CN116120695B - Preparation method and application of stephanine molecular imprinting photonic crystal gel sensor - Google Patents
Preparation method and application of stephanine molecular imprinting photonic crystal gel sensor Download PDFInfo
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- CN116120695B CN116120695B CN202211460012.3A CN202211460012A CN116120695B CN 116120695 B CN116120695 B CN 116120695B CN 202211460012 A CN202211460012 A CN 202211460012A CN 116120695 B CN116120695 B CN 116120695B
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- UEAPAHNNFSZHMW-UHFFFAOYSA-N stepahnine Natural products COC1=CC=CC(C2=C34)=C1CC3N(C)CCC4=CC1=C2OCO1 UEAPAHNNFSZHMW-UHFFFAOYSA-N 0.000 title claims abstract description 61
- UEAPAHNNFSZHMW-CQSZACIVSA-N stephanine Chemical compound CN([C@@H]1CC2=C(C3=C11)C=CC=C2OC)CCC1=CC1=C3OCO1 UEAPAHNNFSZHMW-CQSZACIVSA-N 0.000 title claims abstract description 61
- 239000004038 photonic crystal Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004793 Polystyrene Substances 0.000 claims abstract description 28
- VQAWRQZAAIQXHM-UHFFFAOYSA-N Cepharanthine Natural products O1C(C=C2)=CC=C2CC(C=23)N(C)CCC3=CC=3OCOC=3C=2OC(=CC=23)C(OC)=CC=2CCN(C)C3CC2=CC=C(O)C1=C2 VQAWRQZAAIQXHM-UHFFFAOYSA-N 0.000 claims abstract description 18
- YVPXVXANRNDGTA-WDYNHAJCSA-N cepharanthine Chemical compound C1C(C=C2)=CC=C2OC(=C2)C(OC)=CC=C2C[C@H](C2=C3)N(C)CCC2=CC(OC)=C3OC2=C(OCO3)C3=CC3=C2[C@H]1N(C)CC3 YVPXVXANRNDGTA-WDYNHAJCSA-N 0.000 claims abstract description 18
- 239000004005 microsphere Substances 0.000 claims abstract description 14
- 238000001514 detection method Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 39
- 239000011521 glass Substances 0.000 claims description 29
- 229920002223 polystyrene Polymers 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 229920000344 molecularly imprinted polymer Polymers 0.000 abstract description 4
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241001479578 Packera contermina Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940109262 curcumin Drugs 0.000 description 1
- 235000012754 curcumin Nutrition 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/046—Elimination of a polymeric phase
- C08J2201/0462—Elimination of a polymeric phase using organic solvents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
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Abstract
The invention relates to the technical field of molecularly imprinted polymers, and particularly discloses a preparation method and application of a cepharanthine molecularly imprinted photonic crystal gel sensor. The preparation method provided by the invention comprises the following steps: s1, preparing Polystyrene (PS) microspheres; s2PS photonic crystal preparation; s3, stephanine MIPC is prepared. The obtained stephanine MIPC can perform qualitative and quantitative detection of stephanine without using large instrument, thereby effectively reducing cost and improving detection speed.
Description
Technical Field
The invention relates to the technical field of molecularly imprinted polymers, and particularly discloses a preparation method and application of a cepharanthine molecularly imprinted photonic crystal gel sensor.
Background
Molecularly Imprinted Polymers (MIPs) can selectively isolate target molecules from complex systems. The Photonic Crystal (PC) adhesive is a novel optical sensing material, has optical regulation and control performance, and can observe color change by naked eyes. If the molecular imprinting technology is introduced into the skeleton of the inverse opal structure PC gel, the Molecular Imprinting Photonic Crystal (MIPC) gel sensor is manufactured, not only has the specificity of MIP, but also combines the signal transmission function of the photonic crystal, and can be directly detected through the change of color.
Patent CN 201010556515.1 discloses a high performance liquid chromatography detection method of stephanine. Although this method has high sensitivity and high accuracy, the method requires large-scale equipment, and has a long detection cycle and a complicated pretreatment process, and is difficult to cope with the current detection demands.
Disclosure of Invention
The invention adopts an emulsion polymerization method to prepare polystyrene microspheres, adopts a vertical sedimentation self-assembly method to prepare a photonic crystal template with an opal structure, adopts stephanine as a imprinting molecule, adopts methacrylic acid as a functional monomer to prepare a precursor liquid, fills the precursor liquid into the photonic crystal to initiate polymerization, and elutes the photonic crystal template and the imprinting molecule to obtain the stephanine MIPC gel sensor with an inverse opal structure, and is used for detecting stephanine.
