CN102156119B - Method for detecting potential information in fingerprints by utilizing Raman spectrum - Google Patents
Method for detecting potential information in fingerprints by utilizing Raman spectrum Download PDFInfo
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- CN102156119B CN102156119B CN201110117719XA CN201110117719A CN102156119B CN 102156119 B CN102156119 B CN 102156119B CN 201110117719X A CN201110117719X A CN 201110117719XA CN 201110117719 A CN201110117719 A CN 201110117719A CN 102156119 B CN102156119 B CN 102156119B
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Abstract
The invention belongs to the technical field of detection technology, specifically relates to a method for displaying potential fingerprints and detecting the potential information in fingerprints by utilizing a Raman spectrum. In the invention, while sweat potential fingerprints are displayed, the displayed potential information of specific proteins and the like in fingerprint metabolites is detected by the antibody specificity recognition technology combining with the Raman spectrum analysis. First the antibody of a target metabolite, to be detected, and molecular modified gold nanoparticles with characteristic Raman signals, are selected to be prepared into a detecting probe; the detecting probe is acted with the fingerprints to be detected, so that the antibody is combined with the target metabolite in the detected fingerprints by a specific action for generating immuno reaction; and silvers are reduced on the surface of the fingerprints by argentation, and the Raman spectrum of the sample is tested. The method can accurately detect the existence of a certain feature metabolite of the sweat in fingerprints, and has the advantages that the sensitivity is high, the speed is fast, operations are easy, and specificity is provided.
Description
Technical field
The invention belongs to the detection technique field, be specifically related to manifest laten fingerprints and utilize Raman spectrum to detect the method for the potential information that laten fingerprints carries.
Background technology
Fingerprint identification is one of the method the most reliably of carrying out individual identification, and fingerprint plays important evidential function in forensic science and criminal suit process.Fingerprint not only can be differentiated people's identity, and recently, but the scientist of Britain finds a people's age even life style; Such as often eating what medicine, use any cosmetics, smoking state, life zone at ordinary times etc.; Can reflect (R.Leggett, E.E.Lee-Smith, S.M.Jickells, D .A.Russell through fingerprint; Angew.Chem.Int .Ed.2007,46,4100-4103.).Therefore, through fingerprint except identifying individual identity, can also be through the metabolin in the fingerprint sweat be analyzed; Further detect other individual potential information for example whether smoking, drug abuse etc., obtain more how valuable personal feature information like this, can in crime survey, find information about the person's life style that stays the fingerprint; So that dwindle suspect's scope (P.Hazarika, S.M.Jickells, K.Wolff; D.A.Russell; Angew.Chem.Int.Ed.2008,47,10167-10170).For example can disclose whether the suspect takes drugs, smoking, take medicine and food that he ate or the like, also can make a definite diagnosis some disease simultaneously, help in case judgement with break a case and discern criminal etc. by fingerprint.
Sweat composition in people's the fingerprint is identical, the 98%th, and water, remaining is bodies of gland such as sebum; Composition is some organic substances; Like amino acid, urea etc., also have some dead matter, like some metal cations, negative ion etc.; They are relevant with people's diet mostly, and these all are human homergy's in the normal life products.If the organic product after its metabolism of consume illegal drugs also can be stayed in the sweat gland of fingerprint, also can become one of information of fingerprint identification through pore naturally with sweat.Raman spectrum provides fast, simple, can repeat and the more important thing is undamaged qualitative and quantitative analysis; It need not sample and prepares; Sample can utilize surface enhanced raman technique just can strengthen the sensitivity of Raman spectrum greatly directly through fibre-optical probe or through glass, quartz and optical fiber measurement.Surface enhancement Raman spectroscopy (SERS) has become active in an analyzing and testing research field.Utilize specific antibody and the Markers for Detection probe with Raman signal, the sensitive Raman signal of recognition reaction combination through specific antibody can accurately detect target protein delicately, is a kind of detection method that integrates multiple advantage.Utilize this method that the probe of laten fingerprints through specific antibody and Raman and molecular labeling manifested and detect, obtain the result fingerprint image not only is provided, and fingerprint supplier's individual metabolic information is provided, help in case, judging and identification criminal etc.
