CN109680407B - Preparation method of in-situ polymerized ninhydrin/polyvinyl alcohol nanofiber composite membrane and fingerprint detection method - Google Patents
Preparation method of in-situ polymerized ninhydrin/polyvinyl alcohol nanofiber composite membrane and fingerprint detection method Download PDFInfo
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- CN109680407B CN109680407B CN201811535791.2A CN201811535791A CN109680407B CN 109680407 B CN109680407 B CN 109680407B CN 201811535791 A CN201811535791 A CN 201811535791A CN 109680407 B CN109680407 B CN 109680407B
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- ninhydrin
- polyvinyl alcohol
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 84
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 84
- FEMOMIGRRWSMCU-UHFFFAOYSA-N ninhydrin Chemical compound C1=CC=C2C(=O)C(O)(O)C(=O)C2=C1 FEMOMIGRRWSMCU-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002121 nanofiber Substances 0.000 title claims abstract description 60
- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001514 detection method Methods 0.000 title abstract description 9
- 238000011065 in-situ storage Methods 0.000 title abstract description 8
- 239000000243 solution Substances 0.000 claims description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- 238000010041 electrostatic spinning Methods 0.000 claims description 24
- 238000009987 spinning Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001523 electrospinning Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 abstract description 6
- 210000004243 sweat Anatomy 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000539 amino acid group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000000489 vacuum metal deposition Methods 0.000 description 2
- SPIRTQMOSBLBRD-UHFFFAOYSA-N 3-amino-3H-indene-1,2-dione Chemical compound NC1C(C(C2=CC=CC=C12)=O)=O SPIRTQMOSBLBRD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 229920001872 Spider silk Polymers 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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- A—HUMAN NECESSITIES
- 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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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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Abstract
The invention discloses a preparation method of an in-situ polymerized ninhydrin/polyvinyl alcohol nanofiber composite membrane and a fingerprint detection method. The nanofiber membrane has a large specific surface area, can react with amino acids in sweat, and achieves the purpose of displaying fingerprints.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a material for processing a fingerprint identification and a fingerprint identification method. Can be applied to the technical fields of nano material analysis technology and fingerprint detection.
Background
The fingerprint is the line formed by concave-convex skin on the finger abdomen at the tail end of the finger. The latent fingerprint refers to a finger fold concave-convex pattern left on an object surface after a finger contacts the object. These patterns are objectively unrecognizable by naked eyes, and require a certain processing means to show the original appearance, so they are called latent fingerprints. Fingerprint identification will be the most attractive means of authentication because of the uniqueness and invariance of an individual's fingerprint. Generally, after fingerprints are printed, less substance is left on the surface of a material surface, wherein 99% of water is rapidly evaporated, and about 50% of the rest 1% of the substance is inorganic substances such as sodium chloride, potassium chloride and the like, which have little value on fingerprints; but only organic components such as grease, amino acid and the like and protein can achieve the ability of clearly presenting fingerprints after developing color, so that the search for a reagent and a detection material preparation method which have high sensitivity in interaction with organic residues of fingerprints is an important work for improving the fingerprint appearance rate and the definition.
The physical display extraction method at the present stage mainly comprises a powder display method, a low-temperature technology display extraction method, vacuum metal deposition, a display extraction method, a laser display method, an optical inspection method and the like. The chemical expression and extraction method mainly utilizes the characteristics of a newly generated substance to convert invisible or unrecognizable fingerprints into visible or recognizable fingerprints. Currently, the more common chemical development methods include iodine fumigation, silver nitrate method, ninhydrin, DFO method, and "502" glue method. The traditional latent fingerprint identification method has many defects, such as insufficient sensitivity, easy environmental influence and the like. Secondly, the conventional method requires complicated and cumbersome pretreatment processes such as cyanoacrylate treatment or vacuum metal deposition, and also uses expensive optical equipment in the process of observing and analyzing fingerprints.
