CN101788489B - Sensitive thin-film material used for detecting drugs efficiently and preparation method thereof - Google Patents
Sensitive thin-film material used for detecting drugs efficiently and preparation method thereof Download PDFInfo
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- CN101788489B CN101788489B CN2010101082941A CN201010108294A CN101788489B CN 101788489 B CN101788489 B CN 101788489B CN 2010101082941 A CN2010101082941 A CN 2010101082941A CN 201010108294 A CN201010108294 A CN 201010108294A CN 101788489 B CN101788489 B CN 101788489B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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Images
Abstract
The invention relates to a sensitive thin-film material used for detecting drugs efficiently and a preparation method thereof, which is characterized in that a molecular imprinted polymer sensitive thin-film doped with precious metal nano-particles is formed on the surface of a precious metal thin-film by adopting the in-situ polymerization technology. The sensitive thin-film prepared in the invention is sensitive to drugs of heroin, morphine, cocaine and the like, wherein the limit of detection for the heroin can reach 10<-9>mol/L. The sensitive thin-film material used for detecting drugs efficiently in the invention has the obvious advantages of high sensitivity, quick response time, good repeatability, simple preparation and the like.
Description
Technical field
The invention belongs to the optical sensing field, relate to a kind of sensitive thin-film material and preparation method who is used for detecting drugs efficiently.
Background technology
Drugs mainly be meant opium, heroin, crystal methamphetamine (methamphetamine), morphine, hemp, cocaine and national regulation control other can make the narcotics and the psychotropic agent of humanoid one-tenth addiction.Current, drugs spread unchecked in the whole world, and the drug issue that is on the rise has become global disaster.Drugs spread unchecked the physical and mental health that not only threatens the people, serious harm social stability also.In the face of unusual severe Drug-related crimes situation, national governments go into overdrive on the one hand to declare and lead numerous people away from drugs, the beat drugs crime of going into overdrive on the other hand.As a link of beat drugs crime, drug testing highlights its importance day by day.
Drugs authentication method of the prior art comprises visual testing, chemical analysis method, immunological detection, thin layer chromatography, vapor-phase chromatography, high performance liquid chromatography, chromatogram/mass spectrometry analytic approach.Wherein, Visual testing is the suspicious drugs that meet censorship; At first observe its physical characteristics (form, color, natural scale etc.) and physical state (liquid, powder, tablet, capsule, plant, soft or hard resin, grease etc.), weigh, numbering, its general characteristic of detail record and Packing Condition etc.If suspicious drugs are tablet, the quantity of form, color, visible marking and the tablet of reply tablet is carried out record; Wherein also comprise with microscope and carry out the morphological feature check.There are some plant samples that obvious characteristics is arranged, like the hemp grass, available microscopic examination difference, however there is significant limitation in this method.The chemical analysis method is that color reaction commonly used screened and preliminary experiment during drugs were identified.Specific drugs can produce various colors variation, sediment or crystallization when reacting with different chemical reagent.The result of observing response is to judge whether having certain drugs.Because produce much with the chemical substance of a kind of color or deposition, false-positive situation possibly appear in reaction.So the chemical analysis method just is used for the screening and the preliminary experiment of drugs usually.Immunological detection generally is used for the screening of drugs, also can be used for conclusive evidence.At present, many on-the-spot immunology products that detect of drugs that are used for are arranged both at home and abroad the sixth of the twelve Earthly Branches.Compare with external laboratory, the immunological detection its domestic application is very limited.Thin layer chromatography (TLC) is one of court's the easiest, effective qualitative analysis means in poisonous substance laboratory.With sample point sample on the TLC plate of suspicious drugs or extraction and cleaning, and with standard items as contrast, launch, after the colour developing, measure the Rf value of checking matter and contrast with standard items Rf value, can reach the purpose of qualitative analysis.In recent years, abroad the someone has reported the technology of utilizing area of computer aided TLC that 250 kinds of unknown medicines and drugs are screened.This technology is applicable to serum, blood, urine, and the check of unknown medicine in suspicious drug powder and the tablet.With reference to medicine thin layer plate is divided into 5 migration areas with 4 kinds, to realize location to sample point.Chlorine and HCl steam etc. are used for spot and manifest its detectability scope 5～200ng/spot.Vapor-phase chromatography has characteristics such as good separating effect, highly sensitive, high specificity, analysis speed be fast, and vapor-phase chromatography is a most frequently used detection means during present domestic drugs are identified.The principle and the gas chromatography of high performance liquid chromatography