CN103598890A - High-resolution latent blood fingerprint image collecting method based on scanning electrochemical microscope (SECM) - Google Patents
High-resolution latent blood fingerprint image collecting method based on scanning electrochemical microscope (SECM) Download PDFInfo
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Abstract
The invention relates to a method for using a scanning electrochemical microscope (SECM) in coordination with silver staining to collect latent blood fingerprint image in a high-resolution way and belongs to the technical field of fingerprint identification. The method includes: using the principle that Ag+ ions combines with protein components in the blood of the ridge line are of a fingerprint and is reduced to Ag nano particles with electrochemical activity instead of reacting with the substrate in the valley line area to allow the fingerprint ridge line area and the fingerprint valley line area to form electrochemical activity difference; adding redox medium K3IrCl6 to solution, using the principle that the K3IrCl6 reacts with the Ag metal particles in the ridge line area to generate positive feedback effect instead of reacting with the valley line area to perform blood finger print collection based on SECM. The method has the advantages that image resolution is high, third-level fingerprint information can be collected, and the ideal latent blood fingerprint high-resolution image collecting method is promising in application prospect in the field of fingerprint identification.
Description
Technical field
The method that the present invention relates to adopt scan-type electrochemical microscope (SECM) and silver-colored dyeing technique to combine high-resolution and gather blood latent dactylogram image, belongs to technique of fingerprint indentification field.
Background technology
In the major serious cases such as homicide, robbery, hematochezia fingerprint often can be left in scene, and effectively fingerprint manifestation and image acquisition can provide for the detection of merit important clue and strong evidence.Therefore it is very important, in scene of a crime, finding and extract blood fingerprint.Blood fingerprint is divided into two classes conventionally: a class is visible blood fingerprint, refers to exist compared with large contrast and obvious visible fingerprint between wine-colored blood streakline and substrate background; Another kind of is potential blood fingerprint, refers to less containing blood volume or is retained in the faint or unclear fingerprint on dark substrate surface.For occult blood fingerprint, conventionally need to use special photographic method, chemical reagent and physical material to process, it is manifested or strengthen.
Fingerprint image comprises the information of three levels: the profile of the first level---fingerprint, as whorl, dustpan-shaped stricture of vagina line; The second level---the trend of streakline in fingerprint, as the termination of streakline, bifurcated, island shape stricture of vagina etc.; The 3rd level---shape and the relative position of pore on fingerprint ridge.The fingerprint image of obtaining at present be take the first level and the second level as main, the method that can obtain the 3rd horizontal information in fingerprint is few, and in scene of a crime, the fingerprint that suspect stays is ever-changing, the fingerprint of some of them incompleteness is still not enough to carry out authentication by the information of first and second level, therefore in the urgent need to developing high-resolution image-pickup method and technology.
The process of fingerprint collecting is the process of fingerprint imaging in essence.Its principle is different according to geometrical property, physical features and the biological nature in ridge and valley, to obtain different feedback signals, according to the value of feedback signal, plots fingerprint image.The quality of fingerprint image can directly have influence on the precision of identification and the processing speed of fingerprint recognition system.High-quality fingerprint image can be simplified the algorithm that fingerprint image is processed greatly, improves discrimination.Therefore fingerprint collecting technology is one of key technology of fingerprint recognition system.At present, high-quality fingerprint collecting technology has become the important subject with broad prospect of application.
Fingerprint collecting is mainly divided into three major types according to the difference of signal adapter technology in the market: optical finger print collection, semiconductor fingerprint collection and ultrasound wave fingerprint collecting.But also exist, imaging resolution is not high, cost is higher and gatherer process is loaded down with trivial details.We know, electro-chemical conversion device has higher sensitivity, easily microminiaturized, easy of integrationization, many advantages such as can in muddy solution, operate, and required instrument is simple, cheap, because being widely used in the preparation of sensor, as electrochemical DNA biosensor, electrochemical enzymatic sensor, electrochemical immunosensor, electrochemistry cell sensor etc.But the application of scan-type electrochemical microscope in blood latent dactylogram sample of high-resolution image also do not reported so far.
