CN111879743A - Method for visualizing explosive residues in latent fingerprint - Google Patents

Method for visualizing explosive residues in latent fingerprint Download PDF

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CN111879743A
CN111879743A CN202010728179.8A CN202010728179A CN111879743A CN 111879743 A CN111879743 A CN 111879743A CN 202010728179 A CN202010728179 A CN 202010728179A CN 111879743 A CN111879743 A CN 111879743A
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黄锐
马玉瑶
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Southwest University Of Political Science & Law
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Abstract

A method of visualizing explosive residues in latent fingerprints, comprising the steps of: mixing the HCL solution and the OPD solution uniformly to prepare an A reagent; mixing NaOH solution and cyclodextrin solution uniformly to prepare reagent B, and then using nano ferric oxide powder to make NO-contained2 And (3) displaying the latent fingerprints, immersing the latent fingerprints by using the solution A, standing for 10min, injecting the solution B, taking out the fingerprint carrier after 10min, and naturally drying for displaying. The invention has the beneficial effects that: the method has the advantages of low cost, portable equipment, simple operation, mild conditions, quick and efficient operation process, capability of effectively reducing damage to the evidence and accurately and reliably detecting NO in the latent fingerprint2

Description

Method for visualizing explosive residues in latent fingerprint
Technical Field
The invention relates to the field of public security criminal technology fingerprint identification, in particular to a method for visualizing explosive residues in latent fingerprints.
Background
Fingerprints are formed by the combined action of heredity and environment and have the characteristics of being different among people and unchanging in life. Due to the influence of various factors such as genetic materials, skin tissue structures, pathology, trauma and the like, the mastoid streaks of the fingerprints have specificity, diversity and stability, and the characteristics provide scientific basis for identifying and identifying the human body through analysis, identification and authentication of the fingerprint streaks. Meanwhile, due to the characteristic of object touching and mark retaining, fingerprints left on the object can truly reflect the fingerprint characteristics of the left-behind person, and play an important role in disclosing crime facts, locking criminal suspects, providing investigation directions for investigation personnel and providing scientific basis for trial and judgment in criminal cases.
The explosion case is a case formed by criminal behaviors of killing people, destroying public and private properties and seriously harming public safety by adopting an explosion means. As a criminal case, it seriously endangers the life and property safety of the masses. When a criminal deals with explosives, a certain amount of explosive residues are likely to remain on hands and clothes of the criminal, and when the criminal touches other objects, the explosive residues are transferred through fingerprints of people, so that the detection of the explosive traces in the fingerprints and the qualitative and quantitative analysis of the explosive residues are extremely important.
At present, people use laser-induced breakdown spectroscopy, X-ray reflection spectroscopy and vibration spectroscopy to realize rapid detection of explosive residues in fingerprints.
Lucena et al successfully detected explosive-contaminated latent fingerprints deposited on the surface of aluminum or glass substrates by capturing spectral information from a laser-induced plasma by two-dimensional scanning using a laser-induced breakdown applied spectroscopy (LIBS) sensor at a distance of 31 meters from the target latent fingerprint. However, LIBS sensors do not respond well to old fingerprints, and contaminants in the ambient air can affect the detection capabilities of the sensors.
When Moros et al process LIBS information, explosive components and potentially harmless interfering agents in potential fingerprints contaminated by explosives are effectively distinguished by constructing a multi-stage architecture algorithm. However, the detection capability of LIBS is inherently deficient, for example, for chlorate explosives, low surface concentrations of chlorate in the carrier and low sulfur levels in chlorate formulations can increase the false rate of such explosives. In addition, the detection of fingerprints is affected by factors such as the force applied during the explosive deposition process, the deposition angle, the duration of surface contact, and the adhesion degree of the fingerprint substance and the carrier, and the detection effect is not satisfactory because the factors are easily out of the control range of operators.
Worley et al utilized the spatial elemental imaging capability of micro X-ray fluorescence (MXRF) to visualize latent fingerprints based on the inorganic elements present in the fingerprint, most of the fingerprints examined being imaged by potassium and chlorine in the fingerprint residue. This is a non-destructive inspection technique and is not affected by the color of the underlying fingerprint leaving the carrier, while providing chemical information useful for forensic analysis. There are also limitations to the detection of fingerprints using this method, which cannot be detected if the content of inorganic elements in the fingerprint is below the typical MXRF-ppm detection limit trace level; prior to detection, the approximate location of the latent fingerprint needs to be known; for the detection of the latent fingerprints on the printed matter, the original high-concentration elements on the surface of the printed matter can be detected, so that the recognition of the latent fingerprints is interfered.
