KR101767728B1 - Composite for sweat pore detection sensor using compound indicative of change in color or fluorescence by reacting with sweat gland secretion, thin film using the same and manufacturing method thereof - Google Patents

Composite for sweat pore detection sensor using compound indicative of change in color or fluorescence by reacting with sweat gland secretion, thin film using the same and manufacturing method thereof Download PDF

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KR101767728B1
KR101767728B1 KR1020150102653A KR20150102653A KR101767728B1 KR 101767728 B1 KR101767728 B1 KR 101767728B1 KR 1020150102653 A KR1020150102653 A KR 1020150102653A KR 20150102653 A KR20150102653 A KR 20150102653A KR 101767728 B1 KR101767728 B1 KR 101767728B1
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polymer
solution
compound
color
fluorescence
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KR20160011164A (en
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김종만
이주섭
이찬우
표민경
박동훈
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한양대학교 산학협력단
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/52Use of compounds or compositions for colorimetric, spectrophotometric or fluorometric investigation, e.g. use of reagent paper and including single- and multilayer analytical elements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/76Chemiluminescence; Bioluminescence
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G06K9/00885
    • G07C9/00071

Abstract

The present invention relates to a composition for a pore detection sensor, a thin film using the same and a method for producing the same, and more particularly, to a composition for a pore detection sensor using a compound exhibiting color or fluorescence change by reacting with sweat gland secretion, And a manufacturing method thereof.
According to the present invention, it is possible to provide a sensor for recognizing a position and a pattern of a pore through selective color or fluorescence changes appearing in response to sweat gland secretion. In addition, the present invention recognizes the positions and patterns of pores through changes in color or fluorescence, amplifies and displays the positions and patterns of the pores, and thereby displays a map of the pores.
In addition, according to the present invention, the distribution of pores distributed in the fingerprint ridge can be segmented and recognized, and the fingerprint recognition rate can be drastically increased by comparing and analyzing the characteristic points of the pore through only a small fraction of the fingerprint collection.
Further, the present invention detects moisture, amino acid, ion component, and the like secreted from the sweat glands on the surface of the skin (finger), thereby detecting changes in sweat secretion amount or secretion composition that are generated when an anomaly occurs in a human body, Can be used for analyzing the state of.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for detecting a pore hole using a compound exhibiting color or fluorescence change in response to secretion of sweat glands, a thin film using the same, and a method for producing the same. BACKGROUND ART , THIN FILM USING THE SAME AND MANUFACTURING METHOD THEREOF}

The present invention relates to a composition for a pore detection sensor, a thin film using the same and a method for producing the same, and more particularly, to a composition for a pore detection sensor using a compound exhibiting color or fluorescence change by reacting with sweat gland secretion, And a manufacturing method thereof.

Fingerprint recognition has been used in criminal investigations to capture criminals for centuries. Fingerprint recognition technology is becoming more and more developed and is not confined to criminal investigation, but it is in the trend of expanding its range of applications such as identity verification and access control system. Nowadays, as the recognition of security and personal authentication becomes stronger, fingerprint recognition is used more easily in smart phones and electronic devices that we use in everyday life.

But as the technology of fingerprint recognition develops and gets closer to us, the method of counterfeiting it is getting more and more developed. In order to avoid this, a variety of recognition technologies such as iris recognition, voice recognition, and face recognition have been developed. However, this is a new direction to the fingerprint recognition that has been studied so far, and there is a drawback in using the fingerprint recognition technology as it is.

Therefore, new fingerprint recognition technology is needed to complement existing fingerprint recognition technology. According to the researches so far, the method of fingerprint recognition is divided into three stages according to the degree of difficulty. The first is the method of analyzing the ridge pattern of the fingerprint, the second is the method of analyzing the bifurcation and the end point where the ridge is divided and merged, and the third is the method of analyzing the pattern of the pores distributed on the ridge. As the stages get higher, fingerprints and high-resolution analysis equipment become necessary. Currently, the technique used as fingerprint recognition technology is in the second stage. The third step requires expensive equipment and is not easy to use because it is not easy to get delicate fingerprints from fingerprint providers.

In order to solve the above problems, the present invention proposes various methods for analyzing the pseudo-pouch map, which is the third step only with the existing fingerprint analysis equipment. The only way to obtain a map of the pores using existing chemicals is the "Hydrochromic conjugated polymers for human sweat pore mapping" method (Nature Communications 5, Article number: 3736), which was previously studied in this laboratory.