SECM is a kind of of scanning probe microscopy, and it can utilize the difference of substrate material surface chemical reactivity and the pattern of substrate is carried out to imaging.The present invention is in order to obtain high-resolution blood fingerprint detection image, and the detection for blood latent dactylogram by scan-type electrochemical microscope first, has invented a kind of high-resolution blood fingerprint image acquisition method that can stably obtain fingerprint the 3rd horizontal information.Principle of the present invention is, in blood contained protein ingredient can with Ag
+ions binding is also reduced to the Ag nanoparticle with electro-chemical activity, and human body sweat gland secretion thing also contains protein ingredient, therefore also can be applied in theory the high-resolution imaging of invisible fingerprints of sweat and oily laten fingerprints.
Summary of the invention
The object of the invention is: the image acquisition resolution existing for current blood fingerprint detection technology is low, needs the demand that development can provide the detection technique of the 3rd horizontal finger print information badly, first Scanning electrochemical microscopy is applied to the image acquisition of blood fingerprint.The present invention has simply, can in solution, carry out,, imaging high-resolution advantage harmless to operator.
The present invention adopts scan-type electrochemical microscope to carry out scanning imagery to the blood latent dactylogram of dielectric base (as PVDF membrane, poly-ethylene diester) surface A g nanoparticle label.Be characterized in first utilizing Ag
+the protein ingredient of ion in the blood of fingerprint ridge line region is combined and is reduced to the Ag nanoparticle with electro-chemical activity, and the principle of not reacting with the substrate of valley line region makes fingerprint ridge line and valley line region form electro-chemical activity difference; Recycling scan-type electrochemical microscope carries out image acquisition to the successful blood fingerprint sample of labelling, and principle is in solution, to add redox mediator K
3irCl
6after, the oxidant oxidation Ag metallic that it produces on probe is Ag
+be dissolved in solution, this process can make probe current significantly increase; And fingerprint valley line district and substrate do not have such positive feedback effect because do not contain Ag metallic, thereby realize high-resolution blood latent dactylogram image acquisition.
The method concrete operations comprise the following steps:
1) take sodium carbonate as preparation of raw material stock solution A, ammonium nitrate, silver nitrate, silicon wolframic acid, formaldehyde are preparation of raw material stock solution B, and the certain proportion of usining during reaction mixes the solution as Ag nanoparticle label blood fingerprint.
2) volunteer will hand-wash totally, and finger dips whole blood, restrains fresh blood fingerprint in dielectric base.
3) stock solution step 1) being made is mix homogeneously according to a certain volume, and fingerprint sample is placed in to mixed liquor, carries out labelling in agitator.
4) preparation electrochemical reaction solution, polishing scan-probe, sets sweep parameter, utilizes scan-type electrochemical microscope to carry out image acquisition experiment to the successful blood fingerprint sample of labelling.
Above-mentioned steps 1) specifically comprise the following steps:
(1) 1.25g sodium carbonate is dissolved, be transferred in 25mL volumetric flask, ultra-pure water standardize solution, is called stock solution A.
(2) by 0.05g ammonium nitrate, 0.05g silver nitrate, 0.25g silicon wolframic acid, 125 μ L formaldehyde are put into small beaker and are dissolved, and are transferred in 25mL volumetric flask, and ultra-pure water standardize solution, is called stock solution B.
Above-mentioned steps 2) specifically comprise the following steps:
(1) from hospital, obtain the whole blood of Healthy People.
(2) volunteer will hand-wash only, dry, and finger dips whole blood, and unnecessary blood is erased in the centre of the palm of another hands, smoothens, and with appropriate strength, by being pressed in dielectric base, obtains fresh blood fingerprint.
