CN113582931B - Fluorescent dye probe for latent fingerprint detection and preparation method and application thereof - Google Patents
Fluorescent dye probe for latent fingerprint detection and preparation method and application thereof Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/96—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/117—Identification of persons
- A61B5/1171—Identification of persons based on the shapes or appearances of their bodies or parts thereof
- A61B5/1172—Identification of persons based on the shapes or appearances of their bodies or parts thereof using fingerprinting
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- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Abstract
The invention relates to a fluorescent dye probe for latent fingerprint detection and a preparation method and application thereof, wherein the core chemical structural formula of the probe is shown as formula I:
wherein R is 1 Is an aromatic ring (including aromatic heterocyclic ring) compound or methyl. R 2 And R 3 At least one is a hydrophilic group. The functional fluorescent dye probe molecule can selectively dye DNA and latent fingerprints in the latent fingerprints, and then the latent fingerprints on the surfaces of various objects can be displayed by a method of light excitation of different emission wave bands after dyeing by means of portable light source excitation of various wave bands and a single-lens reflex camera, so that a high-definition latent fingerprint fluorescent image is obtained.
Description
Technical Field
The invention relates to the field of latent fingerprint detection, in particular to a fluorescent dye probe for latent fingerprint detection and a preparation method and application thereof.
Background
Fingerprints are unique patterns on the skin of a finger and are composed of ridges on the skin. The start, end, bifurcation, and union of these ridges are called minutiae. Each person's fingerprint, and even each ridge of a fingerprint, is unique. Therefore, the human fingerprint has three characteristics of basically unchanging in life, uniqueness, necessary trace of touch objects and the like. According to the characteristics that human fingerprints are different and basically invariable throughout life, fingerprint identification has been developed into a very important and reliable method in the field of forensic medicine, and can provide important clues and evidences for judicial identification, especially for confirming crimes and identifying criminals.
However, latent fingerprints, i.e., latent fingerprints, are the most common fingerprints in the field of a case, as compared to visible fingerprints and plastic fingerprints. Such fingerprints are the prints of fingerprints left by natural body secretions, such as sweat, after the surface of the object is contacted by a finger, and are usually not easily found by naked eyes, which results in the need for very specialized techniques for the extraction and identification of latent fingerprints. The existing latent fingerprint developing methods mainly comprise an optical method, a physical developing method, a chemical developing method, a physical and chemical developing method and the like. However, the optical method has the problems of high instrument cost, overlarge volume, constant carrying and the like at present, the powder method, the vacuum metal deposition method and the like which are commonly used in the physical display method have complicated steps, meanwhile, the powder method has poor fingerprint display in a humid environment, the vacuum metal deposition method needs harsh conditions such as vacuumizing, and the like, and the factors restrict the rapid fingerprint display on site. The physical and chemical methods of iodine fumigation and 502 glue fumigation have very large toxicity, and the two methods need special fumigation boxes, for example, the large fumigation boxes need to be customized for the fingerprint display of a particularly large object like a car. Electrochemical methods are a technology which is developed rapidly, however, the electrochemical technology still needs complex electrochemical operations such as electropolymerization and the like, and also needs some special and even expensive electrochemical devices such as a scanning electrochemical microscope and the like. Since many substances (such as amino acids, lipids, and DNA) in fingerprints have very weak autofluorescence themselves, it is difficult for the photoluminescence technology to directly realize the visualization of latent fingerprints. Therefore, the chemical visualization method is a better method for rapidly visualizing the fingerprints in the field at present.