The methods have the defects of high cost and low efficiency, and are difficult to be widely applied in practice due to the inherent defects of the detection method and uncontrollable factors in the environment. The method focuses on detecting the components of the fingerprint substances, and the synchronous display, identification and diagnosis of the fingerprint morphological information and the information of the exogenous carried substances are not completely realized.
Disclosure of Invention
The invention aims to provide a method for visualizing explosive residues in latent fingerprints, which has the advantages of low cost, portable equipment, simple operation, mild conditions, quick and efficient operation process, capability of effectively reducing damage to evidences and accurate and reliable detection of NO in the latent fingerprints2 -
The invention aims to realize the technical scheme that the method for visualizing the explosive residues in the latent fingerprint comprises the following steps:
s1, uniformly mixing 2mol/L HCL solution and 3.0-7.0mg/mL OPD solution according to the volume ratio of 2:3 to prepare a reagent A;
s2, uniformly mixing 1mol/L NaOH solution and 6.0-16.0mg/mL cyclodextrin solution according to the volume ratio of 1:2 to prepare a reagent B;
s3, using nano ferric oxide powder to contain NO2 -Displaying the latent fingerprints;
s4, putting the latent fingerprint carrier into a clean container, injecting the solution A into the container to immerse the latent fingerprint in the solution, and standing for 10 min;
and S5, injecting the solution B into the solution, taking out the fingerprint carrier after 10min, and naturally airing and showing the fingerprint carrier.
Further, step S6 is included, in which the visualized fingerprint is observed by means of a visualization observation system, and the fluorescence fixed fingerprint image is observed.
Further, the method comprises a step S7 of performing data processing on the picture color information by using the program of HSV color space in Matlab to construct the hue, saturation and brightness of the latent fingerprint picture and NO in the latent fingerprint picture2 -Quantitative expression of NO in latent fingerprints2 -And (4) content.
Further, the concentration of OPD solution in S1 was 5 mg/mL.
Further, a 5mg/mL OPD solution was prepared by weighing 0.05g OPD and dissolving in 10mL absolute ethanol.
Further, the cyclodextrin solution of S2 is one or more of beta-CD, HE-beta-CD, HP-beta-CD and SBE-beta-CD.
Further, the concentration of the cyclodextrin solution was 8.0 mg/mL.
Further, step S6 specifically includes:
s601, a display observation system is set up by utilizing a multiband light source, a colored filter and a digital single-lens reflex camera to observe and fix the fingerprint;
s602, under the dark condition, the fingerprint is irradiated by the multiband light source, fluorescence generated by the fingerprint is recorded by the digital single lens reflex through the colored filter lens, and the fingerprint papillary lines and the detailed characteristics thereof are fixed by the picture.
Further, a multiband light source of 415nm is used.
Further, in step S3, the nano ferroferric oxide has excellent magnetic permeability and unique superparamagnetic property, and is made into powder for developing latent fingerprints. When the latent fingerprint on the liner paper is displayed, a proper amount of nano ferroferric oxide powder is uniformly covered on the surface of the latent fingerprint, the nano ferroferric oxide powder is adhered to the pattern lines of the latent fingerprint by using a 'shaking display method', and redundant ink powder is controlled out for later use.
In particular, NO2 -The main site residues of nitrite toxicants and nitrogen-containing explosive residues are widely existed in criminal case sites. The fingerprint as "king of evidence" is a trace reflecting fingerprint structure information and attachment information solidified on the surface of the carrier due to contact between sweat or other attachment substances and the surface of the carrier when a finger touches an object. When a criminal deals with explosives, a certain amount of explosive residues are likely to remain on his hands and clothes, when the criminal touches other objects, the explosive residues are transferred by fingerprints of the criminal, fingerprint substances left at a crime scene usually comprise endogenous substances in human sweat and exogenous substances left by the contact environment of fingers, and the substances are the basis of substances for visualizing the fingerprints and are the key point for mining human information.
In the present invention, OPD itself has fluorescence, but the fluorescence intensity is weak. OPD and NO2 -The derivative reaction is carried out under the acidic condition to generate a fluorescent compound benzotriazole, and the system can emit stronger fluorescence in a weak alkaline medium. HP-beta-CD can be combined with a guest molecule (NO) due to the special cavity space structure of' internal hydrophobicity and external hydrophilicity2 --OPD) to form an inclusion compound, reducing the decrease of fluorescence quantum yield caused by the mutual collision between molecules, hindering the free rotation of the guest molecule, reducing the number of guest excited molecules inactivated by vibrational relaxation, thereby enhancing the fluorescence of the guest molecule. Due to the selectivity of derivatization reaction and inclusion reaction, the analysis method has good specificity, and realizes the purpose of containing NO2 -And (4) visual diagnosis of latent fingerprints.
