liquor through complicated steps of centrifugation, standing, filtration and the like. At present, the modification of SiO by magnetic particles has been studied2The MMIPs are prepared from nanosheets, but the introduction of magnetic particles can cover the imprinting sites and create an uneven distribution, thereby reducing the binding capacity. Meanwhile, the introduction of the imprinted polymer layer easily causes the reduction of saturation magnetization, and the magnetic particles leaked from the MMIPs cannot be reversibly recovered after multiple adsorption-desorption cycles.
Disclosure of Invention
The invention provides a preparation method of a Janus type magnetic imprinting nanosheet adsorbent and realizes selective separation of dA, aiming at solving one of the technical bottlenecks of overlapping functional sites and regions, low selectivity, poor separation effect and the like in the existing MMIPs composite adsorbent.
Firstly, preparing Janus hollow microspheres by a sol-gel method, and obtaining Janus nanosheets with one surface containing amino groups (hydrophilic) and the other surface containing chlorine elements (hydrophobic) by ultrasonic crushing; then, surface chlorine element is used as an initiator of Atom Transfer Radical Polymerization (ATRP), dA is used as a template molecule, 5- (2-methoxyvinyl) -2' -deoxyuridine (AcrU) which forms hydrogen bond with dA and has better matching property is used as a functional monomer, and dA molecularly imprinted polymers (Janus-MIPs) are grafted on the hydrophobic surface of Janus nanosheets; then through the bonding action between amino and carboxyl, Fe coated with oleic acid3O4The particles are combined on the hydrophilic surface of Janus, and the Janus type magnetic molecularly imprinted nanosheet adsorbent (Janus-MMI) is preparedPs) and applying the obtained material to efficient selective adsorption and separation of dA in an aqueous solution.
In order to achieve the technical purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a Bernous-type magnetic molecularly imprinted nanosheet adsorbent (Janus-MMIPs), which comprises the following steps:
(1) carboxy-modified Fe3O4Preparation of the particles:
mixing 0.2 mol/L sodium oleate aqueous solution and 0.2 mol/L ferric chloride aqueous solution according to a certain proportion. Filtering to obtain brown iron oleate complex, dispersing with n-hexane, washing with distilled water, and drying in a dryer. The complex was added to 20mL of ethanol containing a certain amount of oleic acid at room temperature. The mixture was transferred to an autoclave and heated to 180 ℃ for 5 hours. After the reaction was complete, the black oleic acid capped Fe was washed with ethanol3O4Nanoparticles (Fe)3O4NPs) and separated with a magnet. The product was redispersed in toluene at a concentration of 10 mg/mL.
Wherein the volume ratio of the sodium oleate aqueous solution to the ferric chloride aqueous solution is 1 mL:1-2 mL, and the oleic acid content in the ethanol is 10-15%.
(2) Preparation of Janus nanosheets:
an amount of HSMA and water was placed in a beaker as the continuous phase and the pH was adjusted to 3-4 with HCl solution. Taking a certain amount of solid paraffin, adding a certain amount of 3-Aminopropyltriethoxysilane (APTES), a certain amount of 3-Chloropropyltriethoxysilane (CPTES) and a certain amount of tetraethyl orthosilicate (TEOS) as a dispersed phase, heating in 70 water bath, dropwise adding the dispersed phase into the continuous phase by stirring at high speed, stirring for 5 min, and reacting the mixture at 70 ℃ for 12 h. And then, centrifugally collecting, washing away an oil phase, carrying out ultrasonic crushing to obtain a Janus nanosheet, and carrying out vacuum drying.
(3) Preparation of Janus molecularly imprinted polymers (Janus-MIPs):
first, 2 '-deoxyadenosine (dA) and 5- (2-methoxyvinyl) -2' -deoxyuridine (AcrU) were dissolved in DimethineIntroducing nitrogen at normal temperature for 30min in the mixed solution of sulfone and acetonitrile, and performing self-assembly for 1.5h in a dark place; adding Ethylene Glycol Dimethacrylate (EGDMA) and Janus nanosheets, stirring at 30 deg.C for 0.5 h, adding N, N, N, N, N-Pentamethyldiethylenetriamine (PMDEIA) and copper chloride (CuCl)2) And ascorbic acid (VC), the mixed solution is continuously stirred and heated in water bath at 70 ℃ for reaction for 12 h, the product is collected by centrifugation, then Janus-MIPs are washed and purified by using a mixed solution of methanol/hydrochloric acid as an eluent (7: 3, V: V) to remove unreacted template molecules and organic solvents, and finally, at 45 ℃, the mixed solution is washed and purifiedoThe purified Janus-MIPs were dried for 24 h under C.