In a first aspect, the invention provides a preparation method of a cepharanthine molecularly imprinted photonic crystal gel sensor, which specifically comprises the following steps:
s1 preparation of Polystyrene (PS) microspheres: 100 parts by mass of H 2 Mixing O, 0.08-0.12 part by mass of sodium dodecyl sulfate and 0.2-0.3 part by mass of ammonium persulfate, and stirring at a speed of 150-300 r/min to obtain a mixed solution A; under the inert gas atmosphere, adding 22-25 parts by mass of styrene into the mixed solution A, reacting at least 9-h, cleaning and drying the reaction product to obtain PS microspheres;
s2PS photonic crystal preparation: preparing PS microspheres into emulsion with the mass fraction of 1%, vertically inserting the treated glass sheet P1 into the emulsion, and drying at 35-45 ℃ until the solvent is completely evaporated, so that a layer of PS photonic crystal film grows on the surface of the glass sheet, and obtaining a photonic crystal template;
s3, preparing stephanine MIPC: preparing a prepolymerization solution, wherein the prepolymerization solution comprises 5-10 mmol/L of stephanine, 20-40 mmol/L of methacrylic acid (MAA) and 100-200 mmol/L of ethylene glycol dimethacrylate (EDMA), and the prepolymerization solution solvent is acetonitrile; adding Azobisisobutyronitrile (AIBN) into the prepolymer liquid to ensure that the concentration of the azobisisobutyronitrile is 0.2-0.4 g/L, thereby obtaining a precursor liquid; covering and fixing another glass sheet P2 with a photonic crystal template, dripping a precursor liquid from the edge of the glass sheet, placing the glass sheet into a closed container after the template is completely transparent, and filling inert gas, and reacting at 60-70 ℃ to obtain a polymerized glass sheet with a reaction temperature of not less than 24 h; and immersing the polymerized glass sheet in tetrahydrofuran to remove the PS microspheres to obtain a film which can be separated from the glass substrate, and immersing the film in an acid alcohol solution to obtain the stephanine MIPC.
Preferably, in the steps S1 and S3, the inert gas is N 2 And (3) gas.
Preferably, in the step S1, the mixed solution a is prepared with ultrapure water and the reaction product is washed.
Preferably, in the step S2, the reaction temperature range of the mixed solution a and the styrene is 20-100 ℃.
Preferably, in the step S3, the acid-alcohol solution is a mixed solution of methanol and acetic acid with a volume ratio of methanol to acetic acid of 9:1.
Further, SEM and infrared spectrum detection are carried out on the film, and the preparation result is judged by determining the molecular morphology and the infrared spectrum absorption peak change under the SEM.
In a second aspect, a method for qualitative detection of cepharanthine by using the cepharanthine molecularly imprinted photonic crystal gel sensor in the first aspect is provided, which specifically comprises the following steps: immersing stephanine MIPC into the solution, and observing the color change of stephanine MIPC after the stephanine MIPC is stabilized; if the color of the stephanine MIPC film is changed from green to yellow or red, the stephanine MIPC film contains stephanine.
In a third aspect, a method for quantitatively detecting stephanine by using the stephanine molecular imprinting photon crystal gel sensor in the first aspect is provided, which specifically comprises the following steps: immersing stephanine MIPC into the solution, recording the position of Bragg diffraction absorption peak by an ultraviolet-visible spectrophotometer after stabilization, and determining the stephanine concentration in the solution by a linear interpolation method according to the linear relation between the absorption peak displacement value delta lambda and the stephanine concentration in the detected solution.
Preferably, the concentration range of the detected stephanine is 0.02-0.12 mmol/L.
Further, the absorption peak displacement value Deltalambda and the concentration c of stephanine in the detected solution Thousands of plants Is Δλ= 818.57c Thousands of plants +1.5333; the units of Deltalambda are nm, c Thousands of plants In mmol/L.
The invention has the beneficial effects that:
the preparation method and the application of the stephanine molecular imprinting photon crystal gel sensor disclosed by the invention can be used for detecting stephanine without using a large instrument, so that the cost is reduced and the detection speed is improved.
Drawings
FIG. 1 is an infrared spectrum of stephanine MIPC, NIPC and polystyrene microspheres.