Due to the adoption of the technical scheme, the invention has the following advantages: the method has the advantages of low cost, portable equipment, simple operation, mild conditions, quick and efficient operation process, capability of effectively reducing damage to the evidence and accurately and reliably detecting NO in the latent fingerprint2 -(ii) a In addition, an HSV color space is used as a model in MATLAB software to write a program, and the color and fluorescence before and after reaction are identified and digitalized for the nitrogen-containing fingerprint substanceAnd (3) qualitatively analyzing the explosive residues, and establishing a corresponding mathematical algorithm according to the change of the previous data and the next data for semi-quantitatively analyzing the nitrogen-containing explosive residues of the fingerprint substances.
Drawings
FIG. 1 shows HP-beta-CD and NO in the present invention2 -A schematic of the process of forming inclusion complexes with OPD complex molecules.
FIG. 2 is a schematic representation of the latent fingerprint appearance of the present invention;
FIG. 3 is a schematic representation of colors in the Matlab HSV procedure of the present invention.
FIG. 4 shows the use of OPD and NO in the present invention2 --OPD、NO2 -A fluorescence spectrum observed after OPD- (HP- β -CD).
FIG. 5 is a schematic representation of OPD concentration versus latent fingerprint display in the present invention.
FIG. 6 is a graph showing the fluorescence intensity of four cyclodextrin inclusion compounds in the present invention.
FIG. 7 is a graph showing fluorescence intensity of HP- β -CD inclusion compounds of different concentrations in the present invention.
FIG. 8 is a schematic diagram showing a comparison of different ways in which fingerprints appear on plain liner paper in the present invention.
FIG. 9 is a schematic representation of a latent fingerprint image formed by Matlab visualization in accordance with the present invention applied to a fingerprint surface.
FIG. 10 is NO in the latent fingerprint of the present invention2 -A relationship diagram of the surface density, hue value and hue pixel point weighted average.
Detailed Description
The invention is further described below with reference to the figures and examples.
Example 1
A method of visualizing explosive residues in latent fingerprints, comprising the steps of:
s1, uniformly mixing 2mol/L HCL solution and 3.0-7.0mg/mL OPD solution according to the volume ratio of 2:3 to prepare a reagent A;
s2, uniformly mixing 1mol/L NaOH solution and 6.0-16.0mg/mL cyclodextrin solution according to the volume ratio of 1:2 to prepare a reagent B;
s3, using nano ferric oxide powder to contain NO2 -Displaying the latent fingerprints;
s4, putting the latent fingerprint carrier into a clean container, injecting the solution A into the container to immerse the latent fingerprint in the solution, and standing for 10 min;
and S5, injecting the solution B into the solution, taking out the fingerprint carrier after 10min, and naturally airing and showing the fingerprint carrier.
Example 2
S1, uniformly mixing 2mol/L HCL solution and 3.0-7.0mg/mL OPD solution according to the volume ratio of 2:3 to prepare a reagent A;
s2, uniformly mixing 1mol/L NaOH solution and 6.0-16.0mg/mL cyclodextrin solution according to the volume ratio of 1:2 to prepare a reagent B;
s3, using nano ferric oxide powder to contain NO2 -Displaying the latent fingerprints;
s4, putting the latent fingerprint carrier into a clean container, injecting the solution A into the container to immerse the latent fingerprint in the solution, and standing for 10 min;
and S5, injecting the solution B into the solution, taking out the fingerprint carrier after 10min, and naturally airing and showing the fingerprint carrier.
The visualized fingerprint is observed by the visualization observation system at S6 as a fluorescence-fixed fingerprint image.
Example 3
S1, uniformly mixing 2mol/L HCL solution and 3.0-7.0mg/mL OPD solution according to the volume ratio of 2:3 to prepare a reagent A;
s2, uniformly mixing 1mol/L NaOH solution and 6.0-16.0mg/mL cyclodextrin solution according to the volume ratio of 1:2 to prepare a reagent B;
s3, using nano ferric oxide powder to contain NO2 -Displaying the latent fingerprints;
s4, putting the latent fingerprint carrier into a clean container, injecting the solution A into the container to immerse the latent fingerprint in the solution, and standing for 10 min;
and S5, injecting the solution B into the solution, taking out the fingerprint carrier after 10min, and naturally airing and showing the fingerprint carrier.
The visualized fingerprint is observed by the visualization observation system at S6 as a fluorescence-fixed fingerprint image.