are relative, but thermally labile, various drugs not volatile, that have macromolecule are carried out separation detection, and detecting device commonly used at present has UV-detector, PDAD, fluorescence detector etc.It is reported; Abroad the someone uses GC/MS/MS the ultramicron drug abuse is analyzed; Owing to adopted ion trap (MS) 2 technology, to compare with traditional high-sensitive STM or NCI detection, the background of GC/MS/MS is very little; Evaluation to target compound is more accurate, thereby can analyze the drug abuse of ppb level in the blood.The development of GC/MS is ripe, and domestic many laboratories all have been equipped with this instrument, but should not analyze the drugs of strong polarity, higher boiling, difficult gasification and larger molecular weight.Also can pass through the TLC isolation of purified, carry out utilizing the solid sampling bar of GC/MS appearance to analyze behind the scraper plate purifying.In recent years, the detection method of morphine is greatly improved.High performance liquid chromatography (HPLC) widespread use owing to its high sensitivity, the sensitivity of enzyme immunization method is also very high in addition, but owing to keep the required environmental baseline of enzymatic activity very harsh, so cost is higher.Detect morphine with molecular engram (MIP) and highlighted its good stability, highly sensitive, good selective.
Yet these methods all need be carried out pre-service to sample; Remove and disturb impurity; Enrichment trace component to be measured, to complicated, the extensive situation about detecting of sample composition, said method needs technical skill personnel and extensive expensive instrument; Be not suitable for the fast detecting of scene of a crime, and also there are problems such as the bad or specimen preparation excessive cycle of reappearance in the method that has.Under this background, domestic and international new detection technique and the sample pretreating method of forensic science man active development, from then on molecular imprinting is applied to forensic science.This technology has efficiently, quick, low-cost, easy to operate, sample size is few, the high outstanding advantage of selectivity especially should technology and Miniaturized surface plasma resonance instrument coupling, can realize that on-the-spot accurately drugs detect.
Nm of gold (Nanogold) is meant the golden material body of gold particle diameter between 1-100nm.Use because often be dispersed in the water formed aurosol in the immunoassay, so claim collaurum again with gold grain.Nano metal is seen particle in being situated between, and has special electronic structure, on some specific crystal faces, exists surface electronic state, and its Fermi level is positioned at the physical efficiency band structure just among the forbidden band in this crystal orientation.Therefore, the electronics that is in this surface state is because the constraint of work function and the periphery of can not overflowing; Again because the restriction of physical efficiency attitude and can not go deep into internal layer has formed the two-dimentional electron cloud that can only be parallel to the surface direction motion.This is the physical basis of surface effect that nanogold particle has, quantum effect and macro quanta tunnel effect.The color of nm of gold appears red to purple with its diameter and chemical environment on every side different, and has very strong secondary ability.The seventies in last century, because the unique advantage of nm of gold, the thing that serves as a mark is introduced immunological experiment, the nano gold mark of one of modern immunology four big immunolabelling techniques technological, and be used widely.Assemble the back interparticle distance according to nano particle and reduce, caused the change of surface plasma propagation (SPP) mode propagation characteristic.The interaction of local surface plasma (LSP) pattern and SPP pattern, this interaction is along with nano-metal particle also receives the influence of periphery environment dielectric property simultaneously.Its performance as phenomenon such as absorption spectrum generation blue shift occurs.Therefore, people such as Mirkin adopts direct color detection method to analyze the hybridization characteristic of oligonucleotide according to this specific character.They also through changing temperature, cause the biomolecule sex change, observe the dispersion again of the nano particle of original gathering, prove the reversibility of nano gold biological molecular aggregates process.Further research shows that the plasma that metallics produced can strengthen the electric field of its surperficial surrounding environment.The electric field of this enhancing can interact with environment on every side, can significantly change the scattering spectra characteristic of resonant particle and surrounding environment.For example: the Raman spectroscopy (SERS) that the surface strengthens is exactly to utilize the plasma resonance of localization to strengthen its scattering properties.Wherein, the Raman scattering of test material, the near field that utilizes plasma to form strengthens scattering strength.Noble metal nano particles has the local surface plasma enhancement effect; Therefore noble metal nano particles is incorporated into the surface plasma body resonant vibration technology and can strengthens the check signal with molecular imprinting coupling system; Improve detectability, can promote the development of surface plasma body resonant vibration technology in drug testing.