The mass ratio of the 2 '-deoxyadenosine to the 5- (2-methoxyvinyl) -2' -deoxyuridine is as follows: 1: 4-5; the dosage of the mixed solution of the 2' -deoxyadenosine, the dimethyl sulfoxide and the acetonitrile is 1 g: 200-250 mL;
the volume ratio of the dimethyl sulfoxide to the acetonitrile in the mixed solution of the dimethyl sulfoxide and the acetonitrile is as follows: 1: 3-4;
the nitrogen gas introducing time is 30min, and the self-assembly time is 1.5 h;
the dosage of the 2' -deoxyadenosine, the Janus nanosheets and the ethylene glycol dimethacrylate is 1 g: 2-3 g: 10-12 mL;
the dosage of the N, N, N, N, N-pentamethyl diethylenetriamine, the copper chloride and the ascorbic acid is 1.0 mL and 0.2-0.3 g and 0.08-0.1 g.
(4) Preparation of magnetic-type bifunctional molecularly imprinted adsorbent (Janus-MMIPS):
mixing Fe3O4NPs are dissolved in methanol for ultrasonic dispersion, then (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) (EDC) and N-hydroxysuccinimide (NHS) are added into the mixed solution for uniform mixing, Janus-MIPs are added for ultrasonic reaction for 20 min, centrifugal collection is carried out, and then vacuum drying is carried out for 12 h at the temperature of 45 ℃.
The Janus-MIPs and Fe3O4The mass ratio of NPs is 1: 0.1-0.15;
said Fe3O4The mass ratio of the NPs, the N-hydroxysuccinimide and the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 1: 1.5-3 : 1.5-3。
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, AcrU which forms a hydrogen bond with dA and has good matching property is used as a functional monomer, so that the specific recognition property of an imprinting layer is improved, meanwhile, a sol-gel method is adopted to prepare a Janus nano material, and the two sidedness of a Janus nano sheet is utilized to independently design a magnetic separation functional region and a dA molecule recognition functional region, so that the mutual influence of the two functions is effectively avoided. Therefore, the magnetic molecular imprinting adsorption material is constructed, and has the advantages of good selectivity, large adsorption capacity on the target object dA and rapid separation.
Drawings
FIG. 1 is a scanning electron microscope image of Janus nanosheets (a), Janus-MIPs nanosheets (b) and (c), and Janus-MMIPS nanosheets (d) prepared in example 1.
FIG. 2 shows Janus nanosheets (a), Janus-MIPs nanosheets (b), Janus-MMIPs (c), and Fe prepared in example 13O4(d) An infrared spectrum of (1).
FIG. 3 is an energy spectrum of X-ray diffraction (XRD) of Janus nanosheets, Janus-MIPs nanosheets, Janus-MMIPs prepared in example 1.
FIG. 4 is a thermogravimetric analysis (TGA) plot of Janus nanosheets, Janus-MIPs nanosheets, Janus-MMIPs prepared in example 1.
FIG. 5 shows Fe prepared in example 13O4Hysteresis loops of NPs and Janus-MMIPs.
FIG. 6 is a graph of kinetic data and model fit curves for prepared Janus-MMIPs and Janus-MNIPs adsorbing dA at 298K.
FIG. 7 is a graph of equilibrium data and model fit curves for prepared Janus-MMIPs and Janus-MNIPs adsorbing dA at 298K.
FIG. 8 shows the single-component adsorption results of prepared Janus-MMIPs and Janus-MNIPs on dA, dG, AMP and dC.
Detailed Description
In order to better understand the technical solutions of the present invention for those skilled in the art, the following further describes the technical solutions of the present invention with reference to specific embodiments and drawings.