In addition; At present; Drug abuse detects when the personnel that are accused of taking drugs being carried out the biomedicine detection, detects the biological specimens such as urine, blood or hair of sample for the personnel to be detected of collection, researches and develops detection method more simple to operation and detects sample range with expansion; Simplify the operation course, will assert the drug abuse behavior for public security organ provides scientific basis and increases work efficiency.
The present invention has realized when manifesting the sweat laten fingerprints, combines the potential informations such as specific proteins in the fingerprint metabolin after the Raman spectroscopy analyzing and testing manifests with antibody labeling.
Summary of the invention
The objective of the invention is when manifesting the sweat laten fingerprints, combine the potential informations such as specific proteins in the fingerprint metabolin after the Raman spectroscopy analyzing and testing manifests with the antibody specificity recognition technology.
At first selection needs the antibody (as detecting metabolin---the Tianning of nicotine, needing the antibody with anti-Tianning) of the target metabolin of detection, modifies gold nano grain with this target antibody and the molecule with characteristic Raman signal (as to thin basic aniline, to dredging yl benzoic acid etc.); Process detector probe, this probe and fingerprint effect to be measured then makes antibody through the specific effect generation immune response that combines with target metabolin in the tested fingerprint; Rinse out the gold nano grain probe that does not react with big water gaging then; If there is the target metabolin in the fingerprint, the reason that gold nano grain combines with it owing to antibody is stayed in the fingerprint, if do not deposit the target metabolin; Then gold nano grain can be washed off from fingerprint sample; Utilize argentation that silver is reduced on the fingerprint surface then, the silver of generation covers the sweat residual fraction of fingerprint, with this sample test Raman spectrum; If can obtain the Raman signal of characteristic; Then prove to have the target metabolin in the fingerprint sample,, then prove not have the target metabolin in the fingerprint sample if can not get the Raman signal of characteristic.This method can accurately detect the existence of certain characteristic metabolin of sweat in the fingerprint, and is sensitive high, possesses specificity.
To detect the metabolin of nicotine in the individual fingerprint---the method for Tianning is an example:
1, the preparation of probe:
At first utilize citric acid to receive the gold nano grain for preparing 15nm as reductive agent; Be modified at promptly anti-Tianning of the antibody of Tianning and Raman signal molecule (to thin basic aniline, to dredging yl benzoic acid) on the gold nano grain respectively then; Be prepared into the detector probe of Tianning, concrete steps are following:
After the 1mM/L chlorauric acid solution heated and boiled of 100mL, add the 38.8mM/L sodium citrate solution of 10mL while stirring, continue heating after 15 minutes, be stirred to solution temperature and reduce to room temperature, gained solution is red gold nano grain solution, is of a size of 15nm.Get 10 of 4-5mL gold nano grain and 20-50 μ L
-4-10
-6After the anti-Tianning solution of M/L vertically mixes 10-24 hour; Centrifugally discard unreacted antibody and be distributed to the gold nano grain that promptly obtains anti-Tianning mark in the ultrapure water of equivalent again; To add the 0.1mM/L that dredges basic aniline (or to dredging yl benzoic acid) 20-50 μ L then and continue vertical the mixing 10-24 hour; Centrifugally then discard unreacted Raman molecular to dredging basic aniline (or to dredging yl benzoic acid); Again be distributed in the ultrapure water, obtain by anti-Tianning with to dredging the gold nano-probe of basic aniline (or to dredging yl benzoic acid) mark, the i.e. detector probe of specificity sign.