Molecular engram is compared with micro-fluidic chip and photonic crystal, immune labeled chip with surface plasma resonance coupling technique (SPR); All has absolute advantage at the maintenance of preparation, detection, instrument, the aspects such as regeneration of chip; This technical stability is good, practical, cheap, is fit to the national conditions and the public security actual combat demand of China more.The correlative study achievement will solve the instrument and equipment that exists in basic unit's banning drugs work outmoded aging, the technician is deficient, the low inferior problem of case handling efficiency; With the severe poisonous substance Drug-related crimes of hitting of getting the upper hand of soon; The fright offender; Safeguard the long-term stability of society, immeasurable social benefit and practical value are arranged.
Application number 200910119164.5 has disclosed a kind of drug morphia molecular recognition sensitivity chip of optical sensor, this chip and SPR coupling but do not introduce nano particle, and its detection is limited to 10
-8Mol/l.
At present, do not detect the relevant report of drugs both at home and abroad with nano particle technology and molecular imprinting and the coupling of SPR technology.These technology for detection drugs are highly sensitive, reach the international leading level.
Summary of the invention
The object of the present invention is to provide a kind of sensitive thin-film material that is used for detecting drugs efficiently.
For achieving the above object, the present invention adopts following technical scheme:
A kind of sensitive thin-film material that is used for detecting drugs efficiently; This membraneous material is to adopt the in-situ polymerization technology preparation; Promptly on the noble metal film surface; Make function monomer, drug numerator and noble metal nano particles in-situ polymerization, thereby form the molecular imprinting polymer membrane that noble metal nano particles mixes.
Described noble metal nano particles is nano particles such as gold, silver, platinum; Preferred said noble metal nano particles size is 20-100nm.
Said noble metal nano particles prepares through following method: noble metal source and surfactant are mixed in the WS; Under vigorous stirring, dropwise join the toluene solution of 11-sulfydryl undecanoic acid or dropwise be added in the lauryl mercaptan; Add excessive reductive agent then, stirring obtains.
Wherein, the mol ratio 1 of said noble metal source and said surfactant: 1-3; The mol ratio 1 of said noble metal source and said 11-sulfydryl undecanoic acid or lauryl mercaptan: 0.5-2; Described noble metal source is to be selected from one of following compound: gold chloride, silver nitrate or chloroplatinic acid; Said surfactant is to be selected from one of following compound: cetyl ammonium bromide or cetyl chloride ammonium; Reductive agent is to be selected from one of following compound: sodium citrate, sodium borohydride or oxammonium hydrochloride.
Described in-situ polymerization technology is original position thermal polymerization or original position photopolymerization.
Described noble metal film is a kind of in golden film, silverskin, aluminium film or the copper film; Described function monomer is selected from following one or both compounds: acrylic acid, methacrylic acid, methacrylate, trifluoromethyl acrylate, methylene-succinic acid, acrylic amide; Said drug numerator can be to be selected from one of following compound: heroin, morphine, cocaine etc.
