CN104458695A - Rapid Raman spectrum detection method for molecularly imprinted membrane - Google Patents
Rapid Raman spectrum detection method for molecularly imprinted membrane Download PDFInfo
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- CN104458695A CN104458695A CN201410719995.7A CN201410719995A CN104458695A CN 104458695 A CN104458695 A CN 104458695A CN 201410719995 A CN201410719995 A CN 201410719995A CN 104458695 A CN104458695 A CN 104458695A
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Abstract
The invention relates to a Raman spectrum detection method for a molecularly-imprinted membrane (MIM) by use of a Raman spectrometer used as a detection means with the combination of a molecular imprinting technology and a membrane technology and is used for rapidly detecting target molecules-dimethylguanidine hydrochloride and the like in real time. According to the method, a piece of lens paper for an optical lens is used as a substrate (carrier), guanidine hydrochloride or 4-(2-amino ethyl) benzsulfamide is used as an imprinted template, nanogold/silver sol is added in a pre-polymerization solution, and a polymer is directly light-gathered on the lens paper, so as to be convenient to carry and detect. The addition of the nanogold/silver sol is similar to the surface enhanced raman spectroscopy in principle, the response strength of the Raman spectrum can be enhanced and the fluorescence signal interference is reduced; the molecularly-imprinted membrane after and before target adsorption is compared with a standard substance, so that the peaked change in the Raman spectrum can be observed and whether a practical sample contains a target molecule can be judged.
Description
Technical field
Invent a kind of molecularly imprinted composite membrane, and using Raman spectrum as detection means, the i.e. Raman spectrum detection system of molecular engram film (Molecularly-Imprinted Membrane, MIM), for additive illegal in medicine real-time, detect fast.The preparation of molecularly imprinted composite membrane with optical lens lens paper for matrix, optics lens paper is thinner, polymkeric substance attachment better, the interference for target molecule Raman signal can be reduced, nano silver gel solution is added in solution before polymerization, the response intensity of Raman can be strengthened, reduce the detection line of Raman spectrum, reduce the interference of fluorescence signal.
Background technology
Molecularly imprinted polymer (MIPs) is under microsphere (template molecule) exists, and adds function monomer and crosslinking chemical and initiating agent and is polymerized.After polymerization, the method of microsphere physics or chemistry is eluted and on the skeleton of polymkeric substance, just defines one with the molecular recognition position complementary in functional group, spatial structure, shape, size of microsphere, therefore can realize the specific recognition to target molecule.Confirm, MIPs can compare favourably with enzyme and antibody to the specific recognition capability of microsphere.Raman spectrum is a kind of scattering spectrum, based on the Raman scattering effect that India scientist Raman found in nineteen twenty-eight.Raman spectrum provides the normal mode of vibration frequency of material molecule and the information about vibrational energy level, rotation aspect, these information are only relevant with rotational energy level with the molecular vibration of measured matter, therefore Raman spectrum has the fingerprint characteristic of material, and can realize the quick detection of material.
As one of accessory substance that the epoch are progressive, the morbidity rate of the various disease such as diabetes increases year by year, has become the puzzlement of a lot of people at present.Therefore some antidiabetic drugs and health products cause the vast interest of people, in order to identify that whether it is containing active component, adopts Raman spectrum to carry out quick detection and has supplied current needs undoubtedly.
Molecular engram combines with membrane technology by the present invention, and using Raman spectrometer as detection means, namely molecular engram film (Molecularly-Imprinted Membrane, MIM) Raman spectrum detect, for target molecule real-time, detect fast.
Summary of the invention
The object of the invention is to provide a kind of materials and methods that is real-time, detection object fast, to solve the problems such as classic method cost is high, step is complicated.
Object of the present invention is achieved through the following technical solutions:
The preparation of nano silver gel: added in 500ml water by the silver nitrate of 90mg, then boiled by solution, then the sodium citrate 10ml adding 1% wherein, continue to keep its fluidized state 1h.
False template molecule, initiating agent ABVN, the nano silver gel prepared above, monomeric acrylic or acrylamide, crosslinking chemical TRIM is added in certain absolute ethyl alcohol, acetonitrile and toluene.
After solid material dissolves, logical nitrogen 10min, is immersed 30min in the refrigerator of 4 DEG C by the lens wiping paper cut, then taken out by lens wiping paper, be placed between two glass plates, carry out photopolymerization 12h under being put in uviol lamp.