S7, using the program of HSV color space in Matlab to process the picture color information into data, and constructing the hue, saturation, lightness and NO of the latent fingerprint picture2 -Quantitative expression of NO in latent fingerprints2 -And (4) content.
Example 4
S1, uniformly mixing 2mol/L HCL solution and 5.0mg/mL OPD solution according to the volume ratio of 2:3 to prepare a reagent A;
s2, uniformly mixing 1mol/L NaOH solution and 8.0mg/mL cyclodextrin solution according to the volume ratio of 1:2 to prepare a reagent B;
s3, using nano ferric oxide powder to contain NO2 -Displaying the latent fingerprints;
s4, putting the latent fingerprint carrier into a clean container, injecting the solution A into the container to immerse the latent fingerprint in the solution, and standing for 10 min;
and S5, injecting the solution B into the solution, taking out the fingerprint carrier after 10min, and naturally airing and showing the fingerprint carrier.
The visualized fingerprint is observed by the visualization observation system at S6 as a fluorescence-fixed fingerprint image.
S7, using the program of HSV color space in Matlab to process the picture color information into data, and constructing the hue, saturation, lightness and NO of the latent fingerprint picture2 -Quantitative expression of NO in latent fingerprints2 -And (4) content.
Further, in the above examples, 5mg/mL of OPD solution was prepared by weighing 0.05g of OPD and dissolving in 10mL of absolute ethanol.
Further, in the above embodiment, the cyclodextrin solution of S2 is one or more of beta-CD, HE-beta-CD, HP-beta-CD, and SBE-beta-CD.
Further, in the above embodiment, the step S6 specifically includes the following steps:
s601, a display observation system is set up by utilizing a multiband light source, a colored filter and a digital single-lens reflex camera to observe and fix the fingerprint;
s602, under the dark condition, the fingerprint is irradiated by the multiband light source, fluorescence generated by the fingerprint is recorded by the digital single lens reflex through the colored filter lens, and the fingerprint papillary lines and the detailed characteristics thereof are fixed by the picture.
Further, in the above embodiment, the multiband light source used is 415nm band.
Examples of the experiments
Reagent and apparatus
Hydroxypropyl-beta-cyclodextrin (HP-beta-CD), hydroxyethyl-beta-cyclodextrin (HE-beta-CD), sulfobutyl ether-beta-cyclodextrin (SBE-beta-CD), beta-cyclodextrin (beta-CD) are available from Beta Cyclodextrin corporation; sodium nitrite (NaNO)2) O-phenylenediamine (OPD), hydrochloric acid (HCL), and sodium hydroxide (NaOH) are commercially available from Aladdin.
RF-5301PC fluorescence spectrometer (Shimadzu, Japan); Milli-Q ultra-pure water machines (Milli-bo, usa); ESJ200-4B analytical balance (Shenyang Longteng electronics, Inc.); FGGY-V IIA portable multiband light source (Beijing Fenger' an science and technology, Inc.); DZF-6020 vacuum drying oven (Shanghai Shenxian constant temperature plant).
Reagent and preparation method
5mg/mL OPD solution: 0.05g of OPD was weighed out and dissolved in 10mL of absolute ethanol.
8mg/mL of aqueous solutions of beta-CD, HE-beta-CD, HP-beta-CD, SBE-beta-CD: 0.16g of beta-CD, HE-beta-CD, HP-beta-CD and SBE-beta-CD are respectively dissolved in 20mL of deionized water for preparation, and the mixture can be stored for 3 months at normal temperature and in dark place.
2mol/L LHCL solution and 1mol/L NaOH solution.
All the reagents are analytically pure, and the water is deionized water.
NO in aqueous solution2 -Derivatization and inclusion processes
The role of HP-beta-CD in this study was to interact with the guest molecule (NO)2 --OPD) forms a clathrate, sensitizes the fluorescence of the analyte, and increases the sensitivity of the assay. At 2. mu.g/mL NO2 -Adding 0.40mLHCL (2mol/L) solution into the solutionThe solution, 0.60mLOPD (5mg/mL), was shaken, left at room temperature for 20min, and then added with 0.80mLNaOH (1mol/L) solution and 1.60 mLHP-beta-CD (10mg/mL) solution in that order.