The identification performance evaluation in the embodiment of the invention is carried out according to the following method:
the static adsorption experiment was used to complete: adding 5 mL of dA solution with a certain concentration into a centrifuge tube, adding a certain amount of Janus-MMPs adsorbent, placing the centrifuge tube in a constant-temperature water area at 25 ℃ for standing for several hours, measuring the dA content after adsorption by using an ultraviolet-visible spectrophotometer, and calculating the adsorption capacity according to the result; adding 5 mL of dA solution with initial concentration of 300 mu mol/L into a centrifuge tube, adding a certain amount of Janus-MMPs adsorbent, respectively taking out under a certain time gradient, and calculating adsorption capacity according to the result, wherein the dA solution is used for participating in research on the dynamic performance of the Janus-MMPs adsorbent. Several nucleoside compounds with similar structures and properties, such as 2-deoxyguanosine (dG), 2-deoxycytidine (dC), 5' -monophosphate-Adenosine (AMP) and the like, are selected as selective adsorbates and participate in researching the recognition performance of the adsorbents.
The invention is further illustrated by the following examples.
Example 1:
(1) carboxy-modified Fe3O4Preparation of granules
100 mL of a 0.2 mol/L aqueous solution of sodium oleate was mixed with 100 mL of a 0.2 mol/L aqueous solution of iron chloride. Filtering to obtain brown iron oleate complex, dispersing with n-hexane, washing with distilled water for three times, and drying in a dryer. The complex was added to 20.0 mL ethanol containing 10% oleic acid at room temperature. The mixture was transferred to an autoclave and heated to 180 ℃ for 5 hours. After the reaction was complete, the black oleic acid capped Fe was washed with ethanol3O4Nanoparticles (Fe)3O4NPs) and separated with a magnet. The product was redispersed in toluene at a concentration of 10 mg/mL.
(2) Preparation of Janus nanosheet
An amount of 10 wt% HSMA and water was placed in a beaker as the continuous phase and the pH was adjusted to 3-4 with 2 mol/L HCl solution. Taking a certain amount of solid paraffin, adding a certain amount of 3-Aminopropyltriethoxysilane (APTES), a certain amount of 3-Chloropropyltriethoxysilane (CPTES) and a certain amount of tetraethyl orthosilicate (TEOS) as a dispersed phase, heating in a water bath at 70 ℃, stirring at a high speed of 12000 rpm to dropwise add the dispersed phase into a continuous phase, stirring for 5 min, and reacting the mixture at 70 ℃ for 12 h. Subsequently, the mixture is centrifugally collected, washed three times by ethanol and normal hexane, and ultrasonically crushed to obtain Janus nanosheets, and then vacuum-dried at 45 ℃ for 12 hours.
(3) Preparation of Janus molecularly imprinted polymers (Janus-MIPs)
Firstly, 0.1 g of 2 '-deoxyadenosine (dA) and 0.45 g of 5- (2-methoxyvinyl) -2' -deoxyuridine (AcrU) are dissolved in a mixed solution of 5 mL of dimethyl sulfoxide and 15 mL of acetonitrile, nitrogen is introduced for 30min at normal temperature, and self-assembly is carried out for 1.5h in a dark place; then, 1.12 mL of Ethylene Glycol Dimethacrylate (EGDMA) and 0.2 g of Janus nanosheet were added, and after stirring at 30 ℃ for 0.5 h, 0.1 mL of N, N, N, N, N-Pentamethyldiethylenetriamine (PMDEIA) and 0.03 g of copper chloride (CuCl) were added2) And 0.01 g of ascorbic acid (VC), the mixed solution was continuously stirred and heated in a water bath at 70 ℃ for 12 hours of reaction, the product was collected by centrifugation, followed by washing and purification of Janus-MIPs with a mixed solution of methanol/hydrochloric acid as an eluent (7: 3, V: V) to remove unreacted template molecules and organic solvents, and finally, the purified Janus-MIPs were dried at 45 ℃ for 24 hours.
(4) Preparation of magnetic-type bifunctional molecularly imprinted adsorbent (Janus-MMIPS)
0.0025 g of Fe3O4NPs were dissolved in 20mL of methanol and ultrasonically dispersed, 0.0041 g of N-hydroxysuccinimido (NHS) and 0.0041 g of (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) (EDC) were added to the mixed solution, and the mixture was uniformly mixed, followed by addition of 0.02 g of Janus-MIPs, ultrasonic reaction for 20 min, centrifugal collection, and vacuum drying at 45 ℃ for 12 h.