The main principle of the chemical display method is to utilize the specific combination of special chemical reagents and special components in fingerprints, such as amino acids, lipids, DNA or antigens, to identify the fingerprints, and simultaneously utilize the change of color or fluorescence signals before and after combination to achieve the purpose of fingerprint display. Especially, the fluorescence display can obtain clearer fingerprint lines compared with color display due to high sensitivity, and some fingerprint lines can even obtain better three-level characteristics of the fingerprint. Indandione, DFO (1,8-diazafluoren-9-one), IND (1,2-Indanedione) and derivatives thereof are currently commercial chemicals used for fingerprint fluorescence visualization. Although these agents enable clear and rapid development of latent fingerprints, in practice, it is generally necessary to use a very high proportion of organic solvent as a co-solvent, and to use relatively high temperatures (above 80 ℃) to achieve rapid development. The use of organic solvents can be a significant hazard to foreline medical personnel. While higher temperature fumigation requires special equipment such as a heat gun. The organic solvent and the higher temperature are not beneficial to displaying the three-level characteristics of the fingerprint, and can also generate irreversible damage to DNA substances in the fingerprint, so that the subsequent DNA extraction based on the fingerprint is difficult.
In recent years, based on the continuous breakthrough from theory to technology in research on nanotechnology, biotechnology and fluorescent light-emitting materials, a new round of development of chemical agents for developing latent fingerprints has been carried out by a group of domestic and foreign subjects using technologies accumulated in these fields. For example, aggregation Induced Emission (AIE) dye molecules are doped in powder specifically combined with various fingerprints to prepare a latent fingerprint developing reagent, the latent fingerprint developing reagent is developed by combining an antibody technology and an electrochemical technology, a method for imaging latent fingerprints by utilizing a nanophotonics means is utilized, a developing reagent is prepared by utilizing an aptamer identified by specific fingerprints and combining a commercial dye Fluor @ Orange560 to be used for latent fingerprint imaging, and a silane-regulated organic conjugated material is used for latent fingerprint developing. Although the design and synthesis of these agents is beneficial for the development of latent fingerprint developing chemical agents, there are still problems: 1) Most of fluorescent staining reagents are used for clearly showing fingerprint lines after being repeatedly cleaned; 2) Many agents do not clearly reveal the tertiary features of a fingerprint; 3) The nano materials and the like are easy to aggregate, so that the reagent cannot be stored for a long time; 4) Some reagents still require a high proportion of organic solvent to assist in dissolution, resulting in greater toxicity. 5) Latent fingerprint imaging of powdered reagents in humid environments remains difficult.
An amphiphilic dyeing reagent is developed based on an aggregation-induced emission (AIE) principle so far for latent fingerprint imaging, and is a dye molecule capable of realizing efficient, rapid and clear three-level fingerprint imaging of latent fingerprints so far. However, in practice, there are still difficulties in imaging latent fingerprints on some smooth surface objects (acrylic plates of various different dark colors), dark background objects (such as green background rubber), a large portion of artificial leather, and the like. Meanwhile, the excitation spectrum of the dye molecules still stays at about 405nm, so that the autofluorescence of an object (especially a dark object or an object with fluorescence) is easily excited, and a detection signal is interfered. On the other hand, the prior art mainly develops the fingerprint dyeing reagent based on diarylethene compounds. Meanwhile, aromatic heterocyclic cations such as pyridine cations and the like are mainly utilized to reduce the fluorescence of the styrene structure in an aqueous solution, so that off-on detection of latent fingerprints is realized, and the repeated cleaning process is avoided. Except for the reagent, no novel fluorescent compound for latent fingerprint dyeing with high efficiency, rapidness and convenience is reported so far.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a fluorescent dye probe for latent fingerprint detection, which meets the requirements of a rapid, efficient and low-toxicity latent fingerprint staining reagent, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
aiming at the defects in the prior art and the requirement for a new rapid, efficient and low-toxicity latent fingerprint staining reagent, the invention provides an application of a fluorescent dye probe molecule based on a green fluorescent protein chromophore (imidazolinone) skeleton structure in latent fingerprint imaging. The fluorescent dye probe has high biological safety, and can perform rapid (within 30 seconds) and efficient fluorescence color development on latent fingerprints on different objects in an aqueous solution. Meanwhile, through the modification of the imidazolone skeleton, the invention can provide a dyeing reagent with full coverage of excitation and emission wavelengths from 350-1200nm. Furthermore, the innovative point of the structure is that the molecular rotation structure of the imidazolone skeleton is utilized, the skeleton is quickly twisted in the aqueous solution, so that the designed color developing reagent keeps a fluorescent 'dark state' before the aqueous solution is not contacted with a fingerprint area, and the twist inhibition is converted into a fluorescent 'bright state' once the fingerprint area is identified, thereby realizing the high-efficiency 'off-on' fluorescence imaging of the latent fingerprint. The recognition mechanism is not reported in any patent or paper at present. For the first time, the inventor finds and proposes the following specific steps:
a fluorescent dye probe for latent fingerprint detection has a chemical structural formula shown in formula I:
wherein R is 1 Is an aromatic ring (including aromatic heterocyclic ring) compound or methyl, R 3 Is an aromatic ring (including aromatic heterocyclic ring) compound, R 2 Is an alkane group (containing hydrophilic and non-hydrophilic groups), R 2 And R 3 At least one is a hydrophilic group.