Another object of the present invention is to provide a kind of described method that is used for the sensitive thin-film material of detecting drugs efficiently for preparing, and comprising:
(1) preparation of noble metal nano particles: a certain proportion of noble metal source and surfactant are mixed in the WS; Under vigorous stirring, dropwise join 11-sulfydryl undecanoic acid toluene solution or dropwise add in the lauryl mercaptan; Obtain the nano noble metal particles that the surface has different functional groups; Add excessive reductive agent then, stir and obtain noble metal nano particles;
(2) preparation of the molecular imprinting polymer membrane that mixes of noble metal nano particles: noble metal nano particles ultrasonic dissolution and pre-reaction under sealing in pore-foaming agent that function monomer, drug numerator and step (1) are obtained; Add crosslinking chemical, initiating agent, ultrasonic and logical nitrogen; Get mixed drop on the silanization microslide, add support membrane, cover metallic film base, put into beaker, in-situ polymerization is carried out in the blanket of nitrogen sealing; Utilize eluant, eluent to remove and be embedded in the drug numerator in the said functional polymer polymer film, under vacuum condition, be dried to weight.
In step (1), described noble metal source can be one of following compound: gold chloride, silver nitrate or chloroplatinic acid; Surfactant is selected from one of following compound: cetyl ammonium bromide or cetyl chloride ammonium; Reductive agent is selected from one of following compound: sodium citrate, sodium borohydride or oxammonium hydrochloride;
In step (2), described function monomer is selected from following one or both compounds: acrylic acid, methacrylic acid, methacrylate, trifluoromethyl acrylate, methylene-succinic acid, acrylic amide; Drug numerator can be to be selected from one of following compound: heroin, morphine, cocaine etc.; Pore-foaming agent is selected from following one or both compounds: chloroform, methylene chloride, acetonitrile, methyl alcohol, N, dinethylformamide, dimethyl sulfoxide (DMSO); Said crosslinking chemical is selected from one of following compound: ethylene glycol dimethacrylate, N, N '-methylene diacrylate amine, N, N '-1,4-phenylene diacrylamine; Said initiating agent is selected from one of following compound: azoisobutyronitrile, ABVN, benzoyl peroxide; Described eluant, eluent is organic solvent and the mixed liquor of acid or the mixed liquor of organic solvent and water and acid; Described organic solvent is methyl alcohol or acetonitrile, and described acid is acetate, and acid is 1: 1～50 with the volume of organic solvent ratio; Water, acid are 1: 1～10: 1～500 with the volume of organic solvent ratio.
Wherein, each raw material consumption proportion is following:
The mol ratio 1 of described noble metal source and described surfactant: 1-3;
The mol ratio 1 of described noble metal source and described 11-sulfydryl undecanoic acid or lauryl mercaptan: 0.5-2;
Described drug numerator and described function monomer mol ratio 1: 3-7;
Described drug numerator and described crosslinking chemical mol ratio are 1: 1-8;
The mol ratio of described initiating agent and described polymerization reaction monomer is 0.06～0.15: 1;
The mol ratio of drug numerator and noble metal nano particles is 1: 1-1: 2;
The volume ratio of function monomer and pore-foaming agent is 1: 100-1: 300.
Further, the present invention also provides the said application that is used for the sensitive thin-film material of detecting drugs efficiently, and described drugs comprise heroin, morphine, cocaine etc., is to adopt surface plasma body resonant vibration technology (SPR) to detect.
Use conventional method to carry out the SPR experiment; Be generally at first fixing reactant on the vane surface; Make it form the molecule sensitive membrane; Through vane, the situation of intermolecular interaction can be reflected by the change of spr signal the sample that will contain determinand then on the vane with constant flow velocity, and entire reaction course is shown and notes through computing machine.