After polymerization, lens wiping paper is taken out, the square scraps of paper of 3 ╳ 3mm are cut into after drying, absorption 15min is carried out to the actual sample solution of variable concentrations, the side's of taking-up scraps of paper dry and carry out Raman spectrum detection afterwards, contrast with the Raman spectrogram of the square scraps of paper and the Raman spectrogram of object that do not adsorb actual sample, can whether containing object and the Raman spectrum lowest detectable limit for object in judgement sample solution by the change at peak.
Molecular imprinting (MIP) is combined with filter paper, develops molecular engram filter paper, possess the advantage of molecular imprinting and film two technology;
(1) filter paper used comprises optical lens test paper, qualitative filter paper, quantitative filter paper, wipes clean spun laced fabric, template etc.
(2) nm of gold/silver gel add the interference that can make to reduce fluorescence signal in Raman detection; Nanogel can be nm of gold or nano silver gel, reaches the object strengthening Raman response.
(3) nm of gold/silver gel is on the surface of material not as Raman spectrum surface enhanced, but is aggregated in the surface of matrix together, makes its distribution in the polymer more even.
(4) qualitative to selective adsorption target compound on test paper is realized by Raman spectrum, quantitative test; Raman spectrometer is handheld Raman spectrometer (i-RAMANplus (BWTEK)), and determined wavelength scope is 175cm
-1-4000cm
-1, have splendid spectral resolution, highest resolution can reach 3.0cm
-1.
Beneficial effect
Above-mentioned molecular engram film has absorption property to target molecule, and along with the increase of concentration of target molecules, raman spectrum strength becomes large, the object reaching in real time, fast, conveniently detect.
Concrete implementing method
Example 1 takes 0.0487g guanidine hydrochloride, adds 5ml anhydrous alcohol solution, then adds 5ml acetonitrile wherein, 0.1g ABVN, ultrasonic dissolution.1ml nano silver colloidal sol is added again in above-mentioned solution.Finally add 0.416ml acrylic acid wherein, 3.527mlTRIM and 5ml toluene, mixing, logical nitrogen 10min.Then the lens wiping paper cut is immersed above-mentioned solution, in the refrigerator putting into 4 DEG C, soak 30min.Be placed between two glass plates by lens wiping paper after immersion, under being put in uviol lamp, light gathers 12h.After taking-up lens wiping paper dries, film is cut into the square scraps of paper of 3 ╳ 3mm, after at normal temperatures 15min is adsorbed to the solution (solvent is methyl alcohol/acetonitrile=1/1) of actual sample (Dimethyldiguanide hydrochloride enteric solubility tablet and phenformin hydrochloride tablet), the square scraps of paper are taken out and dry, carry out Raman spectrum detection, Raman detection (see Figure of description 1.1 and Fig. 1 .2) is carried out to the square scraps of paper do not adsorbed and standard items simultaneously.They are carried out the contrast peak position, can find out, containing Metformin hydrochloride in actual sample Dimethyldiguanide hydrochloride enteric solubility tablet, containing DB2 in actual sample DB2.
Example 2 takes 0.1011g4-(2-aminoethyl) benzsulfamide, adds 5ml absolute ethyl alcohol and 5ml acetonitrile, ultrasonic dissolution.Adding 0.4352g acrylamide and 0.1g ABVN wherein.Finally in above-mentioned solution, add 3.527mlTRIM, 1ml ultrapure water and 5ml toluene, mixing, logical nitrogen 10min.Then the lens wiping paper cut is immersed above-mentioned solution, in the refrigerator putting into 4 DEG C, soak 30min.Lens wiping paper is placed between two glass plates after immersion, be put in light under uviol lamp to gather 12h. and take out after lens wiping paper dries, film is cut into the square scraps of paper of 3 ╳ 3mm, after 15min is adsorbed at normal temperatures to the solution of actual sample, the square scraps of paper are taken out and dry, carry out Raman spectrum detection, Raman detection (see Figure of description 2.1, Fig. 2 .2 and Fig. 2 .3) is carried out to the square scraps of paper do not adsorbed and standard items simultaneously.They are carried out the contrast peak position, can find out, containing Metformin hydrochloride in actual sample JC1012974, containing insoral in phenformin hydrochloride tablet, containing glibenclamide in sample BC201300380.