Korean Patent Publication No. 10-2013-0043189

The present invention provides a composition for a pore detection sensor sensitive to secretions of sweat glands and a thin film using the same, and provides a technique for detecting a pore map by detecting the pore distribution using the composition. The present invention also provides a composition for the pore detection sensor and a method for producing the thin film using the same.

The present invention provides a composition for a porthole detection sensor comprising a compound that reacts with glandular secretion and exhibits color or fluorescence change.

The compound which reacts with the glandular secretion and exhibits color or fluorescence change,

May be one or more monomolecular compounds included in the following formula (1) or (2).

 [Chemical Formula 1]

Figure 112015070352478-pat00001

(2)

Figure 112015070352478-pat00002

(In the formula 2, the hydrogen ion in the carboxyl group may be substituted with lithium, sodium, potassium, rubidium or cesium ion.)

The sweat gland secretion may include moisture, amino acid, salt, and the like.

The composition for the porthole detection sensor may further include a matrix polymer.

The matrix polymer may include at least one member selected from the group consisting of an acrylic polymer, a vinyl polymer, a cellulose derivative, an alkylene polymer, a glycol polymer, a urea polymer, a melamine polymer and an epoxy polymer. Preferred are polyacrylamide, polyacrylic acid (PAA), poly (vinyl alcohol), polyvinyl alcohol-polyethylene glycol graft copolymer, polyvinyl pyrrolidone (PVP) ), Vinyl pyrrolidone-vinyl acetate copolymer, guar gum, glycogen sodium carboxy methyl cellulose, nitro cellulose, methyl cellulose, microcrystalline cellulose Starch, modified starch, cellulose, cellulose acetate, amylose, amylopectin, ethylcellulose, xanthan gum, starch, carboxymethyl cellulose ), Carboxymethyl ethylcellulose, chitosan, chitin, hydroxymethylcellulose (hydr) hydroxy methyl cellulose, hydroxy methyl cellulose, hydroxypropyl methylcellulose, hydroxypropyl methylcellulose phthalate, hydroxypropyl cellulose, starch, polyethylene oxide (PEO) polystyrene polystyrene (PS) epocros, poly (2-hydroxyethyl methacrylate), poly (L-alanine) polycarboxylic acid, (Poly (ethylene glycol)), polyglycine, and poly (glycolic acid).

More preferably, it is a polymer having -OH, -CONH 2 , COC, COO or the like, which is a nonionic functional group having high hydrophilicity, and is a polymer having a functional group capable of hydrophilic action with respect to the number of carbon atoms at a ratio of 2: And may include at least one member selected from the group consisting of vinyl pyrrolidone (PVP), polystyrene (PS), polyacrylic acid (PAA), polyvinyl alcohol (PVA), and polyethylene oxide (PEO) Vinyl pyrrolidone (PVP).

The water-soluble or hydrophilic polymer easily absorbs moisture from the sweat components discharged from the pores, so that the reactivity of the sensor material is improved and a high-quality image of the pores in the pores can be obtained.

The present invention also relates to a compound capable of reacting with sweat gland secretion to exhibit color or fluorescence change; Matrix polymer; And a solvent. The present invention also provides a composition for a pore-forming sensor.

The composition for a porthole detection sensor is characterized in that,

0.05 to 2% by weight, based on the total weight of the composition for a porthole detection sensor, of a compound which reacts with sweat gland secretion to exhibit color or fluorescence change; 0.1 to 20% by weight of a matrix polymer; And 75 to 99.5% by weight of an organic solvent.

The compound which reacts with the glandular secretion to exhibit color or fluorescence change may be one or more monomolecular compounds included in the above formula (1) or (2).

The matrix polymer used may be the above-mentioned matrix polymer, preferably a hydrophilic polymer as with the -0H, -CONH 2, COC, COO and high non-ionic functional group, to the water and a hydrophilic act on carbon atoms (PVA), polystyrene (PS), polyacrylic acid (PAA), polyvinyl alcohol (PVA), and polyethylene oxide (PEO), wherein the functional groups are present in a ratio of 2: And may include one or more, and most preferably polyvinylpyrrolidone (PVP).

The organic solvent may be one which is capable of dissolving the monomer and the matrix polymer. Specific examples of the solvent include alcohols (methanol, ethanol, etc.), chloroform, dichloromethane, dimethylformamide, hexane, benzene, toluene, But are not limited to, one or more selected from the group consisting of pyrrolidone, acetonitrile, tetrahydrofuran, dimethylsulfoxide, acetone, water, and the like.