Further, said R 1 And R 3 Each independently is an aromatic ring structure comprising one or more of benzene ring, naphthalene ring, thiophene, indole, aniline, diphenylamine, triphenylamine, carbazole or fluorene, and specifically comprises the following components:
further, said R 2 And/or R 4 Comprises the following stepsOne of the groups:
wherein R is 5 ，R 6 And R 7 Hydrogen, alkyl, amino-terminated alkyl or hydroxyalkyl, and various cationic alkane quaternary ammonium salts.
A method for preparing the fluorescent dye probe for latent fingerprint detection comprises the following steps:
(1) Respectively adding N-acetylglycine and R into a reactor 3 Aldehyde, sodium acetate and acetic anhydride are subjected to reflux reaction under the protection of nitrogen, cooled after reaction until solid is separated out, washed by n-hexane to remove anhydride, filtered, possibly washed by cold ethanol, and dried to obtain a product A;
(2) In the reactor, the compounds A and R are added separately 2 And (3) adding amine, and optionally potassium carbonate or pyridine, adding a solvent to the mixture to submerge the solid, refluxing the mixture under the protection of nitrogen for reaction overnight, cooling the mixture after the reaction, removing the solvent under reduced pressure, and separating to obtain a compound B, namely the fluorescent dye probe for latent fingerprint detection.
Further, the preparation method also comprises the following steps:
(3) And respectively adding the compound B, aldehyde and zinc chloride into a reactor, adding a solvent to submerge the solid, carrying out reflux reaction under the protection of nitrogen, cooling after the reaction, removing the solvent under reduced pressure, and separating to obtain a compound C, namely the fluorescent dye probe for latent fingerprint detection.
Further, in the step (1), the N-acetylglycine and R are 3 The molar ratio of aldehyde is (1.1-1.3) to 1; in the step (2), the compounds A and R 2 The molar ratio of the amine is 1 (1.2-1.6); in the step (3), the molar ratio of the compound B to the aldehyde is 1 (1.2-1.6).
Further, in the steps (1) and (3), the reflux reaction time is 2-10h.
The application of the fluorescent dye probe for latent fingerprint detection is applied to latent fingerprint fluorescence imaging, and specifically comprises the following operation steps:
A. contacting a solution containing a fluorescent dye probe with a carrier containing latent fingerprints, so that the structural vibration of the fluorescent dye probe is inhibited after the fluorescent dye probe is targeted to a latent fingerprint area;
for example, a solution containing the fluorescent dye probe is dropped on a carrier containing a latent fingerprint, or a solution containing the fluorescent dye probe is sprayed on a carrier containing a latent fingerprint, or a carrier containing a latent fingerprint is soaked in a solution containing the fluorescent dye probe, so that the solution containing the fluorescent dye probe contacts the carrier containing a latent fingerprint.
For another example, the solution containing the fluorescent dye probe is loaded in a small atomizer, and the solution containing the fluorescent dye probe is atomized and sprayed on a carrier containing the latent fingerprint, so that the solution containing the fluorescent dye probe is contacted with the carrier containing the latent fingerprint, and the purpose of developing the fingerprint area is achieved.
The solution of the fluorescent dye probe is obtained by dissolving the fluorescent dye in a solvent, wherein the solvent is deionized water or an organic solvent or a mixed solvent, and is preferably an aqueous solution.