NO in latent fingerprint2 -Derivatization and inclusion processes
Using an ESJ200-4B analytical balance (accuracy 4 decimal places, 0.0001g), NaNO2 powder was placed on the scale pan and contacted with NaNO2 powder at the finger papilla pattern, the scale reduction being the mass of NaNO2 powder adhered to the finger. The lining paper is put on a scale in advance, the finger print is pressed on the lining paper, and the scale increment is the mass of NaNO2 powder in the latent finger print (the interference of the mass of sweat and grease in the finger print is eliminated through blank experiments), so that the latent finger print left when the nitrogen-containing explosive residues are attached to the fingers of a human body is simulated. Uniformly mixing a 2mol/LHCL solution and a 5mg/mL OPD solution according to a volume ratio of 2:3 to prepare a reagent A; and uniformly mixing a 1mol/L NaOH solution and an 8mg/mL HP-beta-CD solution according to the volume ratio of 1:2 to prepare a reagent B. After the latent fingerprint is displayed by using nano ferric oxide powder, cutting the fingerprint from the liner paper along the edge of the fingerprint, putting the fingerprint into a clean container with a flat bottom, injecting solution A into the container to immerse the latent fingerprint, and standing for 10 min; and injecting the solution B into the solution, taking out the fingerprint after ten minutes, placing the fingerprint on a clean glass slide, and naturally drying the fingerprint.
NO2 -Principle of detection
As shown in fig. 1, OPD itself has fluorescence, but the fluorescence intensity is weak. OPD and NO2 -The derivative reaction is carried out under the acidic condition to generate a fluorescent compound benzotriazole, and the system can emit stronger fluorescence in a weak alkaline medium. HP-beta-CD can be combined with a guest molecule (NO) due to the special cavity space structure of' internal hydrophobicity and external hydrophilicity2 --OPD) to form an inclusion compound, reducing the decrease of fluorescence quantum yield caused by the mutual collision between molecules, hindering the free rotation of the guest molecule, reducing the number of guest excited molecules inactivated by vibrational relaxation, thereby enhancing the fluorescence of the guest molecule. Due to the selectivity of derivatization reaction and inclusion reaction, the analysis method has good specificity, and realizes the purpose of containing NO2 -And (4) visual diagnosis of latent fingerprints.
NO2 -Principle of datamation analysis
The digitalization of fingerprint color information is a precondition for qualitative and quantitative analysis of fingerprint substances, and interference factors such as background, light, color difference and the like need to be eliminated. A program related to HSV color space is created in Matlab software, and as shown in fig. 3, a schematic diagram of the representation related to colors in the Matlab HSV program is shown, wherein an X axis represents hue, and a Y axis represents the number of pixels corresponding to each color in a picture. Taking Hue (Hue), Saturation (Saturation) and brightness (Value) as three standards for identifying each picture, reading H/S/V values of all pixel points in each picture, and calculating the average Value of H/S/V values corresponding to all pixel points in the whole picture so as to pair H/S/V values containing NO2 -And performing HSV color space analysis on the visual latent fingerprint. The HSV color space is a method for representing points in the RGB color space in an inverted cone, is more similar to human sense organ and has richer and more accurate interpretation parameters for images than the RGB. The Matlab software HSV program quantifies the differences in hue, saturation, and lightness of the visualized latent fingerprint fluorograms. The saturation depends on the ratio of the color component and the achromatic component (gray) contained in the color. The larger the color content, the greater the saturation; the larger the achromatic component is, the smaller the saturation is; the characteristics of the hue are determined by the spectral composition of the light source and the perception of the human eye by the ratio of the wavelengths of radiation reflected from the surface of the colored object; lightness refers to the brightness or lightness of a color, and the color varies in brightness and darkness, and usually the lightness of a photograph varies due to factors such as background color, light, and color difference.
In this experiment, the difference in brightness of latent fingerprint images needs to be eliminated as a means for the same background interference. And under the condition that the brightness error is controllable, identifying the hue of each pixel point in the image to obtain a corresponding hue value. The hue value is the basis of qualitative analysis, latent fingerprint images before and after identification are respectively collected, the hue images are compared, and whether the positive judgment threshold value is reached is judged through the difference of the hue images; the weighted average value of hue pixel points is the basis of quantitative analysis to design NO2 -And (3) establishing a relation curve of the weighted average value of the area density-hue pixel points by the area density gradient to realize semi-quantitative analysis.
Fluorescence spectroscopy
The excitation wavelength was set to 410nm, and OPD solution and NO were measured at the excitation wavelength2 -Derivatizing solution (NO)2 --OPD)、NO2 -Derivatization-inclusion solution (NO)2 -Fluorescence intensity of-OPD- (HP- β -CD)), and excitation wavelength, emission wavelength, and fluorescence intensity thereof are shown in FIG. 4.