2, detect the fingerprint metabolin
The gold nano-probe probe of above-mentioned preparation is dropped on the fingerprint sample to be measured; Left standstill 5-20 minute; The antibody that makes gold nano-probe surface fully reacts with Tianning in the residual sweat metabolin of fingerprint, and gold nano-probe is fixed on the fingerprint surface through specific effect, washes fingerprint sample 5-10 minute with a large amount of water then; Unreacted gold nano-probe is rinsed out; The silver of then fingerprint sample being put into new preparation dyed solution 5-15 minute, made under the catalytic action of the Au probe that silver fixedly retains in fingerprint and was reduced and is deposited on the surface of gold nano-probe, thereby strengthened the signal representation of fingerprint; Wash with big water gaging again after taking out fingerprint sample; The Raman spectrum of test fingerprint sample (laser wavelength is at 488nm or 514nm) then then shows the metabolin that nicotine is arranged in the fingerprint sample if obtain the characteristic peak of mark Raman molecular---the existence of Tianning proves the person's smoking that provides the fingerprint; Otherwise do not have the existence of Tianning in the explanation fingerprint sample, prove the person's non-smoking that provides the fingerprint.(silver dyes solution by 0.02 gram nitric acid, and 0.5 gram p-dihydroxy-benzene, 5mL pH are that 3.8 citric acid solution mixes afterwards formulated with 15mL water.)
3, said method is example with the Tianning, this method is also applicable to the detection of the metabolin of medicine, like cannabinol, methadone, ***e, morphine etc., only needs when the preparation probe, select the antibody of corresponding metabolin, and other step is identical.
The present invention has following advantage:
1, sensitive high, quick, easy to operate.
2, do not need large-scale instrument, be convenient to the on-site real-time fast detecting.
Description of drawings
Accompanying drawing 1 is the image that manifests of glass surface smoker laten fingerprints;
Accompanying drawing 2 is Raman spectrum (the smokeless fingerprint of a. smoker fingerprint b.).
Embodiment
Embodiment 1: through fingerprint detection nicotine metabolite thing---Tianning
(1) preparation of probe:
At first utilize citric acid to receive the gold nano grain for preparing 15nm as reductive agent, then with the antibody of Tianning---anti-Tianning and Raman molecular (to dredge basic aniline, to dredging yl benzoic acid) be modified on the gold nano grain, concrete steps are following:
After the 1mM/L chlorauric acid solution heated and boiled of 100mL, add the 38.8mM/L sodium citrate solution of 10mL while stirring, continue heating after 15 minutes, be stirred to solution temperature and reduce to room temperature, gained solution is red gold nano grain solution.Get 4mL gold nano grain and 20 μ L 10
-5The anti-Tianning solution of M/L is vertical to be mixed after 12 hours; Centrifugally discard unreacted antibody and be distributed to the gold nano grain that promptly obtains anti-Tianning mark in the ultrapure water of equivalent again; Then the 0.1mM/L of 20 μ L is added and continues vertical the mixing 12 hours dredging basic aniline solution, centrifugally then discard unreactedly, be distributed in the ultrapure water again dredging basic aniline; Promptly obtain by anti-Tianning with to dredging the gold nano-probe of basic aniline mark, i.e. the detector probe of specificity sign.
(2) detect the fingerprint metabolin
The gold nano-probe of above-mentioned preparation is dropped on the fingerprint sample to be measured, left standstill 10 minutes, the Tianning in the residual sweat metabolin of antibody and fingerprint on gold nano-probe surface is fully reacted; Gold nano-probe is fixed on the fingerprint surface through specific effect, washed fingerprint sample 5 minutes with a large amount of water then, unreacted gold nano-probe is rinsed out; The silver of then fingerprint sample being put into new preparation dyed solution 10 minutes; Make under the catalytic action of the Au probe that in fingerprint, fixedly retains of silver and be reduced and be deposited on the surface of gold nano-probe, thereby strengthened the signal representation of fingerprint, wash with big water gaging again after taking out fingerprint sample; The Raman spectrum of test fingerprint sample then; The testing laser wave band is 488nm, and the characteristic peak that obtains the mark Raman molecular then shows the metabolin that nicotine is arranged in the fingerprint sample---the existence of Tianning proves the person's smoking that provides the fingerprint; Otherwise do not have the existence of Tianning in the explanation fingerprint sample, prove the person's non-smoking that provides the fingerprint.(silver dyes solution by 0.02 gram nitric acid, and 0.5 gram p-dihydroxy-benzene, 5mL pH are that 3.8 citric acid solution mixes afterwards formulated with 15mL water.)