The drugs sensitive chip when testing sample passes through the sensing chip surface, utilizes SPR detection testing sample and the molecular recognition sensitive chip next direct drugs content of measuring in the testing sample of light intensity variation of total reflection light at the interface as the sensing chip of SPR.The concrete operations step is following:
A, the drug numerator of optical sensor identification sensitive chip is fixed among the SPR as sensing chip;
B, organic solvent is flow through the sensing chip surface, treat that reflective light intensity reaches to stablize when constant, reflective light intensity is scanned by angle, note the SPR spectrogram;
C, get the drugs standard solution of variable concentrations,, flow through the surface of surface plasma resonance sensing chip respectively according to by the order of low concentration to high concentration;
The certain density drugs titer of each inflow; With sensing chip reaction 1-5min; Flow through organic solvent then, treat that reflective light intensity reaches to stablize when constant, reflective light intensity is scanned by angle; Note the drugs titer of this concentration and the SPR spectrogram after the sensing chip generation adsorption reaction, so far accomplish the detection of the drugs titer of a concentration;
The rest may be inferred, up to drugs standard solution that obtains each concentration and the reacted SPR spectrogram of sensing chip.
Beneficial effect of the present invention is: the present invention adopts in-situ polymerization technology to form the molecular imprinting polymer membrane that noble metal nano particles mixes on the noble metal film surface; Can be fast; Drugs such as efficient detection heroin, morphine, cocaine wherein, can reach 10 to the detectability of heroin
-9Mol/L.Molecular imprinting polymer membrane physicochemical property of the present invention are stable, can resists very strong mechanical effect, and high temperature resistant, high pressure, acid, alkali and organic solvent are difficult for aspect much, being better than natural biological acceptor molecule by biodegradation destruction; The preparation method is simple, and power consumption is few, and the reaction time is short, and is totally pollution-free, is easy to promote; Be easy to preserve and use than the substrate of biological metal film; Can be repeatedly used, can stable for extended periods of time.The present invention is incorporated into noble metal nano particles in surface plasma body resonant vibration technology and the molecular imprinting coupling system can strengthen the check signal, improves detectability, can promote the development of surface plasma body resonant vibration technology in drug testing.
Description of drawings
Fig. 1 is a kind of sensitive thin-film material structural representation that is used for detecting drugs efficiently of the present invention;
Fig. 2 is the response spectrogram of heroin molecular recognition sensitive thin-film material on SPR among the embodiment 1;
Fig. 3 is the response spectrogram of morphine molecular recognition sensitive thin-film material on SPR among the embodiment 2;
Fig. 4 is the response spectrogram of cocaine molecular recognition sensitive thin-film material on SPR among the embodiment 3;
Fig. 5 is the SPR figure that does not add the sensitive thin-film material of nm of gold in the comparative example 1;
Fig. 6 is the SPR figure that adds the sensitive thin-film material of nm of gold among the embodiment 1.
Embodiment
The sensitive thin-film material that is used for detecting drugs efficiently of the present invention; Be to adopt the in-situ polymerization technology preparation; Promptly on the noble metal film surface; Make function monomer, drug numerator and noble metal nano particles in-situ polymerization, thereby form the molecular imprinting polymer membrane that noble metal nano particles mixes, its structural representation is as shown in Figure 1.
The silanization microslide adopts following method to obtain: with chromic acid lotion, redistilled water and ethanol microslide is not cleaned until having obviously repeatedly at first successively and pollute; Place Piranha solution afterwards, i.e. H
2SO
4: H
2O
2(3: 1, in 50 ℃ of heating 1h, use distilled water, ethanol drip washing more successively, and dry up in mixed solution V/V) with nitrogen; Soaked overnight in the ethanolic solution of 50mM trimethyl chlorosilane makes it silanization at last.
The preparation of support membrane is following: good laboratory is commonly used seals the surface that film tightly is bonded at the silanization microslide with drawing, and marks a square white space with blade at the zone line that seals film again, and the film that seals residual on the microslide is support membrane.
The preparation of metallic film base is following: on the optical cover slide, plate the thick metal film of one deck 47nm through vacuum vapor deposition method, with this as metallic film base.
The aqueous solution of chloraurate of 200ml 15mM and the cetyl ammonium bromide toluene solution of 400ml 1% are mixed; Under vigorous stirring, dropwise join in the 100ml 0.5%11-sulfydryl undecanoic acid toluene solution; The 40mM sodium borohydride that dropwise adds the 100ml new system then stirs 1h and makes the big or small 20nm golden nanometer particle that is.