Above enforcement x example is to describe the present invention in detail, and unrestricted the present invention.
Claims (3)
1. the preparation of guanidine hydrochloride molecularly imprinted composite membrane and use, step is as follows:
The preparation of guanidine hydrochloride molecularly imprinted composite membrane: relate to optical lens lens paper for matrix, polymer poly is incorporated in matrix, in pre-polymerization liquid except adding monomer, crosslinking chemical, initiating agent, also to add appropriate nm of gold/silver gel, object increases the response intensity of composite membrane in Raman spectrum, reduce the interference of fluorescence signal, reduce the detectability of Raman spectrum.Step is as follows:
False template molecule (guanidine hydrochloride), initiating agent ABVN and with nm of gold/silver gel, monomeric acrylic, crosslinking chemical TRIM is added in certain absolute ethyl alcohol, acetonitrile and toluene.
After solid material dissolves, logical nitrogen 10min, is immersed 30min in the refrigerator of 4 DEG C by the lens wiping paper cut, then taken out by lens wiping paper, be placed between two glass plates, carry out photopolymerization 12h under being put in uviol lamp.
After polymerization, lens wiping paper is taken out, the square scraps of paper of 3 ╳ 3mm are cut into after drying, absorption 15min is carried out to the actual sample solution of variable concentrations, the side's of taking-up scraps of paper dry and carry out Raman spectrum detection afterwards, contrast with the Raman spectrum of the square scraps of paper Raman spectrum do not adsorbed and Metformin hydrochloride standard items, can whether containing Metformin hydrochloride and the Raman spectrum lowest detectable limit for Metformin hydrochloride guanidine in judgement sample solution by the change at peak.
The preparation of 2.4-(2-aminoethyl) benzsulfamide molecular engram film and use, step is as follows:
False template molecule (4-(2-aminoethyl) benzsulfamide), initiating agent ABVN, nano silver gel, monomeric acrylamide, crosslinking chemical TRIM is added in certain absolute ethyl alcohol, acetonitrile and toluene.
After solid material dissolves, logical nitrogen 10min, is immersed 30min in the refrigerator of 4 DEG C by the lens wiping paper cut, then taken out by lens wiping paper, be placed between two glass plates, carry out photopolymerization 12h under being put in uviol lamp.
After polymerization, lens wiping paper is taken out, the square scraps of paper of 3 ╳ 3mm are cut into after drying, absorption 15min is carried out to the actual sample solution of variable concentrations, the side's of taking-up scraps of paper dry and carry out Raman spectrum detection afterwards, contrast with the Raman spectrum of the square scraps of paper Raman spectrum do not adsorbed and above-mentioned standard items, can whether containing Metformin hydrochloride or insoral or glibenclamide and the Raman spectrum lowest detectable limit for them in judgement sample solution by the change at peak.
3. method according to claim 1 step, is characterized in that:
(1) molecular imprinting (MIP) is combined with filter paper, develop molecular engram filter paper, possess the advantage of molecular imprinting and film two technology; Filter paper used comprises optical lens test paper, qualitative filter paper, quantitative filter paper, wipes clean spun laced fabric, template etc.
(2) nm of gold/silver gel add the interference that can make to reduce fluorescence signal in Raman detection; Nanogel can be nm of gold or nano silver gel, reaches the object strengthening Raman response.
Nm of gold/silver gel is on the surface of material not, but is aggregated in the surface of matrix together as Raman spectrum surface enhanced, makes its distribution in the polymer more even.