The sweat gland secretion may include moisture, amino acid, salt, and the like.

The present invention also relates to a method for producing a polymer electrolyte membrane, comprising: (a) preparing a first solution by dissolving a matrix polymer in an organic solvent; Preparing a second solution by dissolving a compound exhibiting color or fluorescence change in an organic solvent in response to secretion of glands (step b); And mixing the first solution and the second solution (step c).

The compound which reacts with the glandular secretion to exhibit color or fluorescence change may be one or more monomolecular compounds included in the above formula (1) or (2).

The matrix polymer used may be the above-mentioned matrix polymer, preferably a hydrophilic polymer as with the -0H, -CONH 2, COC, COO and high non-ionic functional group, to the water and a hydrophilic act on carbon atoms (PVA), polystyrene (PS), polyacrylic acid (PAA), polyvinyl alcohol (PVA), and polyethylene oxide (PEO), wherein the functional groups are present in a ratio of 2: And may include one or more, and most preferably polyvinylpyrrolidone (PVP).

The organic solvent may be one which is capable of dissolving the monomer and the matrix polymer. Specific examples of the solvent include alcohols (methanol, ethanol, etc.), chloroform, dichloromethane, dimethylformamide, hexane, benzene, toluene, But are not limited to, one or more selected from the group consisting of pyrrolidone, acetonitrile, tetrahydrofuran, dimethylsulfoxide, acetone, water, and the like.

The sweat gland secretion may include moisture, amino acid, salt, and the like.

The present invention also relates to a thin film base material; And a coating layer formed on the thin film base material, wherein the coating layer includes a compound that exhibits color or fluorescence change by reacting with sweat gland secretion.

As the thin film base material, a glass plate, a plastic substrate, a paper, a metal substrate, a coated substrate, or the like can be used. In the present invention, the base material can be used as a substrate, a support, and the like.

The coating layer may further include a matrix polymer.

The matrix polymer used may be the above-mentioned matrix polymer, preferably a hydrophilic polymer as with the -0H, -CONH 2, COC, COO and high non-ionic functional group, to the water and a hydrophilic act on carbon atoms (PVA), polystyrene (PS), polyacrylic acid (PAA), polyvinyl alcohol (PVA), and polyethylene oxide (PEO), wherein the functional groups are present in a ratio of 2: And may include one or more, and most preferably polyvinylpyrrolidone (PVP).

The compound which reacts with the glandular secretion to exhibit color or fluorescence change may be one or more monomolecular compounds included in the above formula (1) or (2).

The sweat gland secretion may include moisture, amino acid, salt, and the like.

The thin film for a porthole detection sensor can be used repeatedly in reversibility.

The present invention also provides a method for producing a polymer electrolyte membrane, comprising: (a) preparing a first solution by dissolving a matrix polymer in a solvent; Preparing a second solution by dissolving a compound exhibiting color or fluorescence change in a solvent in reaction with glandular secretion (step b); Mixing the first solution and the second solution to produce a third solution (step c); And coating the third solution on the base material (step d). The present invention also provides a method for manufacturing a thin film for a porthole detection sensor.

The compound, solvent, base material, sweat gland secretion and the like which react with the matrix polymer and sweat gland secretion to exhibit color or fluorescence change are the same as those described above, and thus will not be described here.

The coating may be performed by a method selected from the group consisting of spin coating, inkjet printing, doctor blade, and dip-pulling method, and most preferably, spin coating.

After step d,

(E) drying at 50 to 80 DEG C for 5 to 30 minutes. The step (e) may preferably be a step of drying at 70 DEG C for 5 to 30 minutes.

If the temperature is out of the above range, the monomolecular or matrix polymer may be decomposed. Also, it is preferable to keep the drying time for 5 to 30 minutes in order to shorten the manufacturing time of the film in consideration of the time for the solvent to be sufficiently blown.

The coating and drying may be repeated one to six times, more preferably five times.

If the coating is too thin, the fluorescence can be weak. If the coating is too thick, the film becomes thick and the surface may be bent and the fingerprint may not be flattened. Therefore, it is desirable to maintain the above range.

In addition, the present invention provides a sensor for biometric information recognition comprising a compound which reacts with secretion of sweat glands to exhibit color or fluorescence change.