Take by weighing 18.5mg (0.05mmol) heroin and 17.4mg golden nanometer particle, take by weighing the 0.2mmol methacrylic acid, be dissolved in the solvent of 3mL acetonitrile, vibration, mixing, ultrasonic dissolution 10min, sealing, pre-reaction 3h.Add 0.0793g (0.4mmol) ethylene glycol dimethacrylate in the solution after pre-reaction, the 0.0034g azoisobutyronitrile.Behind the ultrasonic degas 10min, logical N
2Gas 10min.Peek is dripped mixed drop on the silanization microslide, adds support membrane, covers golden film substrate.Put into beaker, logical nitrogen 10min, sealing places heat collecting type heated at constant temperature magnetic stirring apparatus in 60 ℃, reacting by heating 6h in the nitrogen atmosphere.Reaction after finishing separates glass sheet, is dried to weight, and utilizing volume ratio is that 8: 2 the methyl alcohol and the mixed liquor of acetate are removed the heroin molecule in the functional polymer polymer film.The sensitive thin-film material that can be used for efficient detection heroin uniformly.Its detectability to heroin can reach 10
-9Mol/L, as shown in Figure 2 according to the response curve of conventional method on SPR.
Embodiment 2
The silver nitrate aqueous solution of 200ml 15mM and the cetyl chloride ammonium toluene solution of 400ml 1% are mixed; Under vigorous stirring, dropwise join in 100ml 0.5% lauryl mercaptan; The 40mM oxammonium hydrochloride that dropwise adds the 100ml new system then, it is the 60nm Nano silver grain that stirring 1h makes size.
Accurately take by weighing 17.4mg Nano silver grain and microsphere morphine 0.0143g (0.05mmol) and 0.2mmol polymerization reaction monomer acrylic acid, be dissolved in the 3.0mL dimethyl sulfoxide (DMSO), behind the ultrasonic hydrotropy 5min; In above-mentioned mixed liquor, add the crosslinking chemical ethylene glycol dimethacrylate of 0.0496g (0.25mmol) and the initiating agent ABVN of 0.0030g again, behind the ultrasonication 5min, logical nitrogen deoxygenation 5mim; Peek is dripped mixed drop on the silanization microslide, adds support membrane, covers the platinum substrate.Put into beaker, logical nitrogen 10min, sealing is at nitrogen atmosphere medium ultraviolet light irradiation reaction 5h.After reaction finishes, glass sheet is separated, utilizing volume ratio is that the mixed liquor of 4: 1: 1 methyl alcohol, acetate and water is removed the morphine molecule in the functional polymer polymer film.After wash-out finishes, under vacuum condition, be dried to weight, be used for the sensitive thin-film material of efficient detection heroin at last uniformly.Detectability can reach 10
-9Mol/L.As shown in Figure 3 according to the response curve of conventional method on surface plasma resonance sensor.
Embodiment 3
The chloroplatinic acid aqueous solution of 200ml 15mM and the cetyl ammonium bromide toluene solution of 400ml 1% are mixed; Under vigorous stirring, dropwise join in 100ml 0.5% lauryl mercaptan; The 40mM sodium citrate that dropwise adds the 100ml new system then stirs 1h and makes the big or small nano platinum particle of 100nm that is.