As can be seen from FIG. 4, OPD has very weak fluorescence intensity at an excitation wavelength of 410nm and an emission wavelength of about 570nm, and NO is added2 -After the solution is dissolved, the peak shapes and the peak positions of the excitation wavelength and the emission wavelength of the solution are basically unchanged, but the fluorescence intensity of the system is obviously enhanced, which shows that OPD and NO are mixed2 -The derivatization reaction is carried out under the acidic condition to form a compound NO2 -OPD and produces strong fluorescence in alkaline environment, and the degree of fluorescence enhancement is in a certain range with NO2 -The amount of (c) is linear. Formation of Complex NO by Inclusion of HP-beta-CD2 -OPD- (HP-beta-CD), the fluorescence intensity of which is lower than that of NO without changing the excitation and emission wavelengths of the complex2 -The OPD compound is obviously enhanced, and a multiband light source is adjusted to 415nm waveband, NO2 -Yellow fluorescence was detected with OPD- (HP- β -CD) under a filter, and the increase in fluorescence intensity facilitated the differential quantification of Matlab.
Influence of acidity and basicity on NO content2 -Fixing OPD and NO when the latent fingerprint is visualized2 -By varying the quantity concentrations of HCL and NaOH, the effect of acidity and alkalinity on the derivatization reaction was examined. The results show that the reaction can not be carried out under the acid-free condition, and the observation and reading and distinguishing of hue, saturation and lightness of the image by the Matlab software HSV program find that the fluorescence intensity of the compound is optimal when the concentration of the HCL substance is 2.00mol/L and the concentration of the NaOH substance is 1.00 mol/L.
Note: the fluorescence intensity of the complex was judged by a "+" sign, which represents no good; "+ +" represents Normal; "+ + + +" indicates good
Figure BDA0002600640960000091
Effect of OPD concentration
The use level of the derivatization reagent directly influences whether the derivatization reaction can be completely carried out, an autonomous photographing system is used for effectively controlling the picture saturation to be a single variable in the experiment, and the visualization fluorescence latent fingerprint image saturation, hue and brightness are read and distinguished through visual observation and a Matlab software HSV program to judge whether the derivatization is completely carried out and determine the optimal concentration of OPD.
As shown in FIG. 5, the saturation value of the picture showing the latent fingerprint is the highest in 5.0mg/mL OPD when the concentration of OPD is in the range of 3.0-7.0mg/mL, and thus the optimum concentration of OPD is 5.0 mg/mL.
Type and concentration of Cyclodextrin
Different types of cyclodextrins including beta-CD, HE-beta-CD, HP-beta-CD, SBE-beta-CD vs NO were investigated in aqueous solution2 -Inclusion effect of OPD. In the same NO2 -Adding an excessive amount of different kinds of CD in equal amount to the OPD complex solution, and measuring the fluorescence intensity of the inclusion compound solution after the inclusion reaction.
As shown in FIG. 6, it was found that addition of HP-beta-CD was induced in response to NO2 -The fluorescence sensitization effect of the OPD complex is optimal. In the presence of NO2 -The influence of the addition concentration of HP-beta-CD in the range of 6.0-16.0mg/mL on the inclusion effect is examined in the latent fingerprint and the water solution, as shown in FIG. 7, when the concentration of HP-beta-CD is 8.0mg/mL, the fluorescence intensity of the inclusion compound is the best, and the experiment finally selects HP-beta-CD with the concentration of 8.0mg/mL in the inclusion system to carry out the inclusion reaction.
Latent fingerprint display method optimization
The experiment mainly considers the appearance of the latent fingerprint on the surface of the permeable object, and smooth liner paper is selected as a latent fingerprint carrier in the experiment process. In order to explore different latent fingerprint showing methods, experiments compare three methods of showing latent fingerprints, namely a 'dripping method' of dripping A, B reagent on the surface of a latent fingerprint by using a rubber head dropper, a 'spraying method' of uniformly spraying A, B reagent on the surface of the latent fingerprint by using a nanometer spraying instrument, and a 'soaking method' of sequentially soaking smooth lining paper printed with the latent fingerprint in A, B reagent, the effect is shown in figure 8, the different showing methods of the fingerprint on the smooth lining paper are compared and schematically shown, the 'spraying method', the dripping method 'and the soaking method' are arranged from left to right, and the latent fingerprint lines shown by the soaking method are clearer and more complete.