The electrostatic spinning nanofiber membrane is formed by three-dimensionally stacking different-thickness nanofibers, and has a large specific surface area. The Chinese patent of invention CN 102115953A, an electrostatic spinning nanofiber membrane, a preparation method and a method for detecting fingerprints, provides a method for rapidly detecting potential fingerprints by using the electrostatic spinning nanofiber membrane. The method has the advantages that the fluorescein dye is expensive, the spinning of water-soluble polymers such as polyvinyl alcohol (PVA), polyvinylpyrrolidone and the like is used, the fingerprint identification reaction can be only carried out under the catalysis conditions of no water and water vapor, and the fingerprint display condition is harsh. Therefore, it is necessary to develop a new material carrier with a wide application range, a preparation method and a detection method to simply realize the rapid detection of fingerprints.
Disclosure of Invention
The invention solves the defects and problems in the prior art, provides a preparation method of an in-situ polymerized ninhydrin/PVA nanofiber composite membrane, and solves the problems of an electrostatic spinning nanofiber membrane and a fingerprint detection method in the prior art. The method is simple, rapid, high in sensitivity, non-toxic and harmless, and does not need to borrow large-scale instruments. The prepared fiber membrane has the advantages of wide application range, convenient operation, easily obtained raw materials and easy mass production.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an in-situ polymerized ninhydrin/polyvinyl alcohol nano-fiber composite membrane comprises the following steps: the preparation method comprises the steps of compounding hydrochloric acid, glutaraldehyde, polyvinyl alcohol and ninhydrin in a certain molar ratio to form a spinning solution, loading ninhydrin on a nanofiber membrane by an electrostatic spinning method, and uniformly dispersing the ninhydrin on the nanofiber membrane to obtain an in-situ crosslinking nano-film material, namely an in-situ polymerization ninhydrin/PVA nanofiber composite membrane, namely a crosslinking PVA nanofiber membrane containing the ninhydrin, and can be used for extracting and identifying fingerprints with high definition, sensitivity and rapidness.
According to the technical scheme, the preparation method of the spinning solution preferably comprises the following steps:
(1) uniformly mixing 10-12.5wt% of PVA aqueous solution with 25-35wt% of ninhydrin aqueous solution or ninhydrin ethanol solution in a volume ratio of 8:2 to obtain PVA/ninhydrin composite solution with the PVA content of 8-10wt% and the ninhydrin content of 5-7 wt%;
(2) uniformly mixing hydrochloric acid and glutaraldehyde according to the molar ratio of glutaraldehyde to HCl (4.5-5.5) to 1 to obtain glutaraldehyde/HCl composite solution;
(3) mixing the PVA/ninhydrin composite solution and the glutaraldehyde/HCl composite solution before spinning according to the molar ratio of glutaraldehyde to PVA of (0.01-1) to (85-90) to obtain a spinning solution.
According to the technical scheme, the preparation method of the PVA aqueous solution preferably comprises the following steps: PVA is dissolved in deionized water to prepare 10-12.5wt% PVA water solution, and the PVA water solution is stirred at 90-100 deg.c until the solution is transparent.
According to the technical scheme, preferably, 10-12.5wt% of PVA aqueous solution, 25-35wt% of ninhydrin aqueous solution or ninhydrin ethanol solution are prepared, and the 10-12.5wt% of PVA aqueous solution and the 25-35wt% of ninhydrin aqueous solution or ninhydrin ethanol solution are uniformly mixed in a volume ratio of 8:2 to obtain PVA/ninhydrin composite solution with PVA of 8-10wt% and ninhydrin of 5-7 wt%.
According to the technical scheme, the electrostatic spinning method can adopt a needle-free electrostatic spinning method or a needle-head electrostatic spinning method.
According to the technical scheme, the preferable conditions of the needle-free electrostatic spinning are as follows: the voltage of the needle-free electrostatic spinning equipment is 60-80kV, the speed of a solution box is 80-150mm/s, and the spinning time is 40-120 min.
According to the technical scheme, preferably, the needle type electrostatic spinning conditions are as follows: the voltage of the needle type electrostatic spinning equipment is 20-30kV, the solution extrusion speed is 0.5-1ml/h, the spinning time is 100-.
The ninhydrin/PVA nanofiber composite membrane (the crosslinked PVA nanofiber membrane containing ninhydrin) obtained by the preparation method can be applied to fingerprint detection, and can be used for high-definition and sensitive fingerprint identification.