Above-mentioned steps 3) specifically comprise the following steps:
(1) use 1% sodium acetate or alcoholic solution to the fixing 15min of fingerprint, after taking-up, with ultra-pure water, rinse 1～2min; Put into again 0.1% hypo solution and activate 15min, after taking-up, with ultra-pure water, rinse 1～2min.
(2) by stock solution A and B 1:1 mix homogeneously by volume, fingerprint sample is placed in to mixed liquor, in agitator, carries out labelling.
(3) after fingerprint manifestation, sample is put into 10% acetic acid solution 10min reaction is stopped, after taking-up, with ultra-pure water, rinsing, dry.
Above-mentioned steps 4) specifically comprise the following steps:
(1) preparation is with KNO
3as supporting electrolyte, with certain density K
3irCl
6(maybe can produce other compound of oxidable silver) is as the electrochemical reaction solution of redox mediator; Preparation KNO
3method as electrochemical reaction liquid is: take 0.0261g K
3irCl
6with 0.2528g KNO
3, dissolve, being mixed with concentration is 2mmol/L K
3irCl
6+ 0.1mol/L KNO
3.
(2) by the disk platinum microelectrode that sand paper is 25 μ m by the diameter of bottom end seal, polish, make its tip become taper shape, and meet glass shell radius and be less than 10 with the ratio of tip radius, as the probe of blood fingerprint image acquisition.
(3) before imaging, microelectrode state is characterized, and utilize asymptotic curve near substrate.
(4) take the Microdisk electrode that diameter is 25 μ m is working electrode, the Ag silk reference electrode that is as the criterion, Pt silk is that setting probe current potential is that 0.8V, sweep speed are 640 μ m/s to electricity level, select suitable sweep limits, under feedback model, carry out scan-type electrochemical microscope imaging experiment.
Described Ag nanoparticle label blood fingerprint can replace with copper nano particles labelling blood fingerprint, just changes Ag nano-particle into Cu nano-particle, and silver nitrate changes copper nitrate or copper sulfate into.In principle, can be also that other metal materials are as the blood latent dactylogram of the labellings such as ferrum, lead, aluminum, magnesium, zinc.
Described sample substrate is permeability or semipermeable materials, as PVDF membrane (PVDF), and poly-ethylene diester (PET) etc.
The present invention utilizes scan-type electrochemical microscope to carry out image acquisition to blood latent dactylogram, has enriched the method kind that blood latent dactylogram manifests, and perfect current blood latent dactylogram process for show is in the disappearance providing aspect the 3rd horizontal information.The method has the following advantages:
(1) agents useful for same is stable, little to operator's healthy injury;
(2) Ag nanometer particle to mark blood fingerprint technique is simple;
(3) manifest the fingerprint image resolution of rear collection high, the finger print information of secondary level and three grades of levels clearly can be provided;
(4) the method can be used for permeability or semipermeability substrate;
(5) in the method principle, can be used for blood latent dactylogram, invisible fingerprints of sweat and oily laten fingerprints.
Utilize scan-type electrochemical microscope to obtain high-resolution blood latent dactylogram image, pore size, shape, relative position and distribution situation on fingerprint ridge are high-visible.
Accompanying drawing explanation
Fig. 1 is that the present invention carries out Ag metallic labelling front and back effect contrast figure to blood fingerprint.(a) be labelling effect contrast figure in PVDF membrane (PVDF) substrate, (b) be labelling effect contrast figure in poly-ethylene diester (PET) substrate, two pictures left-half are the fresh blood fingerprint before labelling, and right half part is the fingerprint after labelling.