B. Under the irradiation of exciting light, the fluorescent dye probe emits emitting light to realize the fluorescent imaging of latent fingerprints.
Further, the concentration of the solution is 0.1 to 10mol/L, preferably 30 to 2mol/L; the wavelength of the excitation light and the emission light is 350-1200nm, preferably 405-633nm for the excitation light and 500-1200nm for the emission light.
Further, before irradiation of exciting light, the fluorescent dye probe stays on the latent fingerprint for 5s-5min, preferably 10-60s of developing time, after staying for a period of time, the fluorescent dye probe is irradiated by the exciting light again, so that the latent fingerprint on the surface of an object can show brighter fluorescence, and then fluorescent fingerprint imaging with low background noise, high brightness and high definition can be obtained more simply, conveniently and directly by using a common single-lens reflex camera.
The invention utilizes the fluorescent dye probe to lead the operation of potential fingerprint imaging to be rapid and portable; the latent fingerprint is imaged clearly and no influence or loss is caused on the latent fingerprint. There is little background fluorescence under excitation light illumination. The invention can simply operate under the collecting background of different colors to obtain clear fingerprint imaging with high identification degree.
Compared with the prior art, the invention has the following advantages:
(1) The invention provides an application of a functional fluorescent dye probe based on an imidazolidinone skeleton in latent fingerprint display; by R 1 And R 3 At two conjugate junctions, the conjugated system can be expanded to provide dyes of different excitation and emission wavelengths from visible to near infrared; at the same time, by R 2 The derivation of the position can connect various better cationic groups which can interact with the substances in the latent fingerprint area, thus realizing the purpose of specifically showing the latent fingerprint;
(2) Based on the rapid torsion of the imidazolone skeleton in the aqueous solution, the designed color developing reagent keeps a fluorescent 'dark state' before the aqueous solution is not contacted with a fingerprint area, and the torsion inhibition is converted into a fluorescent 'bright state' once the fingerprint area is identified, so that the high-efficiency 'off-on' fluorescence imaging of latent fingerprints is realized, and the repeated flushing of other color developing reagents in the latent fingerprint imaging is avoided;
(3) The imidazolinone skeleton is the core chromophore of green fluorescent protein and is formed through amino acid condensation, and has very low toxicity. The biological safety and low toxicity of the reagent are ensured, and the subsequent DNA detection is not interfered.
Drawings
FIG. 1 is a graph showing the color development effect of FLYSTracker @ yellow prepared in example 1 on latent fingerprints on different objects;
FIG. 2 is the color development effect of FLYSTracker @ Red prepared in example 2 on latent fingerprints on different objects;
FIG. 3 shows the color development effect of Nt-OH prepared in example 3 on latent fingerprints on different objects.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
A fluorescent dye probe for latent fingerprint detection is similar to molecular structures of the fluorescent dye probe FLYSTracker @ yellow and the probe FLYSTracker @ yellow of the embodiment, and the chemical structural formula of the probe is shown as formula I:
wherein R is 1 Is an aromatic ring (including aromatic heterocyclic ring) compound or methyl, R 3 Is an aromatic ring (including aromatic heterocyclic ring) compound, R 2 Are alkane groups (containing both hydrophilic and non-hydrophilic groups).
In some embodiments, R 1 And R 3 Each independently is an aromatic ring structure comprising one or more of benzene ring, naphthalene ring, thiophene, indole, aniline, diphenylamine, triphenylamine, carbazole or fluorene as follows:
in some embodiments, R is 2 And/or R 4 Comprising one of the following groups:
wherein R is 5 ，R 6 And R 7 Is hydrogen, alkyl, terminal aminoalkyl or terminal hydroxyalkyl.