The method for detecting fingerprints by using the ninhydrin/PVA nanofiber composite membrane comprises the following steps:
(1) directly pressing a finger on a ninhydrin/PVA nanofiber composite membrane (a crosslinked PVA nanofiber membrane containing ninhydrin), or directly covering the ninhydrin/PVA nanofiber composite membrane (the crosslinked PVA nanofiber membrane containing ninhydrin) on a smooth object with a potential fingerprint, and applying certain pressure to obtain the potential fingerprint;
(2) the ninhydrin/PVA nanofiber composite membrane (crosslinked PVA nanofiber membrane containing ninhydrin) containing potential fingerprints is moved away from an object and is put in a hot steam condition of 90-100 ℃ with the pH value of 5.5-6.5 for 60-300s to obtain a fingerprint pattern which can be clearly seen by naked eyes under visible light, and the obtained fingerprint image specimen can be stored for a long time.
According to the above technical solution, preferably, in the step (2), the ninhydrin/PVA nanofiber composite membrane (crosslinked PVA nanofiber membrane containing ninhydrin) containing the latent fingerprint is removed from the guest and heated under the conditions of 90-100 ℃ and pH 5.5-6.5 for 60-300s, so as to obtain the fingerprint pattern clearly visible to the naked eye under visible light, and the obtained fingerprint pattern specimen can be stored for a long time.
Ninhydrin is a reagent used to detect ammonia or primary and secondary amines. The fingerprint sweat contains amino acid residue, and ninhydrin is heated together with amino acid in weakly acidic solution to undergo decarboxylation and hydrolysis reaction to generate ninhydrin with amino group. Finally, the aminoindandione and ninhydrin are condensed to produce a purple material.
The invention has the beneficial effects that:
1. the prepared raw materials are easy to obtain, the PVA cost is low, and no toxic or side effect exists.
2. The in-situ crosslinked nanofiber membrane has the advantages of improved strength, simple preparation method and wide application range.
3. The nanofiber membrane has a large specific surface area, and the loaded ninhydrin nanofiber membrane can efficiently perform a color reaction with amino acids in sweat, so that the purpose of fingerprint extraction is achieved.
4. The fingerprint displaying process is quick and convenient, and the displaying process only needs less than 5 minutes under the humid and hot air.
5. No special optical equipment is required.
6. After the fingerprint is displayed, the specimen is stable, and the specimen still has no abnormality after being placed at room temperature for several months.
7. The fingerprint contrast is clear, and the naked eye can distinguish under the natural light.
Drawings
FIG. 1(a) is SEM photograph of electrospun nanofiber membrane obtained in example 1;
FIG. 1(b) is SEM photograph of electrospun nanofiber membrane obtained in example 2;
FIG. 1(c) is an SEM photograph of an electrospun nanofiber membrane obtained in example 3;
FIG. 2 shows the reaction mechanism for ninhydrin with amino acids;
FIG. 3(a) is an optical photograph of a fingerprint of the nanofiber film of example 1 after color development;
FIG. 3(b) is an optical photograph of a fingerprint after color development of the nanofiber membrane of example 2;
FIG. 4 is a cross-linking mechanism of PVA with glutaraldehyde;
FIG. 5(a) is an optical photograph of example 3 in which an extracted fingerprint is pressed on a glass surface;
FIG. 5(b) is an optical photograph of a fingerprint obtained after color development of the nanofiber film of example 3.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
The embodiment of the invention selects the following materials and devices:
PVA model-1788; HCl mass ratio concentration 37 wt%; the mass ratio concentration of the glutaraldehyde is 50 wt%.