Fig. 2 be the present invention in different base, utilize scanning electron microscope (SEM) and the contrast of scan-type electrochemical microscope (SECM) technology to the blood fingerprint collecting image of Ag metallic labelling.(a) be the blood fingerprint of Ag metallic labelling in PVDF membrane (PVDF) substrate, (b) be the SEM image of Ag metallic labelling blood fingerprint in PVDF membrane (PVDF) substrate, (c) be the SECM image of Ag metallic labelling blood fingerprint in PVDF membrane (PVDF) substrate, (d) be the blood fingerprint of Ag metallic labelling in poly-ethylene diester (PET) substrate, (e) be the SEM image of Ag metallic labelling blood fingerprint in poly-ethylene diester (PET) substrate, (f) be the SECM image of Ag metallic labelling blood fingerprint in poly-ethylene diester (PET) substrate.
The specific embodiment
Below in conjunction with example, further illustrate the present invention, this example is only for illustrating, and is not limited only to practical ranges of the present invention.
Embodiment 1
The surperficial blood fingerprint detection of semipermeability substrate PVDF membrane (PVDF) of take is example, and concrete operations have following steps:
(1) 1.25g sodium carbonate is dissolved, be transferred in 25mL volumetric flask, ultra-pure water standardize solution, is called stock solution A.
(2) by 0.05g ammonium nitrate, 0.05g silver nitrate, 0.25g silicon wolframic acid, 125 μ L formaldehyde are put into small beaker and are dissolved, and are transferred in 25mL volumetric flask, and ultra-pure water standardize solution, is called stock solution B.
(3) pvdf membrane first soaks 1～2s in methanol, soaks 1～2min after soaking in water again, must keep film body moistening before restraining fingerprint.
(4) volunteer will hand-wash only with fancy soap, dry, and finger dips healthy human body whole blood, and unnecessary blood is erased in the centre of the palm of another hands, smoothens, and with appropriate strength, by being pressed on moistening pvdf membrane, obtains fresh blood fingerprint.
(5) use 1% sodium acetate solution to the fixing 15min of fingerprint, after taking-up, with ultra-pure water, rinse 1～2min; Put into again 0.1% hypo solution and activate 15min, after taking-up, with ultra-pure water, rinse 1～2min.
(6) by stock solution A and B 1:1 mix homogeneously by volume, fingerprint sample is placed in to mixed liquor, in agitator, carries out labelling.
(7) after fingerprint manifestation, sample is put into 10% acetic acid solution 10min reaction is stopped, after taking-up, with ultra-pure water, rinsing, dry.
(8) take 0.0261g K
3irCl
6with 0.2528g KNO
3, dissolve, being mixed with concentration is 2mmol/L K
3irCl
6+ 0.1mol/L KNO
3as electrochemical reaction liquid.
(9) by the disk platinum microelectrode that sand paper is 25 μ m by the diameter of bottom end seal, polish, make its tip become taper shape, and meet glass shell radius and be less than 10 with the ratio of tip radius.Before imaging, microelectrode state is characterized, and utilize asymptotic curve near substrate.
(10) take the Microdisk electrode that diameter is 25 μ m is working electrode, the Ag silk reference electrode that is as the criterion, Pt silk is that setting probe current potential is that 0.8V, sweep speed are 640 μ m/s to electricity level, select suitable sweep limits, under feedback model, carry out scan-type electrochemical microscope imaging experiment.
Embodiment 2
The blood fingerprint detection on the poly-ethylene diester (PET) of the semipermeability substrate of take surface is example, and concrete operations have following steps:
(1) 1.25g sodium carbonate is dissolved, be transferred in 25mL volumetric flask, ultra-pure water standardize solution, is called stock solution A.
(2) by 0.05g ammonium nitrate, 0.05g silver nitrate, 0.25g silicon wolframic acid, 125 μ L formaldehyde are put into small beaker and are dissolved, and are transferred in 25mL volumetric flask, and ultra-pure water standardize solution, is called stock solution B.
(3) PET difference ultrasonic cleaning 15min in second alcohol and water, nitrogen dries up.