Fig. 2 is an SEM image of PS photonic crystals.
Fig. 3 is an SEM image of stephanine MIPC.
FIG. 4 is an ultraviolet absorption spectrum of stephanine MIPC.
FIG. 5 is an ultraviolet absorption spectrum of NIPC.
Description of the embodiments
The present invention will be further described in detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent.
It should be noted that the present invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The starting materials are commercially available from the public unless otherwise specified.
Examples
The preparation method of stephanine MIPC comprises the following specific steps:
step 1, preparing Polystyrene (PS) microspheres by an emulsion polymerization method: adding 100 mL ultrapure water, 0.08 g sodium dodecyl sulfate and 0.25 g ammonium persulfate into a four-neck flask, stirring at a speed of 100 r/min, and filling N 2 At a temperature of 70℃25 mL styrene was added dropwise and reacted 6 h. Repeatedly cleaning the product with ultrapure water for multiple times for standby.
Step 2, preparing the PS photonic crystal by using a vertical deposition self-assembly method: diluting the PS emulsion to 1% by mass, placing the PS emulsion in a beaker, vertically inserting the treated glass sheet into the emulsion, drying the glass sheet at 35 ℃ without vibration, and growing a layer of film on the surface of the glass sheet after the solvent is completely evaporated, namely PS photonic crystals.
Step 3, MIPC preparation: 0.5 mmol of cepharanthine, 2mmol of methacrylic acid (MAA) and 10mmol of ethylene glycol dimethacrylate (EDMA) were dissolved in acetonitrile to form a prepolymer solution. Adding 0.02 g Azodiisobutyronitrile (AIBN) into the prepolymer to obtain a precursor solution for later use. And (3) taking another glass sheet to cover the photonic crystal template, and fixing the photonic crystal template by using a clamp to prepare a sandwich structure. Dripping the precursor liquid from the edge of the glass sheet, putting the glass sheet into a flask after the template is completely transparent, and filling N 2 15 min, reaction 24 h in an oven at 65 ℃. And (3) soaking the two polymerized glass sheets in tetrahydrofuran to remove PS spheres to obtain a film which can be separated from a glass substrate, and soaking the film in methanol/acetic acid solution with the volume ratio of 9:1 to remove the template molecule stephanine, thus obtaining the stephanine MIPC.
The preparation method of the non-molecularly imprinted photonic crystal (NIPC) gel film comprises the following specific steps:
step 1 and step 2 are the same as step 1 and step 2 of example 1;
step 3, NIPC preparation: 2mmol of methacrylic acid (MAA) and 10mmol of ethylene glycol dimethacrylate (EDMA) were dissolved in acetonitrile to form a prepolymer solution. Adding 0.02 g Azodiisobutyronitrile (AIBN) into the prepolymer to obtain a precursor solution for later use. And (3) taking another glass sheet to cover the photonic crystal template, and fixing the photonic crystal template by using a clamp to prepare a sandwich structure. Dripping the precursor liquid from the edge of the glass sheet, putting the glass sheet into a flask after the template is completely transparent, and filling N 2 15 min, reaction 24 h in an oven at 65 ℃. And (3) immersing the two polymerized glass sheets in tetrahydrofuran, removing PS spheres to obtain a film which can be separated from the glass substrate, and immersing the film in a methanol/acetic acid solution with the volume ratio of 9:1 to obtain the NIPC.
The infrared spectrum test was performed on stephanine MIPC of example 1, NIPC of comparative example 1 and Polystyrene (PS) microspheres, and the test results are shown in fig. 1.
In FIG. 1, (a), (b) and (c) are the IR spectra of PS, MIPC and NIPC, respectively. (a) Spectrum at 1600, 1500, 1450 cm -1 There is a characteristic peak, which is a skeleton vibration characteristic absorption peak of benzene ring, at 757, 698 and 698 cm -1 A set of absorption peaks occurring nearby indicate that the benzene ring is monosubstituted, indicating that PS has been successfully prepared and is free of impurities. Whereas the change in the absorption peak of the spectra of (b) and (c) indicates that both MIPC and NIPC have been successfully prepared.
SEM test was performed on the PS photonic crystal obtained in step 2 of example 1 and the cepharanthine MIPC obtained in step 3, and the results are shown in FIGS. 2 and 3.