Latent fingerprint rendering and image processing
All fingerprint samples are provided by the same printer. To ensure that the same amount of natural oil and sweat is present in the fingerprint, the finger print applicator washes the hands clean and dries 15 minutes before each experiment, and performs normal daily work. After 15 minutes, the mastoid pattern surface of the right thumb is placed in the NaNO in the scale pan of the electronic scale2The powder is adhered with NaNO of different quality according to the magnitude of pressing force and the length of pressing time2Powder, the mass of NaNO2 powder remaining on the scale pan was weighed to determine the mass of NaNO2 powder adhering to the fingerprint of the printing person. Applying a finger print to the backing paper by the printer to obtain the NO content2 -While weighing and recording NO in latent fingerprint2 -The quality of (c). The fingerprint sample is deposited in clean tray, and the sample is put the interval and is moderately avoided the adhesion. In order to simulate the latent fingerprints on the actual case site as much as possible, the experimental fingerprint sample is stored in a natural state.
After the latent fingerprint is displayed by using nano ferric oxide powder, cutting the fingerprint from the liner paper along the edge of the fingerprint, putting the fingerprint into a clean container with a flat bottom, injecting solution A into the container to immerse the latent fingerprint, and standing for 10 min; and injecting the solution B into the solution, taking out the fingerprint after ten minutes, placing the fingerprint on a clean glass slide, and naturally drying the fingerprint. The multi-band light source, the colored filter and the digital single-lens reflex camera are used for independently constructing the display observation system, the distance and the angle between the camera and a shooting target and the height and the angle of the multi-band light source are kept fixed, and the display observation system is used in dark conditionsThen, a multi-band light source is adjusted to 415nm band, and NO-containing substances expressed by OPD and HP-beta-CD are irradiated2 -And latent fingerprint, wherein orange yellow fluorescence generated by the fingerprint is recorded by the digital single lens reflex through the colored filter, the fingerprint mastoid line and the detail characteristics thereof are fixed, and other stray light which does not reflect the fingerprint characteristics cannot penetrate through the colored filter and cannot be recorded by the camera. And then, the photo is subjected to command enhancement processing such as 'curve' and the like by using Photoshop image processing software, so that fluorescent fingerprint lines in the photo are clearer and more distinguishable, and inspection and identification are more facilitated. NO in latent fingerprints2 -During semi-quantitative analysis, the latent fingerprint needs to be placed in a pure black background for shooting, and Photoshop image processing software is used for adjusting the white balance of the photo by adopting a 'curve' command to the photo so as to ensure that the background black has no color cast, thereby ensuring that all photos have normal hue and similar lightness; before the Matlab program is recorded, unnecessary parts of the latent fingerprint pictures are removed, only the center patterns and the upper parts of the center patterns of the fingerprints are reserved, and all the pictures are adjusted to 900 multiplied by 900 pixels, wherein the resolution ratio is 300 pixels/cm.
NO in latent fingerprint2 -Areal density of
NaNO in the course of experiment2The powder is presented in solid form in the latent print, thus building up NO2 -The relationship curve of the weighted average value of the area density-hue pixel points is more reasonable. To which NO is adhered2 -The finger has a loss of substance during the process of transferring the fingerprint, NO on the finger2 -Content and latent fingerprint surface formed NO2 -There is a difference in the construction of NO2 -When the areal density gradient is used, the difference between the two should be fully considered.
In the operation of developing process containing NO 2-latent fingerprint, recording the mass (m) of NaNO2 powder transferred from NaNO2 powder adhered to finger to liner paper latent fingerprint, measuring the area (S) of liner paper latent fingerprint, and calculating the residual NO of the latent fingerprint by the formula rho ═ m/S2 -Areal density (ρ). Multiple repeat experiments were performed as described above with varying mass of the finger-adhered NaNO2 powder.
Differential quantification of latent fingerprints by Matlab
The latent fingerprint picture is recorded into a Matlab software HSV program after the latent fingerprint is displayed and processed in an image processing mode, and a relationship map of each hue and a corresponding color pixel point is obtained, as shown in fig. 9. In the experiment, the fluorescent color is yellow orange, so only a map with the hue of yellow orange is intercepted, the unit of the hue is the degree, no specific numerical value represents each specific color, and the hues of red to yellow parts are artificially specified to be 1-10 in sequence for facilitating later calculation. And respectively calculating the hue average value of the nine pictures and the weighted average value of hue pixel points. The hue average value represents the hue value with the largest pixel number of the whole picture, namely the biased color of the whole picture; the weighted average of hue pixel points represents the pixel value under the average hue. The combination of the two can better display the NO2 -Areal Density relationship, as shown in FIG. 10, with X-axis being NO in latent fingerprint2 -The surface density, left Y axis is hue value, right Y axis is hue pixel point weighted average, it can be seen that in the large trend, with NO2 -The increase of the surface density reduces the weighted average value of the hue pixel points, and the hue value moves from yellow to red.