The overall method of the preparation method of the fluorescent dye probe for latent fingerprint detection is similar to the FLYSTracker @ yellow and the probe FLYSTracker @ yellow in the embodiment, and when fingerprint imaging is performed by adopting the same or similar method, a better fingerprint imaging effect can be obtained, and the method comprises the following steps:
(1) Respectively adding N-acetylglycine and R into a reactor 3 Aldehyde, sodium acetate and acetic anhydride are subjected to reflux reaction under the protection of nitrogen, cooled after reaction until solid is separated out, washed to remove the anhydride, filtered, washed and dried to obtain a product A; N-Acetylglycine and R 3 The molar ratio of aldehyde is (1.1-1.3): 1, the reflux reaction time is 2-10h, and the reaction formula is as follows:
(2) In the reactor, the compounds A and R are added separately 2 Adding an amine, adding a solvent to submerge the solid, carrying out reflux reaction overnight under the protection of nitrogen, cooling after the reaction, removing the solvent under reduced pressure, and separating to obtain a compound B, namely the fluorescent dye probe for latent fingerprint detection; compounds A and R 2 The molar ratio of the amine is 1 (1.2-1.6), and the reaction formula is as follows:
it is also possible to include the following steps:
(3) Respectively adding a compound B, aldehyde and zinc chloride into a reactor, adding a solvent to submerge the solid, carrying out reflux reaction under the protection of nitrogen, cooling after the reaction, removing the solvent under reduced pressure, and separating to obtain a compound C, namely the fluorescent dye probe for latent fingerprint detection; the molar ratio of the compound B to the aldehyde is 1 (1.2-1.6), the reflux reaction time is 2-10h, and the reaction formula is as follows:
the application of the fluorescent dye probe for latent fingerprint detection is applied to latent fingerprint fluorescence imaging, and specifically comprises the following operation steps:
A. contacting a solution containing a fluorescent dye probe with a carrier containing latent fingerprints, so that the structural vibration of the fluorescent dye probe is inhibited after the fluorescent dye probe is targeted to a latent fingerprint area; the concentration of the solution is 0.1 mu mol/L-10mol/L, preferably 30 mu mol/L-2mol/L; at high concentrations, the dye, which is poorly soluble, can be placed in an ultrasonic cleaner for ultrasonic mixing to aid in dissolution until the solution is clear and transparent.
For example, a solution containing the fluorescent dye probe is dropped on a carrier containing a latent fingerprint, or a solution containing the fluorescent dye probe is sprayed on a carrier containing a latent fingerprint, or a carrier containing a latent fingerprint is soaked in a solution containing the fluorescent dye probe, so that the solution containing the fluorescent dye probe contacts the carrier containing a latent fingerprint.
For another example, the solution containing the fluorescent dye probe is loaded in a small atomizer, atomized and sprayed on a carrier containing latent fingerprints, so that the solution containing the fluorescent dye probe is contacted with the carrier containing the latent fingerprints, and the purpose of developing the color of the fingerprint area is achieved.
The solution of the fluorescent dye probe is obtained by dissolving the fluorescent dye in a solvent, wherein the solvent is deionized water or an organic solvent or a mixed solvent, and is preferably an aqueous solution.
B. Under the irradiation of exciting light, for example, an LED lamp with a certain wavelength or a small-power (5W) laser is used for irradiating the object, and the fluorescent dye probe emits emitting light to realize the fluorescent imaging of the latent fingerprint. The wavelengths of the excitation light and the emission light are 350-1200nm, preferably 405-633nm for excitation light and 500-1200nm for emission light. Before the irradiation of exciting light, the fluorescent dye probe can stay on the latent fingerprint for 5s-5min, preferably 10-60s of color development time, and after the stay for a period of time, the fluorescent dye probe is irradiated by the exciting light again, so that the latent fingerprint on the surface of an object can show brighter fluorescence.