Fig. 1 is a scanning electron microscope image of a Janus nanosheet (a), Janus-MIPs nanosheets (b) and (c), and Janus-MMIPs nanosheets (d) prepared in this example. The successful preparation of the molecularly imprinted polymer is shown in the figure, and meanwhile, the other side of the nanosheet is obviously connected with the magnetic particles, so that the successful preparation of the magnetic molecularly imprinted polymer is shown.
FIG. 2 shows Janus nanosheets (a), Janus-MIPs nanosheets (b), Janus-MMPs (c) and Fe prepared in this example3O4(d) An infrared spectrum of (1). 3200 + 3500 cm in a, b, c-1And 2918 cm-1A broad absorption band appears, believed to be a stretching vibration of the N-H and O-H bonds of the material, at 1715 cm-1The peak at (A) was considered to be a characteristic peak of an amide bond, and the peak at both 701cm-1 was considered to be a characteristic peak of a C-Cl bond, 509 cm in C and d-1Shows a peak, which corresponds to Fe3O4The characteristic peak of (A) indicates that the magnetic molecularly imprinted polymer is successfully prepared.
FIG. 3 is an energy spectrum diagram of X-ray diffraction (XRD) of Janus nanosheets, Janus-MIPs nanosheets and Janus-MMIPs prepared in the example, wherein Fe exists in the Janus-MMIPs3O4Structure of (1) with Fe3O4With the same peaks located at 30.2 °, 35.6 °, 43.4 °, 50.1 °, 54.1 °, 57.3 ° and 62.6 °, corresponding to their indices (111), (220), (311), (400), (422), (511), (440) and (511). Indicating that the magnetic polymer was successfully prepared.
FIG. 4 is a thermogravimetric analysis (TGA) plot of Janus nanosheets, Janus-MIPs nanosheets, Janus-MMIPs prepared in this example, with the final heat loss of the Janus-MMIPs being about 16% lower than that of the Janus-MIPs, which is mainly due to the Janus-MIPs surface-modified magnetic particles, i.e., the Janus-MIPs surface-modified Fe3O4The amount of (c) is about 16%. The final heat loss of the Janus-MIPs is about 12% lower than that of the Janus nano-sheets, and the heat loss at the stage proves that a printing layer of dA exists on the surface of the Janus-MIPs.
FIG. 5 shows Fe prepared in this example3O4Hysteresis loops of NPs and Janus-MMIPs, two curves without hysteresis, Fe3O4NPs and Janus-MMIPs are superparamagnetic, Fe3O4The saturation magnetization (Ms) values obtained at room temperature for NPs and Janus-MMPs were 49.71 emu/g and 12.23 emu/g, respectively, indicating that the Janus-MMPs had sufficient magnetic force to satisfy the requirement for magnetic separation.
Example 2:
(1) carboxy-modified Fe3O4Preparation of granules
100 mL of a 0.2 mol/L aqueous solution of sodium oleate was mixed with 150 mL of a 0.2 mol/L aqueous solution of iron chloride. Filtering to obtain brown iron oleate complex, dispersing with n-hexane, washing with distilled water for three times, and drying in a dryer. The complex was added to 20.0 mL ethanol containing 12.5% oleic acid at room temperature. The mixture was transferred to an autoclave and heated to 180 ℃ for 5 hours. After the reaction was complete, the black oleic acid capped Fe was washed with ethanol3O4Nanoparticles (Fe)3O4NPs) and separated with a magnet. The product was redispersed in toluene at a concentration of 10 mg/mL.
(2) Preparation of Janus nanosheet
An amount of 10 wt% HSMA and water was placed in a beaker as the continuous phase and the pH was adjusted to 3-4 with 2 mol/L HCl solution. Taking a certain amount of solid paraffin, adding a certain amount of 3-Aminopropyltriethoxysilane (APTES), a certain amount of 3-Chloropropyltriethoxysilane (CPTES) and a certain amount of tetraethyl orthosilicate (TEOS) as a dispersed phase, heating in a water bath at 70 ℃, stirring at a high speed of 12000 rpm to dropwise add the dispersed phase into a continuous phase, stirring for 5 min, and reacting the mixture at 70 ℃ for 12 h. Subsequently, the mixture is centrifugally collected, washed three times by ethanol and normal hexane, and ultrasonically crushed to obtain Janus nanosheets, and then vacuum-dried at 45 ℃ for 12 hours.