Scanning Electron Microscope (SEM): a super-high resolution thermal field emission scanning electron microscope JSM-780DF, Japanese Electron JEDL;
needle-free electrospinning apparatus: nano spider silk electrostatic spinning machine, czech ELMARCO company;
needle type electrostatic spinning equipment: FM-1206 type electrostatic spinning equipment, Beijing Fuyou Makou Tech Limited liability company;
example 1
PVA was dissolved in deionized water to prepare 80ml of a 10wt% aqueous PVA solution, which was then stirred at 90 ℃ until the solution became transparent. Preparing 20ml of a 25 wt% ninhydrin aqueous solution, and uniformly mixing the 20ml of ninhydrin aqueous solution with 80ml of PVA aqueous solution on a magnetic stirrer to obtain a PVA/ninhydrin composite solution, wherein the content of PVA in the composite solution is 8% and the content of ninhydrin is 5%. Mixing hydrochloric acid and glutaraldehyde at room temperature according to the molar ratio of glutaraldehyde to HCl of 5:1, and uniformly stirring to obtain a glutaraldehyde/HCl composite solution. Mixing the PVA/ninhydrin composite solution and the glutaraldehyde/HCl composite solution before spinning according to the molar ratio of glutaraldehyde to PVA of 0.01:90 to obtain a spinning solution. And (3) carrying out electrostatic spinning on the spinning solution by adopting a needleless electrostatic spinning device, wherein the electrostatic spinning voltage is 80kV, the solution box speed is 120mm/s, and the spinning time is 60min, so as to prepare the ninhydrin-containing cross-linked PVA nanofiber membrane, namely the ninhydrin/PVA nanofiber composite membrane, wherein the SEM is shown in figure 1(a), and the average diameter of the nanofiber is 176 nm.
A finger was placed directly on the ninhydrin-containing crosslinked PVA nanofiber membrane, and pressed with a force of 10Kg applied to the hand until the ninhydrin-containing crosslinked PVA nanofiber membrane had a depressed profile of the fingerprint on the surface to obtain a latent fingerprint. The crosslinked PVA nanofiber membrane containing ninhydrin having latent fingerprints was placed in hot steam at 100 ℃ at pH 5.5 for 180 seconds to obtain a fingerprint pattern clearly visible to the naked eye under visible light, and the fingerprint image was photographed as shown in fig. 3 (a). Ninhydrin is a reagent used to detect ammonia or primary and secondary amines. The fingerprint sweat contains amino acid residues, the amino acid and the ninhydrin are subjected to display reaction under specific conditions, the reaction product is purple, and the color development mechanism is shown in figure 2.
Example 2
PVA was dissolved in deionized water to prepare 80ml of a 10wt% aqueous PVA solution, which was then stirred at 90 ℃ until the solution became transparent. Preparing 20ml of 25 wt% ninhydrin ethanol solution, and uniformly mixing the 20ml ninhydrin ethanol solution with the PVA aqueous solution on a magnetic stirrer to obtain the PVA/ninhydrin composite solution, wherein the content of the PVA in the composite solution is 8%, and the content of the ninhydrin is 5%. Mixing hydrochloric acid and glutaraldehyde at room temperature according to the molar ratio of glutaraldehyde to HCl of 5:1, and uniformly stirring to obtain a glutaraldehyde/HCl composite solution. Mixing the PVA/ninhydrin composite solution and the glutaraldehyde/HCl composite solution before spinning according to the molar ratio of glutaraldehyde to PVA of 0.01:90 to obtain a spinning solution. And (3) carrying out electrostatic spinning on the spinning solution by adopting a needleless electrostatic spinning device, wherein the electrostatic spinning voltage is 80kV, the solution box speed is 120mm/s, and the spinning time is 60min, so as to prepare the ninhydrin-containing cross-linked PVA nanofiber membrane, namely the ninhydrin/PVA nanofiber composite membrane, wherein the SEM is shown in figure 1(b), and the average diameter of the nanofiber is 193 nm.
A finger was placed directly on the ninhydrin-containing crosslinked PVA nanofiber membrane, and pressed with a force of 10Kg applied to the hand until the ninhydrin-containing crosslinked PVA nanofiber membrane had a depressed profile of the fingerprint on the surface to obtain a latent fingerprint. The crosslinked PVA nanofiber membrane containing ninhydrin, which contains a latent fingerprint, was placed in hot steam at 90 ℃ at pH 6 for 180 seconds to obtain a fingerprint pattern clearly visible to the naked eye under visible light, and the fingerprint image was photographed as shown in fig. 3 (b).