As shown in fig. 2, the PS photonic crystal is a photonic crystal with an opal structure, and PS particles are densely and orderly stacked in a face-centered cubic structure; FIG. 3 shows the MIPC with inverse opal structure obtained by washing off stephanine template molecules, and the PS microspheres are completely etched, still keep a regular face-centered cubic structure, and present a three-dimensional orderly mutually communicated macroporous structure, which facilitates rapid molecular transmission, and causes the change of gel volume by adsorbing target molecules, thereby causing the change of color and the displacement of diffraction peaks, and realizing qualitative and quantitative analysis of target objects.
The color change was observed by immersing stephanine MIPC of example 1 and the NIPC of comparative example 1 in 0.10mmol/L of stephanine solution, 0.10mmol/L of coumarone solution and 0.10mmol/L of stephanine solution, respectively.
The stephanine MIPC changes from green to red in 0.10mmol/L stephanine solution, and has no color change in 0.10mmol/L coumarone solution and 0.10mmol/L stephanine solution.
NIPC has no color change in 0.10mmol/L cepharanthine solution, 0.10mmol/L coumarone alkali solution and 0.10mmol/L senecio alkali solution.
Cepharanthine MIPC can specifically recognize Cepharanthine.
The stephanine MIPC of example 1 and the stephanine NIPC of comparative example 1 were immersed in a stephanine solution of gradient concentration of 0 to 0.12mmol/L, and after stabilization, were measured by an ultraviolet-visible spectrophotometer, and the results are shown in FIG. 4 and FIG. 5.
The stephanine MIPC and NIPC have good absorption peak, and the maximum absorption wavelength is 516 nm. FIGS. 4 and 5 are graphs showing absorption spectra of MIPC and NIPC, respectively, in different concentrations of cepharanthine.
As can be seen from FIG. 4, the absorption peak of MIPC gradually red-shifts from green to yellow to red as the concentration of cepharanthine increases, and when the concentration is 0.12mmol/L, the absorption peak position is at 613 nm, the concentration continues to rise, and the peak position is no longer changed, and the maximum displacement amount is 97 nm. The imprinting holes matched with the curcumin in shape exist in the MIPC, the cepharanthine is easy to adsorb, and after adsorption, the gel swells to cause the change of lattice spacing in the MIPC, so that the absorption peak is displaced and the obvious color change is accompanied; when the blotting cavity reaches adsorption saturation, the absorption peak position is not changed any more.
The NIPC has no imprinting holes, has little absorption to cepharanthine and no obvious swelling, so the absorption peak position is almost unchanged, and the color is unchanged.
In the concentration range of 0.02-0.12 mmol/L, the MIPC absorption peak displacement value Deltalambda and the stephanine concentration c Thousands of plants There is a good linear relationship with the equation Δλ= 818.57c Thousands of plants +1.5333, correlation coefficient R 2 0.9819. The target concentration corresponding to the absorption peak shift of 2 nm was set as the detection limit of MIPC, and the detection limit of the obtained method was 0.57. Mu. Mol/L (0.3 mg/kg).
Claims (9)
1. The preparation method of the stephanine molecular imprinting photon crystal gel sensor is characterized by comprising the following steps of:
s1 preparation of Polystyrene (PS) microspheres: 100 parts by mass of H 2 Mixing O, 0.08-0.12 part by mass of sodium dodecyl sulfate and 0.2-0.3 part by mass of ammonium persulfate, and stirring at a speed of 150-300 r/min to obtain a mixed solution A; under the inert gas atmosphere, adding 22-25 parts by mass of styrene into the mixed solution A, reacting at least 9 and 9 hWashing and drying the reaction product to obtain PS microspheres;
s2PS photonic crystal preparation: preparing PS microspheres into emulsion with the mass fraction of 1% by taking water as a solvent, vertically inserting a glass sheet P1 with a clean and dry surface into the emulsion, and drying at 35-45 ℃ until the solvent is completely evaporated, so that a layer of PS photonic crystal film grows on the surface of the glass sheet P1, and obtaining a photonic crystal template;
s3, preparing stephanine MIPC: preparing a prepolymerization solution, wherein the prepolymerization solution comprises 5-10 mmol/L stephanine, 20-40 mmol/L methacrylic acid and 100-200 mmol/L ethylene glycol dimethacrylate, and the prepolymerization solution solvent is acetonitrile; adding azodiisobutyronitrile into the prepolymerization solution to ensure that the concentration of the azodiisobutyronitrile is 0.2-0.4 g/L, thereby obtaining a precursor solution; covering and fixing another glass sheet P2 with a photonic crystal template, dripping a precursor liquid from the edge of the glass sheet, placing the glass sheet into a closed container after the template is completely transparent, and filling inert gas, and reacting at 60-70 ℃ to obtain a polymerized glass sheet with a reaction temperature of not less than 24 h; and immersing the polymerized glass sheet in tetrahydrofuran to remove the PS microspheres to obtain a film which can be separated from the glass substrate, and immersing the film in an acid alcohol solution to obtain the stephanine MIPC.