(4) volunteer will hand-wash only with fancy soap, dry, and finger dips healthy human body whole blood, and unnecessary blood is erased in the centre of the palm of another hands, smoothen, upper by being pressed in PET with appropriate strength, obtain fresh blood fingerprint.
(5) with the fixing fingerprint of dehydrated alcohol, after taking-up, with ultra-pure water, rinse 1～2min; Put into again 0.1% hypo solution and activate 15min, after taking-up, with ultra-pure water, rinse 1～2min.
(6) by stock solution A and B 1:1 mix homogeneously by volume, fingerprint sample is placed in to mixed liquor, in agitator, carries out labelling.
(7) after fingerprint manifestation, sample is put into 10% acetic acid solution 10min reaction is stopped, after taking-up, with ultra-pure water, rinsing, dry.
(8) take 0.0261g K
3irCl
6with 0.2528g KNO
3, dissolve, being mixed with concentration is 2mmol/L K
3irCl
6+ 0.1mol/L KNO
3as electrochemical reaction liquid.
(9) by the disk platinum microelectrode that sand paper is 25 μ m by the diameter of bottom end seal, polish, make its tip become taper shape, and meet glass shell radius and be less than 10 with the ratio of tip radius.Before imaging, microelectrode state is characterized, and utilize asymptotic curve near substrate.
(10) take the Microdisk electrode that diameter is 25 μ m is working electrode, the Ag silk reference electrode that is as the criterion, Pt silk is that setting probe current potential is that 0.8V, sweep speed are 640 μ m/s to electricity level, select suitable sweep limits, under feedback model, carry out scan-type electrochemical microscope imaging experiment.
Claims (8)
1. the high-resolution blood latent dactylogram image-pickup method based on scan-type electrochemical microscope, is characterized in that, first utilizes Ag
+the protein ingredient of ion in the blood of fingerprint ridge line region is combined and is reduced to the Ag nanoparticle with electro-chemical activity, and the principle of not reacting with the substrate of valley line region makes fingerprint ridge line and valley line region form electro-chemical activity difference; Then in solution, add redox mediator K
3irCl
6, utilize K
3irCl
6react with ridge line region Ag metallic and produce positive feedback effect, and the principle of not reacting with valley line region is carried out the blood fingerprint image acquisition based on SECM technology; Step is as follows:
1) take sodium carbonate becomes stock solution A as preparation of raw material, and take ammonium nitrate, silver nitrate, silicon wolframic acid, formaldehyde is preparation of raw material stock solution B, usings certain proportion mixing A and the B solution as Ag nanoparticle label blood fingerprint during reaction;
2) volunteer will hand-wash totally, and finger dips whole blood, restrains fresh blood fingerprint in substrate;
3) stock solution step 1) being made is mix homogeneously according to a certain volume, and blood fingerprint sample is placed in to mixed liquor, carries out labelling in agitator;
4) preparation electrochemical reaction solution, polishing scan-probe, sets sweep parameter, utilizes scan-type electrochemical microscope to carry out image acquisition to the successful blood fingerprint sample of labelling.
2. the high-resolution blood latent dactylogram image-pickup method based on scan-type electrochemical microscope according to claim 1, is characterized in that: described step (1) specifically comprises:
Sodium carbonate liquor is mixed with to the solution of concentration range 0.45-0.50mol/L, is called stock solution A; Preparation contains each constituent concentration than ammonium nitrate: silver nitrate: the solution of silicon wolframic acid: formaldehyde=6:3:1:50, is called stock solution B; When silver dyes labelling blood fingerprint by stock solution A and B mix homogeneously according to a certain volume.
3. the high-resolution blood latent dactylogram image-pickup method based on scan-type electrochemical microscope according to claim 1, is characterized in that: described step (2) specifically comprises:
Volunteer will hand-wash only, dry, and finger dips whole blood, and unnecessary blood is erased in the centre of the palm of another hands, smoothens, and with appropriate strength, by being pressed in substrate, obtains fresh blood fingerprint.