Embodiment 2: through fingerprint detection anaesthetic morphine
(1) preparation of probe:
At first utilize citric acid to receive the gold nano grain for preparing 15nm as reductive agent, will resist the antibody of morphine then---anti-morphine and Raman molecular (to dredge basic aniline, to dredging yl benzoic acid) be modified on the gold nano grain, concrete steps are following:
After the 1mM/L chlorauric acid solution heated and boiled of 100mL, add the 38.8mM/L sodium citrate solution of 10mL while stirring, continue heating after 15 minutes, be stirred to solution temperature and reduce to room temperature, gained solution is red gold nano grain solution.Get 4mL gold nano grain and 20 μ L 10
-5The anti-morphine solution of M/L is vertical to be mixed after 12 hours; Centrifugally discard unreacted antibody and be distributed to the gold nano grain that promptly obtains anti-morphine mark in the ultrapure water of equivalent again; Then the 0.1mM/L of 20 μ L is added and continues vertical the mixing 12 hours dredging basic aniline solution, centrifugally then discard unreactedly, be distributed in the ultrapure water again dredging basic aniline; Promptly obtain by anti-morphine with to dredging the gold nano-probe of basic aniline mark, i.e. the detector probe of specificity sign.
(2) detect the fingerprint metabolin
The gold nano-probe of above-mentioned preparation is dropped on the fingerprint sample to be measured, left standstill 10 minutes, the morphine in the residual sweat metabolin of antibody and fingerprint on gold nano-probe surface is fully reacted; Gold nano-probe is fixed on the fingerprint surface through specific effect, washed fingerprint sample 5 minutes with a large amount of water then, unreacted gold nano-probe is rinsed out; The silver of then fingerprint sample being put into new preparation dyed solution 10 minutes; Make under the catalytic action of the Au probe that in fingerprint, fixedly retains of silver and be reduced and be deposited on the surface of gold nano-probe, thereby strengthened the signal representation of fingerprint, wash with big water gaging again after taking out fingerprint sample; The Raman spectrum of test fingerprint sample then; The testing laser wave band is 488nm, and the characteristic peak that obtains the mark Raman molecular then shows the existence that morphine is arranged in the fingerprint sample, and proving provides the fingerprint person took morphine; Otherwise do not have the existence of morphine in the explanation fingerprint sample, proving provides the fingerprint person did not obey morphine.(silver dyes solution by 0.02 gram nitric acid, and 0.5 gram p-dihydroxy-benzene, 5mLpH are that 3.8 citric acid solution mixes afterwards formulated with 15mL water.)
Claims (1)
1. utilize Raman spectrum to detect the method for potential information in the fingerprint, it is characterized in that:
1), the preparation of probe:
At first utilize sodium citrate to prepare the gold nano grain of 15nm as reductive agent; Then with promptly anti-Tianning of the antibody of Tianning and Raman signal molecule p-Mercaptoaniline or be modified on the gold nano grain respectively to mercaptobenzoic acid; Be prepared into the detector probe of Tianning, concrete steps are following:
After the 1mM/L chlorauric acid solution heated and boiled of 100mL; The 38.8mM/L sodium citrate solution that adds 10mL while stirring; Continue heating after 15 minutes, be stirred to solution temperature and reduce to room temperature, gained solution is red gold nano grain solution; Be of a size of 15nm, get 10 of 4-5mL gold nano grain and 20-50 μ L
-4-10
-6After the anti-Tianning solution of M/L fully mixes 10-24 hour; Centrifugally discard unreacted antibody and be distributed to the gold nano grain that promptly obtains anti-Tianning mark in the ultrapure water of equivalent again; Add with p-Mercaptoaniline or to the 0.1mM/L of mercaptobenzoic acid 20-50 μ L then and continue vertical the mixing 10-24 hour; Centrifugally then discard unreacted Raman molecular p-Mercaptoaniline or to mercaptobenzoic acid; Again be distributed in the ultrapure water, obtain by anti-Tianning and p-Mercaptoaniline or to the gold nano-probe of mercaptobenzoic acid mark, the i.e. detector probe of specificity sign;