(3) Preparation of Janus molecularly imprinted polymers (Janus-MIPs)
Firstly, 0.1 g of 2 '-deoxyadenosine (dA) and 0.40 g of 5- (2-methoxyvinyl) -2' -deoxyuridine (AcrU) are dissolved in a mixed solution of 5 mL of dimethyl sulfoxide and 17.5 mL of acetonitrile, nitrogen is introduced for 30min at normal temperature, and self-assembly is carried out for 1.5h in the dark; then 1 mL of Ethylene Glycol Dimethacrylate (EGDMA) and 0.2 g of Janus nano-sheet are added, after stirring for 0.5 h at 30 ℃, 0.10 mL of N, N, N, N, N-Pentamethyldiethylenetriamine (PMDEIA) and 0.02 g of copper chloride (CuCl) are added2) And 0.008 g of ascorbic acid (VC), the mixed solution is continuously stirred and heated in a water bath at 70 ℃ for reaction for 12 hours, the product is collected by centrifugation, and then Janus-MIPs are washed and purified by using a mixed solution of methanol/hydrochloric acid as an eluent (7: 3, V: V) to remove the unreacted ascorbic acid (VC)The corresponding template molecule and organic solvent, and finally, the purified Janus-MIPs were dried at 45 ℃ for 24 h.
(4) Preparation of magnetic-type bifunctional molecularly imprinted adsorbent (Janus-MMIPS):
0.002 g of Fe3O4NPs were dissolved in 20mL of methanol and dispersed by sonication, 0.003 g of N-hydroxysuccinimide (NHS) and 0.003 g of (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) (EDC) were added to the mixed solution, mixed well, and after addition of 0.02 g of Janus-MIPs, sonicated for 20 min, collected by centrifugation, and then dried in vacuo at 45 ℃ for 12 h.
Example 3:
(1) carboxy-modified Fe3O4Preparation of granules
100 mL of a 0.2 mol/L aqueous solution of sodium oleate was mixed with 200 mL of a 0.2 mol/L aqueous solution of iron chloride. Filtering to obtain brown iron oleate complex, dispersing with n-hexane, washing with distilled water for three times, and drying in a dryer. The complex was added to 20.0 mL ethanol containing 15% oleic acid at room temperature. The mixture was transferred to an autoclave and heated to 180 ℃ for 5 hours. After the reaction was complete, the black oleic acid capped Fe was washed with ethanol3O4Nanoparticles (Fe)3O4NPs) and separated with a magnet. The product was redispersed in toluene at a concentration of 10 mg/mL.
(2) Preparation of Janus nanosheet
An amount of 10 wt% HSMA and water was placed in a beaker as the continuous phase and the pH was adjusted to 3-4 with 2 mol/L HCl solution. Taking a certain amount of solid paraffin, adding a certain amount of 3-Aminopropyltriethoxysilane (APTES), a certain amount of 3-Chloropropyltriethoxysilane (CPTES) and a certain amount of tetraethyl orthosilicate (TEOS) as a dispersed phase, heating in a water bath at 70 ℃, stirring at a high speed of 12000 rpm to dropwise add the dispersed phase into a continuous phase, stirring for 5 min, and reacting the mixture at 70 ℃ for 12 h. Subsequently, the mixture is centrifugally collected, washed three times by ethanol and normal hexane, and ultrasonically crushed to obtain Janus nanosheets, and then vacuum-dried at 45 ℃ for 12 hours.
(3) Preparation of Janus molecularly imprinted polymers (Janus-MIPs)
Firstly, 0.1 g of 2 '-deoxyadenosine (dA) and 0.5 g of 5- (2-methoxyvinyl) -2' -deoxyuridine (AcrU) are dissolved in a mixed solution of 5 mL of dimethyl sulfoxide and 20mL of acetonitrile, nitrogen is introduced for 30min at normal temperature, and self-assembly is carried out for 1.5h in a dark place; then 1.2 mL of Ethylene Glycol Dimethacrylate (EGDMA) and 0.2 g of Janus nano-sheet were added, and after stirring at 30 ℃ for 0.5 h, 0.10 mL of N, N, N, N, N-Pentamethyldiethylenetriamine (PMDEIA) and 0.025 g of copper chloride (CuCl) were added2) And 0.008 g of ascorbic acid (VC), the mixed solution was continuously stirred and heated in a water bath at 70 ℃ for 12 hours of reaction, the product was collected by centrifugation, followed by washing and purification of Janus-MIPs with a mixed solution of methanol/hydrochloric acid as an eluent (7: 3, V: V) to remove unreacted template molecules and organic solvents, and finally, the purified Janus-MIPs were dried at 45 ℃ for 24 hours.