Example 1
Synthesis of fluorescent dye Probe FLYSTracker @ yellow:
(1) Preparation of compound 1:
in a 100mL round-bottom flask, N-acetylglycine (500mg, 4.27mmol), p-dimethylaminobenzaldehyde (530mg, 3.56mmol) and sodium acetate (437mg, 5.33mmol) were added, respectively, and acetic anhydride (6 mL) was reacted under reflux under nitrogen for 3 hours. After cooling to room temperature, a solid precipitated, which was washed with 15ml of n-hexane to remove the anhydride, filtered, washed with cold ethanol and dried in a vacuum desiccator at 60 ℃ overnight to give the product as a dark red solid with a yield of 65%. 1 H NMR(400MHz,CDCl 3 )δ8.00(d,J＝8.9Hz,2H),7.09(s,1H),6.70(d,J＝9.0Hz,2H),3.09(s,6H),2.37(s,3H)。
(2) Preparation of compound 2:
in a 100mL round-bottom flask, compound 1 (500mg, 2.17mmol), N, N-dimethylethylenediamine (474. Mu.L, 4.34 mmol), potassium carbonate (495mg, 3.25mmol), and ethanol (15 mL) were added, and the mixture was refluxed for 10 hours under nitrogen protection. Cooled and the solvent removed under reduced pressure. Column chromatography with dichloromethane afforded an orange yellow solid with a yield of 45%. 1 H NMR(400MHz,CDCl 3 )δ7.45-7.43(m,2H),7.23-7.19(m,2H),7.07(s,1H),6.80-6.88(d,J＝7.8Hz,1H),3.61(t,J＝6.6Hz,2H),2.98(s,6H),2.42(t,J＝6.3Hz,2H),2.33(s,3H),2.20(s,6H)。
(3) Preparation of FLYSTracker @ yellow fluorescent dye probe for latent fingerprint imaging:
compound 2 (300mg, 1mmol) was dissolved in 150ml of methylene chloride, heated to be completely dissolved, and filtered while hot. Methyl iodide (1.7ml, 27mmol) was added to the filtrate and stirred at room temperature for 48 hours. Precipitate is separated out from the reaction solution and centrifuged to obtain the target product, namely a dark red solid with the yield of 78 percent.
The basic data for the probe are as follows:
dark red solid powder
1 H NMR(400MHz,CD 3 OD),δ7.63(s,1H),7.43(d,J＝8.1Hz,1H),7.27(t,J＝8.1Hz,1H),7.08(s,1H),6.89-6.86(dd,J＝10.5Hz,1H),4.16(t,J＝5.7Hz,2H),3.66(t,J＝7.2Hz,2H),3.3(s,9H),2.97(s,6H),2.49(s,3H)；
13 CNMR(101MHz,CD 3 OD)，δ172.41,163.55,152.57,138.71,135.71,131.07,130.49,122.65,117.57,116.89,64.34,54.29,41.08,35.76,15.90.HRMS(ES+):C 18 H 27 N 4 O + [M]Calculated values are: 315.2179, actual value: 315.2186.
FLYSTracker @ yellow color development on latent fingerprints
An aqueous solution of a fluorescent dye probe was prepared. The fluorescent dye probe was dissolved in a predetermined amount of aqueous solution to a concentration of 90. Mu. Mol/L. The solution can be put into an ultrasonic cleaner for ultrasonic mixing to accelerate dissolution until the solution is clear and transparent. The dye is used for subsequent latent fingerprint color development after being prepared. Wherein the dye is the fluorescent dye probe FLYSTracker @ yellow of the invention.
The aqueous dye solution was loaded into a small atomizer and atomized against the object with the fingerprint left for 30 seconds. The object was irradiated with a small power (5W) laser at 405 nm. The image was taken by a camera through a filter (light having a wavelength of 500nm or less transmitted through the filter) and recorded. The clearer fingerprint lines and 3-level features can be recorded. FIG. 1 shows the effect of FLYSTracker @ yellow on latent fingerprints on different objects.
Example 2
Synthesis of fluorescent dye probe FLYSTracker @ Red:
(1) Preparation of compound 3:
in a 100mL round-bottom flask, each of the examples was chargedCompound 2 (500mg, 1.6mmol) in 1, p-dimethylaminobenzaldehyde (358mg, 2.4mmol), zinc chloride (2.2g, 1695mmol), dioxane (20 mL) were refluxed for 2-4 hours under nitrogen protection. Cooled and the solvent removed under reduced pressure. Column chromatography with dichloromethane gave a magenta solid in 60% yield. 1 H NMR(400MHz,CDCl 3 )δ9.73(s,1H),7.99(d,J＝8.8Hz,2H),7.73(d,J＝8.8Hz,2H),7.08(s,1H),6.71(s,5H),3.07(s,18H),2.36(s,4H).