(4) qualitative to selective adsorption target compound on test paper is realized by Raman spectrum, quantitative test; Raman spectrometer is handheld Raman spectrometer (i-RAMANplus (BWTEK)), and determined wavelength scope is 175cm
-1-4000cm
-1, have splendid spectral resolution, highest resolution can reach 3.0cm
-1.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106370644A (en) * | 2016-12-01 | 2017-02-01 | 无锡艾科瑞思产品设计与研究有限公司 | Detection method and test paper strip for sulfadimidine in animal tissue |
| CN106947018A (en) * | 2017-03-09 | 2017-07-14 | 江苏大学 | A kind of high-performance and highly controllable hud typed trace sensor and preparation method and purposes |
| CN107266628A (en) * | 2017-07-05 | 2017-10-20 | 浙江工业大学 | Gold-nanoparticle-containing molecularly imprinted hydrogel and preparation method and application thereof |
| CN107860759A (en) * | 2017-10-31 | 2018-03-30 | 江苏大学 | A kind of preparation method of molecular engram sensor with SERS activity and application |
| CN108579696A (en) * | 2018-03-12 | 2018-09-28 | 中国人民解放军第二军医大学 | A kind of theophylline molecular engram material and its preparation method and application of silver nano-grain doping |
| CN109187490A (en) * | 2018-11-09 | 2019-01-11 | 中国农业科学院农业质量标准与检测技术研究所 | Based on SERS technology detection Atrazine, chlopyrifos, the method for triazolone and kit |
| CN109580575A (en) * | 2018-05-14 | 2019-04-05 | 江苏经贸职业技术学院 | It is a kind of based on molecular engram-Raman spectrum antibiotic detection method |
| CN110018142A (en) * | 2019-03-20 | 2019-07-16 | 西南交通大学 | Composite fluorescence substrate, the preparation method and application of composite fluorescence substrate |
| CN110146498A (en) * | 2019-06-13 | 2019-08-20 | 东北大学 | A kind of ion transducer and its preparation method and application detecting thiocyanate radical by naked eyes according to color change |
| CN110470649A (en) * | 2019-09-23 | 2019-11-19 | 济南大学 | A kind of paper base trace Raman sensor preparation and its application in imidacloprid detection |
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Cited By (15)
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|---|---|---|---|---|
| CN106370644A (en) * | 2016-12-01 | 2017-02-01 | 无锡艾科瑞思产品设计与研究有限公司 | Detection method and test paper strip for sulfadimidine in animal tissue |
| CN106947018B (en) * | 2017-03-09 | 2019-02-05 | 江苏大学 | A kind of high-performance and highly controllable hud typed trace sensor and preparation method and purposes |
| CN106947018A (en) * | 2017-03-09 | 2017-07-14 | 江苏大学 | A kind of high-performance and highly controllable hud typed trace sensor and preparation method and purposes |
| CN107266628A (en) * | 2017-07-05 | 2017-10-20 | 浙江工业大学 | Gold-nanoparticle-containing molecularly imprinted hydrogel and preparation method and application thereof |
| CN107860759A (en) * | 2017-10-31 | 2018-03-30 | 江苏大学 | A kind of preparation method of molecular engram sensor with SERS activity and application |
| CN108579696A (en) * | 2018-03-12 | 2018-09-28 | 中国人民解放军第二军医大学 | A kind of theophylline molecular engram material and its preparation method and application of silver nano-grain doping |
| CN109580575A (en) * | 2018-05-14 | 2019-04-05 | 江苏经贸职业技术学院 | It is a kind of based on molecular engram-Raman spectrum antibiotic detection method |
| CN109580575B (en) * | 2018-05-14 | 2020-07-24 | 江苏经贸职业技术学院 | Antibiotic detection method based on molecular imprinting-Raman spectroscopy |
| CN109187490A (en) * | 2018-11-09 | 2019-01-11 | 中国农业科学院农业质量标准与检测技术研究所 | Based on SERS technology detection Atrazine, chlopyrifos, the method for triazolone and kit |
| CN110018142A (en) * | 2019-03-20 | 2019-07-16 | 西南交通大学 | Composite fluorescence substrate, the preparation method and application of composite fluorescence substrate |
| CN110018142B (en) * | 2019-03-20 | 2021-10-22 | 西南交通大学 | Composite fluorescent substrate, preparation method and application thereof |
| CN110146498A (en) * | 2019-06-13 | 2019-08-20 | 东北大学 | A kind of ion transducer and its preparation method and application detecting thiocyanate radical by naked eyes according to color change |
| CN110146498B (en) * | 2019-06-13 | 2021-03-26 | 东北大学 | Ion sensor for detecting thiocyanate through naked eyes according to color change and preparation method and application thereof |
| CN110470649A (en) * | 2019-09-23 | 2019-11-19 | 济南大学 | A kind of paper base trace Raman sensor preparation and its application in imidacloprid detection |
| CN110470649B (en) * | 2019-09-23 | 2021-12-28 | 济南大学 | Preparation of paper-based imprinted Raman sensor and application of paper-based imprinted Raman sensor in imidacloprid detection |
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Application publication date: 20150325 |