Conclusion
Derivatization reagents OPD and NO were used in this study2 -Forming benzotriazole with certain fluorescence, and then adopting HP-beta-CD molecules to perform inclusion on the formed benzotriazole. Due to the selectivity of the derivatization and inclusion reactions, the analysis method has good specificity, and the Matlab software HSV program quantifies the differences of the visual latent fingerprint fluorescence image in hue, saturation and lightness. Accordingly, a NO was established2 -Derivatization inclusion technology is combined with detection of NO in latent fingerprint through hue, saturation and lightness maps2 -And a new semi-quantitative analysis method is carried out. The test optimizes OPD derivatization, HP-beta-CD inclusion derivatives and latent fingerprint display methods, and determines the dosage of OPD in derivatization reaction, the dosage of HP-beta-CD in inclusion reaction and the latent fingerprint display method. The analysis method is simple to operate, mild in condition, good in selectivity and capable of accurately and reliably detecting the latent fingerprintsNO in (1)2 -
The exogenous carrier information refers to a large amount of contact information retained by the finger according to the Rockard substance exchange principle, and may include all substances except human metabolites such as drugs, poisons, explosives and the like. The synchronous diagnosis of fingerprint and exogenous carrier information is that the exogenous matter in the fingerprint is identified and tested while latent fingerprint is shown. In the invention, the supermolecule is used for carrying out visual synchronous identification on the two-dimensional form of the fingerprint and the information of the exogenous carried object, and meanwhile, the HSV color space model is used for carrying out data analysis and diagnosis on the material information in the latent fingerprint.
In practical application, the method can be used for visual identification of latent fingerprints left on explosion case site and content NO2 -The qualitative and quantitative analysis breaks through a two-dimensional form display mode which takes the identification of fingerprints, lines, characteristics and other features as the final aim in the current judicial practice, and more information of the left-over persons is mined through the fingerprints, so that the qualitative and quantitative analysis has important significance for crime scene reconstruction, judgment of fingerprint leaving time, depiction of the left-over persons and the like.

Claims (9)

1. A method for visualizing explosive residues in latent fingerprints, comprising the steps of:
s1, uniformly mixing 2mol/L HCL solution and 3.0-7.0mg/mL OPD solution according to the volume ratio of 2:3 to prepare a reagent A;
s2, uniformly mixing 1mol/L NaOH solution and 6.0-16.0mg/mL cyclodextrin solution according to the volume ratio of 1:2 to prepare a reagent B;
s3, using nano ferric oxide powder to contain NO2 -Displaying the latent fingerprints;
s4, putting the latent fingerprint carrier into a clean container, injecting the solution A into the container to immerse the latent fingerprint in the solution, and standing for 10 min;
and S5, injecting the solution B into the solution, taking out the fingerprint carrier after 10min, and naturally airing and showing the fingerprint carrier.
2. The method for visualizing the explosive residues in latent fingerprints according to claim 1, further comprising a step S6, wherein the visualized fingerprints are used for observing fluorescent fixed fingerprint images by means of a visualization observation system.
3. The method for visualizing the explosive residues in the latent fingerprint according to claim 2, further comprising a step S7 of performing data processing on the picture color information by programming HSV color space in MATLAB to construct hue, saturation, brightness and NO in the latent fingerprint picture2 -Quantitative expression of NO in latent fingerprints2 -And (4) content.
4. The method for visualizing explosive residues in latent fingerprints according to claim 1, wherein the concentration of the OPD solution in S1 is 5 mg/mL.
5. The method of visualizing explosive residues in latent fingerprints according to claim 4, wherein the 5mg/mL OPD solution is prepared by weighing 0.05g OPD in 10mL absolute ethanol.
6. The method for visualizing explosive residues in latent fingerprints according to claim 1, 2, 3, 4 or 5, wherein the cyclodextrin solution in S2 is one or a combination of more than one of beta-CD, HE-beta-CD, HP-beta-CD and SBE-beta-CD.
7. The method for visualizing explosive residues in latent fingerprints according to claim 6, wherein the concentration of the cyclodextrin solution is 8.0 mg/mL.
8. The method for visualizing the explosive residues in the latent fingerprint according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the step S6 specifically comprises:
s601, a display observation system is set up by utilizing a multiband light source, a colored filter and a digital single-lens reflex camera to observe and fix the fingerprint;
s602, under the dark condition, the fingerprint is irradiated by the multiband light source, fluorescence generated by the fingerprint is recorded by the digital single lens reflex through the colored filter lens, and the fingerprint papillary lines and the detailed characteristics thereof are fixed by the picture.
9. The method for visualizing the explosive residues in the latent fingerprint according to claim 8, wherein a multi-band light source is used in the 415nm band.
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