(4) Preparation of magnetic-type bifunctional molecularly imprinted adsorbent (Janus-MMIPS)
0.003 g of Fe3O4NPs were dissolved in 20mL of methanol and dispersed by sonication, and then 0.009g of N-hydroxysuccinimido (NHS) and 0.009g of (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) (EDC) were added to the mixed solution, mixed well, and after further addition of 0.02 g of Janus-MIPs, sonicated for 20 min, collected by centrifugation, and then dried in vacuo at 45 ℃ for 12 h.
Test example 1:
respectively adding 5 mL of dA solution with initial concentration of 300 mu mol/L into a centrifuge tube, respectively adding 5 mg of Janus-MMIPs adsorbent prepared in example 1, and respectively taking out at the time of 10 min, 20 min, 30min, 60 min, 120 min, 240 min, 360 min and 480 min; the blot adsorbent was separated from the solution by a magnet. The concentration of dA in the filtrate was determined by calculation using an ultraviolet spectrophotometer at 259 nm, and from the results, FIG. 6 was obtained, where FIG. 6 is the kinetic data and model fitting curve of adsorption of dA by Janus-MMIPs and Janus-MNIPs prepared in example 1 at 298K, and the time to reach adsorption equilibrium was calculated; the results show that the adsorption capacity of Janus-MMIPs and Janus-MNIPs increases rapidly during the first 60 min, indicating that the template molecules can diffuse easily into the adsorbent. Furthermore, the adsorption efficiency of Janus-MMIPs is obviously faster than that of Janus-MNIPs, and the adsorption capacity of dA is larger than that of Janus-MNIPs, which indicates that a large number of empty imprinting sites are arranged on the surfaces of Janus-MMIPs. After rapid adsorption, the adsorption rate dropped sharply and reached equilibrium at 2.0 h due to the drop in dA concentration and the reduction in the number of binding sites.
Test example 2:
5 mL of dA solutions with initial concentrations of 50, 100, 150, 200, 300, 500, 700, 900 and 1000. mu. mol/L are taken and added into a centrifuge tube, 5 mg of Janus-MMIPs adsorbent prepared in example 1 is added respectively, the test solution is placed in a water bath at 25 ℃ and is kept still for 10 h, the imprinted adsorbent and the solution are separated by a magnet, the concentration of the unadsorbed dA molecules is measured by an ultraviolet-visible spectrophotometer at a wavelength of 259 nm respectively, and according to the results, a graph 7 is obtained, and the graph 7 is equilibrium data and a model fitting curve of the adsorbed dA of Janus-MMIPs and Janus-MNIPs in example 1 at 298K, accords with Langmuir and Freundich adsorption models, and simultaneously calculates the adsorption capacity. The result shows that the maximum adsorption capacity of the Janus-MMIPs to dA is 61.22 mu mol/g when the adsorption equilibrium is reached, the maximum adsorption capacity of the Janus-MNIPs to dA when the adsorption equilibrium is reached is 42.36 mu mol/g respectively, and the maximum adsorption capacity of the Janus-MMPs to dA is higher than that of the Janus-MNIPs at the same temperature, thereby proving that the Janus-MMPs are an adsorbent for effectively identifying dA MMI.
Test example 3:
2-deoxyguanosine (dG), 2-deoxycytidine (dC) and 5' -monophosphate-Adenosine (AMP) were selected as selective adsorbate controls, solutions of the above three compounds were prepared at a concentration of 700. mu. mol/L, 5 mL of each was added to a centrifuge tube, 5 mg of the imprinted adsorbent and the non-imprinted adsorbent prepared in example 1 were added, respectively, the test solution was placed in a water bath oscillator at 25 ℃ for 10 hours, the imprinted adsorbent and the solution were separated by a magnet, the concentration of unadsorbed dA molecules was measured by an ultraviolet-visible spectrophotometer at a wavelength of 259 nm, and FIG. 8 was obtained based on the results. The result shows that the adsorption capacity of the Janus-MMIPs on the four compounds follows the sequence of dA Tg > dG Tg > AMP Tg > dC, so that the fact that imprinted sites with the shape and the size consistent with that of dA exist on the surface of the Janus-MMIPs can be inferred, and the Janus-MMIPs have good adsorption specificity on dA.