Take by weighing 15.15mg (0.05mmol) cocaine and 17.4mg nano platinum particle, 0.2mmol polymerization reaction monomer methylene-succinic acid is dissolved in the solvent of 3mL methylene chloride, vibration, mixing, ultrasonic dissolution 10min, sealing, pre-reaction 3h.The crosslinking chemical ethylene glycol dimethacrylate that adds 0.1189g (0.6mmol) in the solution after pre-reaction, the 0.0034g benzoyl peroxide.Behind the ultrasonic degas 10min, logical N2 gas 10min.Peek is dripped mixed drop on the silanization microslide, adds support membrane, covers the silverskin substrate.Put into beaker, logical nitrogen 10min, sealing places heat collecting type heated at constant temperature magnetic stirring apparatus in 60 ℃, reacting by heating 6h in the nitrogen atmosphere.Reaction after finishing separates glass sheet, and utilizing volume ratio is that 7: 3 the methyl alcohol and the mixed liquor of acetate are removed the cocaine molecule in the functional polymer polymer film.The sensitive thin-film material that can be used for the efficient detection cocaine uniformly.Detectability can reach 10
-9Mol/L.As shown in Figure 4 according to the response curve of conventional method on surface plasma resonance sensor.
Comparative example 1
Method according to application number 200910119164.5 prepares the sensitive thin-film material that does not add nm of gold, and its response curve on SPR is as shown in Figure 5.
Fig. 6 is the SPR figure of the sensitive thin-film material of embodiment 1 gained adding nm of gold.Visible like Fig. 5 and Fig. 6, do not add nm of gold, detectability is 10
-8Mol/l has added the nm of gold detectability 10
-9Mol/l, and TM type optical waveguide spike appears, more help quantitative test.
Claims (11)
1. sensitive thin-film material that is used for detecting drugs efficiently; It is characterized in that this membraneous material is to adopt the in-situ polymerization technology preparation; Promptly on the noble metal film surface; Make function monomer, drug numerator and noble metal nano particles in-situ polymerization, thereby form the molecular imprinting polymer membrane that noble metal nano particles mixes.
2. the sensitive thin-film material that is used for detecting drugs efficiently as claimed in claim 1 is characterized in that described noble metal nano particles is gold, silver, nano platinum particle.
3. the sensitive thin-film material that is used for detecting drugs efficiently as claimed in claim 1 is characterized in that, said noble metal nano particles size is 20-100nm.
4. like each said sensitive thin-film material that is used for detecting drugs efficiently among the claim 1-3; It is characterized in that said noble metal nano particles prepares through following method: noble metal source and surfactant are mixed in the WS; Under vigorous stirring, dropwise join the toluene solution of 11-sulfydryl undecanoic acid or dropwise be added in the lauryl mercaptan; Add excessive reductive agent then, stirring obtains.
5. like the said sensitive thin-film material that is used for detecting drugs efficiently of claim 4, it is characterized in that: the mol ratio of said noble metal source and said surfactant is 1: 1-3; The mol ratio of said noble metal source and said 11-sulfydryl undecanoic acid or lauryl mercaptan is 1: 0.5-2; Described noble metal source is to be selected from one of following compound: gold chloride, silver nitrate or chloroplatinic acid; Surfactant is to be selected from one of following compound: cetyl ammonium bromide or cetyl chloride ammonium; Reductive agent is to be selected from one of following compound: sodium citrate, sodium borohydride or oxammonium hydrochloride.
6. the sensitive thin-film material that is used for detecting drugs efficiently as claimed in claim 1 is characterized in that: described in-situ polymerization technology is original position thermal polymerization or original position photopolymerization.
7. the sensitive thin-film material that is used for detecting drugs efficiently as claimed in claim 1 is characterized in that: described noble metal film is a kind of in golden film, silverskin, aluminium film or the copper film; Described function monomer is selected from following one or both compounds: acrylic acid, methacrylic acid, methacrylate, trifluoromethyl acrylate, methylene-succinic acid, acrylic amide; Said drug numerator is to be selected from one of following compound: heroin, morphine, cocaine.