(2) Preparation of FLYSTracker @ Red fluorescent dye probe for latent fingerprint imaging:
compound 3 (100mg, 0.23mmol) was dissolved in 80ml of methylene chloride, heated to be completely dissolved, and filtered while hot. Methyl iodide (0.57ml, 6.26mmol) was added to the filtrate and stirred at room temperature for 48 hours. Precipitate is separated out from the reaction solution and centrifuged to obtain a target product, namely a black solid with the yield of 48 percent.
The basic data for the probe are as follows:
black solid powder
1 H NMR(400MHz,DMSO-d 6 )δ8.17(d,J＝5.9Hz,2H),7.90(d,J＝12.2Hz,1H),7.74(d,J＝9.8Hz,2H),7.00–6.89(m,2H),6.82–6.72(m,4H),4.28(s,2H),3.66(t,J＝7.3Hz,2H),3.24(s,9H),3.03(d,J＝12.2Hz,12H)；
13 C NMR(101MHz,DMSO-d 6 )δ151.39,151.17,140.03,134.01,130.13,125.77,122.04,111.73,111.68,107.12,62.59,52.40,39.65,39.60,33.42,28.86.
HRMS(ES+):C27H36N5O + [M]Calculated values: 446.2914, actual value: 446.2921.
FLYSTracker @ Red developing color for latent fingerprints
An aqueous solution of a fluorescent dye probe was prepared. The fluorescent dye probe was dissolved in a predetermined amount of aqueous solution to a concentration of 90. Mu. Mol/L. The solution can be put into an ultrasonic cleaner for ultrasonic mixing to accelerate dissolution until the solution is clear and transparent. The dye is used for subsequent latent fingerprint color development after being prepared. Wherein the dye is the fluorescent dye probe FLYSTracker @ Red of the invention.
The aqueous dye solution was loaded into a small atomizer and atomized for 30 seconds against the object with the fingerprint left. The object was irradiated with a small power (5W) laser at 405 nm. The image was taken by a camera through a filter (light having a wavelength of 500nm or less transmitted through the filter) and recorded. The clearer fingerprint lines and 3-level features can be recorded. FIG. 2 shows FLYSTracker @ Red latent fingerprint color rendering effects on different objects.
Example 3:
synthesis of fluorescent dye probe Nt-OH:
(1) Preparation of Compound A
In a 100mL round-bottom flask were added in this order sodium acetate (622.5mg, 0.75mmol), N-acetylglycine (587 mg,0.5 mmol), 2-naphthaldehyde (781mg, 0.5 mmol), and acetic anhydride (10 mL). The reaction was heated to 110 ℃ under nitrogen atmosphere and stirred for 5 hours. Water/ethanol (2/1,v/v, 50 mL) was added to the reaction and cooled to 25 ℃. Stirring was carried out at 0 ℃ for 30 minutes, and filtration while washing with ethanol gave a yellow solid. The filter residue was dried in a vacuum oven at 50 ℃ overnight to give compound 3 as a golden yellow solid (924 mg, 78% yield) for the next step without further purification.
(2) Preparation of Compound B
In a 100ml round bottom flask, compound A (100mg, 0.42mmol), methylaminoethanol (4 ml, containing 30wt% methylamine) were added and stirred at 25 ℃ under nitrogen for 2h and evaporated in vacuo to give a white residue. Pyridine (5 ml) was added to the solid and refluxed at 110 ℃ for 8 hours. The solvent was evaporated in vacuo. The crude mixture was purified by column chromatography (5:1-2:1, petroleum ether: ethyl acetate) to give compound B (59 mg, 56% yield) as a yellow solid. 1 H NMR(400MHz,CDCl 3 )δ8.42(s,2H),7.85(s,3H),7.49(s,2H),7.25(s,1H),3.14(s,3H),2.36(s,3H).