Claims (10)
1. A preparation method of a Bernoulli-type magnetic molecularly imprinted nanosheet adsorbent, comprising the following steps:
(1) preparation of carboxyl-modified Fe3O4NPs；
(2) Preparing Janus nanosheets;
(3) preparation of Janus molecularly imprinted polymer:
firstly, dissolving 2 '-deoxyadenosine and 5- (2-methoxyvinyl) -2' -deoxyuridine in a mixed solution of dimethyl sulfoxide and acetonitrile, introducing nitrogen at normal temperature, and then, self-assembling in a dark place; adding ethylene glycol dimethacrylate and Janus nanosheets, stirring and uniformly mixing, adding N, N, N, N, N-pentamethyldiethylenetriamine, copper chloride and ascorbic acid, continuously stirring the mixed solution, heating in a water bath for reaction, centrifuging to collect a product, washing and purifying Janus-MIPs by using the mixed solution of methanol and hydrochloric acid as an eluent to remove unreacted template molecules and organic solvents, and drying the product;
(4) preparing a magnetic Bernoulli type bifunctional molecularly imprinted adsorbent:
mixing Fe3O4NPs are dissolved in methanol for ultrasonic dispersion, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide are added into the mixed solution, the mixture is uniformly mixed, Janus-MIPs are added for ultrasonic reaction, centrifugal collection is carried out, and then vacuum drying is carried out.
2. The method for preparing a magnetic molecularly imprinted nanosheet adsorbent of the bernoulli type according to claim 1, wherein the mass ratio of 2 '-deoxyadenosine to 5- (2-methoxyvinyl) -2' -deoxyuridine in step (3) is: 1: 4-5.
3. The preparation method of the magnetic molecular imprinting nano-sheet adsorbent of the bernoulli type according to claim 1, wherein the dosage of the mixed solution of 2' -deoxyadenosine, dimethyl sulfoxide and acetonitrile in the step (3) is 1 g: 200-250 mL;
the volume ratio of the dimethyl sulfoxide to the acetonitrile in the mixed solution of the dimethyl sulfoxide and the acetonitrile is as follows: 1: 3-4;
the nitrogen gas introducing time is 30min, and the self-assembly time is 1.5 h.
4. The preparation method of the magnetic molecular imprinting nano-sheet adsorbent of the bernoulli type according to claim 1, wherein the dosage of the 2' -deoxyadenosine, the Janus nano-sheets and the ethylene glycol dimethacrylate in the step (3) is 1 g: 2-3 g: 10-12 mL;
after the ethylene glycol dimethacrylate and the Janus nanosheets are added, stirring is carried out for 0.5 h at the temperature of 30 ℃.
5. The preparation method of the magnetic molecular imprinting nano-sheet adsorbent of the bernoulli type according to claim 1, wherein the N, N, N, N, N-pentamethyldiethylenetriamine, the copper chloride and the ascorbic acid are used in an amount of 1.0 mL: 0.2-0.3 g: 0.08-0.1 g;
the water bath heating reaction condition is that the water bath heating reaction is carried out for 12 hours at 70 ℃.
6. The method for preparing the magnetic molecular imprinting nano-sheet adsorbent of the bernoulli type according to claim 1, wherein in the step (4), the Janus-MIPs and Fe are adopted3O4The mass ratio of NPs is 1: 0.1-0.15.
7. The method for preparing a magnetic molecular imprinting nano-sheet adsorbent of the bernoulli type according to claim 1, wherein the Fe in step (4)3O4The mass ratio of the NPs to the N-hydroxysuccinimide to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 1: 1.5-3: 1.5-3.
8. The preparation method of the magnetic molecular imprinting nano-sheet adsorbent of the bernoulli type according to claim 1, wherein the ultrasonic reaction in the step (4) is carried out for 30 min.
9. The bernoulli-type magnetic molecular imprinting nanosheet adsorbent prepared by the method according to any one of claims 1 to 8, wherein the adsorbent has superparamagnetism, and the material has both hydrophilic and hydrophobic properties.
10. The magnetic molecular imprinting nano-sheet adsorbent of the bernoulli type as claimed in claim 1, which is used for adsorptive separation of 2' -deoxyadenosine.
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