8. one kind prepares the method that is used for the sensitive thin-film material of detecting drugs efficiently as claimed in claim 1, it is characterized in that:
(1) preparation of noble metal nano particles: a certain proportion of noble metal source and surfactant are mixed in the WS; Under vigorous stirring, dropwise join the toluene solution of 11-sulfydryl undecanoic acid or dropwise add in the lauryl mercaptan; Obtain the nano noble metal particles that the surface has different functional groups; Add excessive reductive agent then, stir and obtain noble metal nano particles;
(2) preparation of the molecular imprinting polymer membrane that mixes of noble metal nano particles: noble metal nano particles ultrasonic dissolution and pre-reaction under sealing in pore-foaming agent that function monomer, drug numerator and step (1) are obtained; Add crosslinking chemical, initiating agent, ultrasonic and logical nitrogen; Get mixed drop on the silanization microslide, add support membrane, cover metallic film base, put into beaker, in-situ polymerization is carried out in the blanket of nitrogen sealing; Utilize eluant, eluent to remove and be embedded in the drug numerator in the said functional polymer polymer film, under vacuum condition, be dried to constant weight.
9. preparation method as claimed in claim 8 is characterized in that:
In step (1), described noble metal source is one of following compound: gold chloride, silver nitrate or chloroplatinic acid; Surfactant is selected from one of following compound: cetyl ammonium bromide or cetyl chloride ammonium; Reductive agent is selected from one of following compound: sodium citrate, sodium borohydride or oxammonium hydrochloride;
In step (2), described function monomer is selected from following one or both compounds: acrylic acid, methacrylic acid, methacrylate, trifluoromethyl acrylate, methylene-succinic acid, acrylic amide; Drug numerator is to be selected from one of following compound: heroin, morphine, cocaine; Pore-foaming agent is selected from following one or both compounds: chloroform, methylene chloride, acetonitrile, methyl alcohol, N, dinethylformamide, dimethyl sulfoxide (DMSO); Said crosslinking chemical is selected from one of following compound: ethylene glycol dimethacrylate, N, N '-methylene diacrylate amine, N, N '-1,4-phenylene diacrylamine; Said initiating agent is selected from one of following compound: azoisobutyronitrile, ABVN, benzoyl peroxide; Described eluant, eluent is organic solvent and the mixed liquor of acid or the mixed liquor of organic solvent and water and acid; Described organic solvent is methyl alcohol or acetonitrile, and described acid is acetate, and acid is 1: 1～50 with the volume of organic solvent ratio; Water, acid are 1: 1～10: 1～500 with the volume of organic solvent ratio.
10. like claim 8 or 9 described preparation methods, it is characterized in that each raw material consumption proportion is following:
The mol ratio of described noble metal source and described surfactant is 1: 1-3;
The mol ratio of described noble metal source and described 11-sulfydryl undecanoic acid or lauryl mercaptan is 1: 0.5-2;
Described drug numerator and described function monomer mol ratio 1: 3-7;
Described drug numerator and described crosslinking chemical mol ratio are 1: 1-8;
The mol ratio of described initiating agent and described function monomer is 0.06～0.15: 1;
The mol ratio of drug numerator and noble metal nano particles is 1: 1-1: 2;
The volume ratio of function monomer and pore-foaming agent is 1: 100-1: 300.
11. a kind of application that is used for the sensitive thin-film material of detecting drugs efficiently as claimed in claim 1, it is characterized in that: described drugs comprise heroin, morphine, cocaine, adopt the surface plasma body resonant vibration technology for detection.
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| CN105675563B (en) * | 2016-01-20 | 2018-06-26 | 广州阳普医疗科技股份有限公司 | A kind of cocaine fast quantitative measurement method for detecting suitable for Site Detection |
| CN106568744A (en) * | 2016-10-08 | 2017-04-19 | 浙江警察学院 | Method for detecting cocaine based on SPR technology |
| CN107238713A (en) * | 2017-06-23 | 2017-10-10 | 浙江诺迦生物科技有限公司 | The detection method of trace hemp and the SPR chips used in a kind of saliva sample |
| CN107930599B (en) * | 2017-08-23 | 2021-03-16 | 公安部物证鉴定中心 | Magnetic material for pretreatment of aqueous solution drug test material and preparation method thereof |
| CN109465466A (en) * | 2018-12-21 | 2019-03-15 | 江苏经贸职业技术学院 | A kind of synthetic method based on oxidation-reduction method reduction simple substance silver nanoclusters |
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