(1) Preparation of Compound C
2-bromoethanol (750mg, 6mmol), 4-pyridylaldehyde (428mg, 4mmol) and acetonitrile (10 mL) were sequentially added to a 100-mL round-bottomed flask. The mixture was heated to 70 ℃ under nitrogen atmosphere and stirred for 20h, then the reaction was concentrated to 25 ℃ under reduced pressure. The crude mixture was purified by column chromatography (10: 1 to 5:1, dichloromethane: methanol) to give compound 1 (256 mg, 42% yield) as a pale yellow oil. 1 H NMR(400MHz,D2O)δ8.81(d,J＝6.4Hz,2H),8.10(d,J＝6.2Hz,2H),6.16(s,1H),4.02-3.99(m,2H),3.26(s,2H).
(2) Preparation of fluorescent dye probe Nt-OH
A100 mL round-bottom flask was charged with Compound B (250mg, 1mmol) and Compound C (100mg, 0.66mmol), 1,4-dioxane (3 mL), znCl 2 (860mg, 6.6 mmol). The mixture was heated to 80 ℃ and stirred under nitrogen atmosphere for 3 hours. After 3h, the volatiles were removed under reduced pressure. The crude mixture was purified by column chromatography (20: 5:1, dichloromethane: methanol) to afford Nt-OH (198 mg, 78% yield) as a black solid. HRMS (ES +: C) 24 H 22 N 3 O 2 +[M]Calculated values: 384.1707, actual value: 384.1713.
Nt-OH color development on latent fingerprints
An aqueous solution of a fluorescent dye probe was prepared. The fluorescent dye probe was dissolved in a predetermined amount of aqueous solution to a concentration of 250. Mu. Mol/L. The solution can be put into an ultrasonic cleaner for ultrasonic mixing to accelerate dissolution until the solution is clear and transparent. The dye is used for subsequent latent fingerprint color development after being prepared. Wherein the dye is the fluorescent dye probe Nt-OH of the invention.
The aqueous dye solution was loaded into a small atomizer and atomized against the object with the fingerprint left for 30 seconds. The object was irradiated with a small power (5W) laser at 405 nm. The image was taken by a camera through a filter (light having a wavelength of 500nm or less transmitted through the filter) and recorded. The clearer fingerprint lines and 3-level features can be recorded. FIG. 3 shows the color development effect of the latent Nt-OH fingerprints on different objects.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (4)
1. A fluorescent dye probe for latent fingerprint detection is characterized in that the chemical structural formula of the probe is as follows:
2. The application of the fluorescent dye probe for latent fingerprint detection according to claim 1, which is applied to latent fingerprint fluorescence imaging, and comprises the following steps:
A. contacting a solution containing a fluorescent dye probe with a support containing a latent fingerprint;
B. under the irradiation of exciting light, the fluorescent dye probe emits emitting light to realize the fluorescent imaging of latent fingerprints.
3. The use of the fluorescent dye probe for latent fingerprint detection according to claim 2, wherein the concentration of the solution is 0.1 μmol/L to 10mol/L; the wavelengths of the excitation light and the emission light are 350-1200nm.
4. The use of a fluorescent dye probe for latent fingerprint detection according to claim 3, wherein the fluorescent dye probe stays on the latent fingerprint for 5s-5min before the irradiation of the excitation light.
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Non-Patent Citations (4)
| Title |
|---|
| 《HOBDI和BODIPY染料衍生荧光探针的设计合成及活细胞成像应用》;李晓林;《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》;20180815(第8期);B014-183 * |
| 《基于点击化学的比率型荧光团-RNA复合物和三（2-羧乙基）膦近红外荧光探针》;郭慧;《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》;20200615(第6期);B014-896 * |
| 《基于荧光蛋白发色团的Aβ蛋白荧光探针的构建及其生物成像应用》;孙涵;《中国优秀硕士学位论文全文数据库 (医药卫生科技辑)》;20210215(第2期);E071-77 * |
| 《绿色荧光蛋白荧光团HBDI分子及变体结构分子的修饰、表征和性能研究》;杜涵;《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》;20160115(第1期);B014-419 * |
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