2), detect the fingerprint metabolin:
The gold nano-probe probe of above-mentioned preparation is dropped on the fingerprint sample to be measured; Left standstill 5-20 minute, the Tianning in the residual sweat metabolin of antibody and fingerprint on gold nano-probe surface is fully reacted, gold nano-probe is fixed on the fingerprint surface through specific effect; Washed fingerprint sample 5-10 minute with a large amount of water then; Unreacted gold nano-probe is rinsed out, then fingerprint sample is put into by 0.02 gram silver nitrate 0.5 gram p-dihydroxy-benzene; 5mLpH is that 3.8 citric acid solution and 15mL water mix the formulated silver in back and dyed in the solution 5-15 minute; Make the surface that is reduced and is deposited on gold nano-probe under the catalytic action of the Au probe that in fingerprint, fixedly retains of silver, wash with big water gaging after taking out fingerprint sample again, the test fingerprint sample is at 488nm or 514nm Raman spectrum then; If the characteristic peak that obtains the mark Raman molecular then shows the existence of metabolin-Tianning that nicotine is arranged in the fingerprint sample; The proof person's smoking that provides the fingerprint, otherwise do not have the existence of Tianning in the explanation fingerprint sample proves the person's non-smoking that provides the fingerprint.
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| CN106770178A (en) * | 2017-01-23 | 2017-05-31 | 吉林大学 | A kind of kit of utilization fingerprint quick detection diabetes |
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| CN103536297B (en) * | 2013-10-18 | 2015-06-17 | 浙江大学 | Immune colloidal gold based latent fingerprint imaging method |
| CN103536296B (en) * | 2013-10-18 | 2015-06-17 | 浙江大学 | Method of detecting human sweat secretion |
| CN103784149B (en) * | 2014-03-05 | 2015-09-23 | 北京科技大学 | A kind of many metal deposition technique manifest the method for laten fingerprints |
| CN105388140B (en) * | 2015-12-01 | 2017-05-10 | 杭州中车车辆有限公司 | Measuring instrument for site invisible fingerprint display and contained substance thereof |
| CN106841150B (en) * | 2017-03-17 | 2019-10-15 | 浙江警察学院 | A kind of method that fingerprint leaves a variety of illicit drugs identifications and fingerprint imaging |
| CN107328757B (en) * | 2017-08-25 | 2020-01-03 | 西南大学 | Composite membrane for latent fingerprint transfer, development or inclusion integrated full-dry state detection and detection method |
| CN114354570A (en) * | 2021-12-16 | 2022-04-15 | 安徽中科赛飞尔科技有限公司 | SERS (surface enhanced Raman scattering) detection method for drug molecule movement of drug on fingerprint surface of drug addict |
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| CN1763529A (en) * | 2005-09-26 | 2006-04-26 | 东北师范大学 | Preparation process for semiconductor nanocrystal using Raman signal to marking organism |
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| WO2007119197A1 (en) * | 2006-04-13 | 2007-10-25 | Koninklijke Philips Electronics N.V. | Surface enhanced resonant raman spectroscopy |
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| CN106770178B (en) * | 2017-01-23 | 2019-07-23 | 吉林大学 | A kind of kit quickly detecting diabetes using fingerprint |
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Inventor after: Wang Chungang Inventor after: Su Zhongmin Inventor after: Chai Fang Inventor after: Luo Shunrui Inventor after: Wang Tingting Inventor after: Li Lu Inventor before: Su Zhongmin Inventor before: Chai Fang Inventor before: Wang Chungang Inventor before: Luo Shunrui Inventor before: Wang Tingting Inventor before: Li Lu |
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Free format text: CORRECT: INVENTOR; FROM: SU ZHONGMIN CHAI FANG WANG CHUNGANG LUO SHUNRUI WANG TINGTING LI LU TO: WANG CHUNGANG SU ZHONGMIN CHAI FANG LUO SHUNRUI WANG TINGTING LI LU |
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