2. The method according to claim 1, wherein in the steps S1 and S3, the inert gas is N 2 And (3) gas.
3. The method according to claim 1, wherein in the step S1, the mixed solution a is prepared with ultrapure water and the reaction product is washed.
4. The method according to claim 1, wherein in the step S2, the reaction temperature of the mixed solution a and styrene is 20 to 100 ℃.
5. The method according to claim 1, wherein in the step S3, the acid-alcohol solution is a methanol-acetic acid mixed solution with a volume ratio of methanol to acetic acid of 9:1.
6. A method for qualitative detection of cepharanthine using the cepharanthine molecularly imprinted photonic crystal gel sensor prepared by the method according to any one of claims 1 to 5, characterized by comprising the following steps: immersing stephanine MIPC into the solution, and observing the color change of stephanine MIPC after the stephanine MIPC is stabilized; if the color of the stephanine MIPC film is changed from green to yellow or red, the stephanine MIPC film contains stephanine.
7. A method for quantitatively detecting stephanine by using the stephanine molecular imprinting photonic crystal gel sensor prepared by the method according to any one of claims 1 to 5, which is characterized by comprising the following steps: immersing stephanine MIPC into the solution, recording Bragg diffraction absorption peak position by ultraviolet-visible spectrophotometer after stabilization, and measuring stephanine concentration c in the detected solution according to absorption peak displacement value Deltalambda Thousands of plants The concentration of cepharanthine in the solution was determined by linear interpolation.
8. The method for quantitative detection according to claim 7, wherein the concentration of the detected stephanine is in the range of 0.02 to 0.12 mmol/L.
9. The method according to claim 8, wherein the absorption peak displacement value Deltalambda is equal to the concentration c of cepharanthine in the solution to be detected Thousands of plants Is Δλ= 818.57c Thousands of plants +1.5333; the units of Deltalambda are nm, c Thousands of plants In mmol/L.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675531A (en) * | 2011-03-07 | 2012-09-19 | 孟子晖 | Molecularly-imprinted photonic crystal for detecting organophosphorus toxicants |
| CN103499548A (en) * | 2013-09-17 | 2014-01-08 | 南昌大学 | Method for determining vanillin by virtue of photonic-crystal molecular imprinting hydrogel |
| CN111303476A (en) * | 2020-04-20 | 2020-06-19 | 昆明理工大学 | Preparation method of molecularly imprinted photonic crystal hydrogel film for simetryn detection |
| WO2022060865A1 (en) * | 2020-09-17 | 2022-03-24 | Iaterion, Inc. | Methods and compositions for treating viral infections with double and triple combinations of antiviral and immune modulating compounds |
-
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- 2022-11-17 CN CN202211460012.3A patent/CN116120695B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675531A (en) * | 2011-03-07 | 2012-09-19 | 孟子晖 | Molecularly-imprinted photonic crystal for detecting organophosphorus toxicants |
| CN103499548A (en) * | 2013-09-17 | 2014-01-08 | 南昌大学 | Method for determining vanillin by virtue of photonic-crystal molecular imprinting hydrogel |
| CN111303476A (en) * | 2020-04-20 | 2020-06-19 | 昆明理工大学 | Preparation method of molecularly imprinted photonic crystal hydrogel film for simetryn detection |
| WO2022060865A1 (en) * | 2020-09-17 | 2022-03-24 | Iaterion, Inc. | Methods and compositions for treating viral infections with double and triple combinations of antiviral and immune modulating compounds |
Non-Patent Citations (2)
| Title |
|---|
| Cepharanthine alleviates liver injury in a rodent model of limb ischemia-reperfusion;Yin-Kuang Chang等;《Acta Anaesthesiologica Taiwanica》;第54卷(第1期);11-15 * |
| 中药青风藤、川穹中生物碱的分析研究;郭婷婷;《中国优秀硕士学位论文全文数据库 医药卫生科技辑》(第S1期);E057-135 * |
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