4. the high-resolution blood latent dactylogram image-pickup method based on scan-type electrochemical microscope according to claim 1, is characterized in that: described step (3) concrete steps comprise:
(1) use 1% sodium acetate or alcoholic solution to the fixing 15min of fingerprint, after taking-up, with ultra-pure water, rinse 1～2min; Put into again 0.1% hypo solution and activate 15min, after taking-up, with ultra-pure water, rinse 1～2min;
(2) by stock solution A and B 1:1 mix homogeneously by volume, blood fingerprint sample is placed in to mixed liquor, in agitator, carries out labelling;
(3) after fingerprint manifestation, blood fingerprint sample is put into 10% acetic acid solution 10min reaction is stopped, after taking-up, with ultra-pure water, rinsing, dry.
5. the high-resolution blood latent dactylogram image-pickup method based on scan-type electrochemical microscope according to claim 1, is characterized in that: described step (4) specifically comprises:
Preparation is with KNO
3as supporting electrolyte, with certain density K
3irCl
6electrochemical reaction solution as redox mediator; By the disk platinum microelectrode that sand paper is 25 μ m by the diameter of bottom end seal, polish, make its tip become taper shape, and meet glass shell radius and be less than 10 with the ratio of tip radius, as the probe of blood fingerprint image acquisition.
6. the high-resolution blood latent dactylogram image-pickup method based on scan-type electrochemical microscope according to claim 1, is characterized in that: the electrochemical cell of described scan-type electrochemical microscope forms and sweep parameter is:
Working electrode: diameter is the Microdisk electrode of 25 μ m; Accurate reference electrode: Ag silk; To electric grade: Pt silk; Probe current potential: 0.8V; The blood fingerprint sample of silver label note is fixed on the bottom of electrolyzer; Scan-type electrochemical microscope is set as feedback model.
7. the high-resolution blood latent dactylogram image-pickup method based on scan-type electrochemical microscope according to claim 1; it is characterized in that: described Ag nanoparticle label blood fingerprint can replace with copper nano particles labelling blood fingerprint; just change Ag nano-particle into Cu nano-particle, silver nitrate changes copper nitrate or copper sulfate into.
8. the high-resolution blood latent dactylogram image-pickup method based on scan-type electrochemical microscope according to claim 1, is characterized in that: described substrate PVDF membrane or poly-ethylene diester.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502388A (en) * | 2014-11-19 | 2015-04-08 | 华中科技大学 | Photoelectrochemical kinetics test system and method based on scanning electrochemical microscope |
| CN107560541A (en) * | 2017-08-28 | 2018-01-09 | 中国电子技术标准化研究院 | The measuring method and device of picture centre deviation |
| CN109557066A (en) * | 2019-01-25 | 2019-04-02 | 西南政法大学 | Copper nano-cluster Sweat latent fingerprint shows preparation method of reagent thereof and Sweat latent fingerprint process for show |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502388A (en) * | 2014-11-19 | 2015-04-08 | 华中科技大学 | Photoelectrochemical kinetics test system and method based on scanning electrochemical microscope |
| CN104502388B (en) * | 2014-11-19 | 2017-02-22 | 华中科技大学 | Photoelectrochemical kinetics test system and method based on scanning electrochemical microscope |
| CN107560541A (en) * | 2017-08-28 | 2018-01-09 | 中国电子技术标准化研究院 | The measuring method and device of picture centre deviation |
| CN109557066A (en) * | 2019-01-25 | 2019-04-02 | 西南政法大学 | Copper nano-cluster Sweat latent fingerprint shows preparation method of reagent thereof and Sweat latent fingerprint process for show |
| CN109557066B (en) * | 2019-01-25 | 2021-06-15 | 西南政法大学 | Preparation method of copper nano-cluster sweat latent fingerprint developing reagent and sweat latent fingerprint developing method |
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Application publication date: 20140226 |