Example 3
PVA was dissolved in deionized water to prepare 80ml of a 12.5wt% aqueous PVA solution, which was then stirred at 90 ℃ until the solution became clear. Preparing 20ml of 35wt% ninhydrin aqueous solution, and uniformly mixing 20ml of ninhydrin ethanol solution and PVA aqueous solution on a magnetic stirrer to obtain PVA/ninhydrin composite solution, wherein the content of PVA in the composite solution is 10% and the content of ninhydrin is 7%. Mixing hydrochloric acid and glutaraldehyde at room temperature according to the molar ratio of glutaraldehyde to HCl of 5:1, and uniformly stirring to obtain a glutaraldehyde/HCl composite solution. Mixing the PVA/ninhydrin composite solution and the glutaraldehyde/HCl composite solution before spinning according to the molar ratio of glutaraldehyde to PVA of 1:90 to obtain a spinning solution. In a needle type electrostatic spinning device with the voltage of 20kV, the solution extrusion speed of 0.5ml/h, the spinning time of 200min, the needle type (No. 17), and the distance between a spinning nozzle (needle) and a receiving plate of 20cm, a cross-linked PVA nanofiber membrane containing ninhydrin, namely a ninhydrin/PVA/nanofiber composite membrane, is prepared, as shown in FIG. 2. SEM is shown in figure 1(c), the average diameter of the nano-fiber is 210nm, obvious cross-linking occurs between fibers, and the cross-linking mechanism is shown in figure 4.
The ninhydrin-containing crosslinked PVA nanofiber film was directly covered on the glass surface with latent fingerprint, and pressed with a force of 20Kg until the surface of the ninhydrin-containing crosslinked PVA nanofiber film had the contour of fingerprint depression to obtain a latent fingerprint, as shown in fig. 5 (a). The ninhydrin-containing crosslinked PVA nanofiber film containing latent fingerprints was placed in hot steam at 100 ℃ at pH 6 for 300s to give a fingerprint pattern clearly visible to the naked eye under visible light, and the fingerprint image was photographed as shown in fig. 5 (b).
Claims (2)
1. A method for detecting fingerprints by a ninhydrin/polyvinyl alcohol nanofiber composite membrane is characterized by comprising the following steps:
(1) directly pressing a finger on the ninhydrin/polyvinyl alcohol nanofiber composite membrane nanofiber membrane, or directly covering the ninhydrin/polyvinyl alcohol nanofiber composite membrane on a smooth object with a potential fingerprint, and applying certain pressure to obtain the potential fingerprint;
(2) the ninhydrin/polyvinyl alcohol nanofiber composite membrane containing the latent fingerprints is removed from the guest and is put in a hot steam condition of 90-100 ℃ with the pH =5.5-6.5 for 60-300 seconds, and then the fingerprint pattern which can be clearly seen by naked eyes under visible light can be obtained;
according to the preparation method of the ninhydrin/polyvinyl alcohol nanofiber composite membrane, hydrochloric acid, glutaraldehyde, polyvinyl alcohol and ninhydrin are compounded into a spinning solution, and a ninhydrin/polyvinyl alcohol nanofiber composite membrane is obtained by a needle-free electrostatic spinning method;
the preparation method of the spinning solution comprises the following steps:
(1) uniformly mixing 10-12.5wt% of polyvinyl alcohol aqueous solution with 25-35wt% of ninhydrin aqueous solution or ninhydrin ethanol solution in a volume ratio of 8:2 to obtain 8-10wt% of polyvinyl alcohol and 5-7wt% of ninhydrin/ninhydrin composite solution;
(2) uniformly mixing hydrochloric acid and glutaraldehyde according to the molar ratio of glutaraldehyde to HCl (4.5-5.5) to 1 to obtain glutaraldehyde/HCl composite solution;
(3) mixing the polyvinyl alcohol/ninhydrin composite solution with the glutaraldehyde/HCl composite solution according to the molar ratio of glutaraldehyde to polyvinyl alcohol of (0.01-1) to (85-90) to obtain a spinning solution.
2. The method of claim 1, wherein the needle-free electrospinning conditions are: the voltage of the needle-free electrostatic spinning equipment is 60-80kV, the speed of a solution box is 80-150mm/s, and the spinning time is 40-120 min.
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