The compound that exhibits color or fluorescence change in response to secretion of glands may be one or more monomolecular compounds contained in the above formula (1) or (2).

The sweat gland secretion may include moisture, amino acid, salt, and the like.

The sensor for biometric information recognition can be used for pore mapping, and can be manufactured as a reversible sensor capable of repeated use. In this case, it can be used for security devices such as door security systems.

According to the present invention, it is possible to provide a sensor for recognizing a position and a pattern of a pore through selective color or fluorescence changes appearing in response to sweat gland secretion. In addition, the present invention recognizes the positions and patterns of pores through changes in color or fluorescence, amplifies and displays the positions and patterns of the pores, and thereby displays a map of the pores.

In addition, according to the present invention, the distribution of pores distributed in the fingerprint ridge can be segmented and recognized, and the fingerprint recognition rate can be drastically increased by comparing and analyzing the characteristic points of the pore through only a small fraction of the fingerprint collection.

In addition, the color and fluorescence of the fingerprint sensor and the sensor film react with each other when the fingerprint sensor and the sensor film are in contact with each other. When the finger is released, the sensor film is reused because the moisture and the color of the sensor film are returned to their original state. Also, the method can be repeatedly used by turning the used sensor film into a normal state by heating, solvent exposure, rubbing, press, or the like. And can be used for a door sensor or a security device for identifying an identity by using it.

Further, the present invention detects moisture, amino acid, ion component, and the like secreted from the sweat glands on the surface of the skin (finger), thereby detecting changes in sweat secretion amount or secretion composition that are generated when an anomaly occurs in a human body, Can be used for analyzing the state of.

Fig. 1 (a) is a fluorescence-increasing molecular structure mechanism of water-contact of fluorescein used in Examples 1-5, and Fig. 1 (b) is a fluorescence graph before and after the addition of water.
2 is a photograph of a thin film for a pore detection sensor manufactured according to Example 3. Fig. (a) is a thin film according to Example 3-1, (b) is a thin film according to Example 3-2, and (c) is a thin film according to Example 3-3.
Fig. 3 is an image of pores observed with a fluorescence microscope after a fingerprint is taken on a film produced according to Example 3-1 ((a) optical image, (b) fluorescence image, and (c) corrected image).
4 is an image of a pore observed with a fluorescence microscope after a fingerprint is taken on a film produced according to Example 3-2 ((a) fluorescence image and (b) corrected image).
5 is an image of a pore observed with a fluorescence microscope after a fingerprint is taken on a film produced according to Example 3-3 ((a) fluorescence image and (b) corrected image).
6 is an image of a pore observed with a fluorescence microscope after a fingerprint is taken on a film produced according to Example 3-4 ((a) optical image, (b) fluorescence image, and (c) corrected image).
7 is an image ((e) obtained by analyzing ninhydrin with an image ((a) optical image, (b) fluorescent image, (c) corrected image) after fingerprinting on a film produced according to Example 3-2 ) Optical image, (f) fluorescence image, and (g) corrected image).
8 (a) is an image of a pore of an entire fingerprint observed with a fluorescence microscope after a fingerprint is taken on a film produced according to Example 3-5, (b) shows the position of an actual pore of some fingerprint, (The red circle indicates the portion where the pores are present but the sweat does not come out).
9 is an image showing a result of matching with an image analyzed with ninhydrin after the image of the fingerprint is taken on the film produced according to Example 3-5.
10 is an optical image and a fluorescence image after a fingerprint is formed on a film produced according to Example 3-5.
Fig. 11 is a flowchart for explaining how a sensor film reversible to moisture is produced and repeatedly used for detection of a pore fingerprint.
12 is an image showing reversible characteristics of a thin film (Example 3-7) prepared by using the solution composition according to Example 2-2. (1) is a thin film according to Example 3-7, (2) is a state in which water is sucked by using a capillary, the capillary is taken on the film of (1) (4) shows a state in which water is evaporated by heating the film of (3) in a temperature range in which the characteristics of the monomolecular or polymer are not changed.
13 is an image obtained by repeatedly examining the reversible characteristics of the thin film (Example 3-7) prepared using the solution composition in Example 2-2 by moisture. (a) is not exposed to moisture or moisture, and (b) is exposed to moisture.
14 is an image observed with a fluorescence microscope after fingerprints were taken on a film prepared according to Example 3-5 and after 0 day, 1 day, 3 days, 5 days, 7 days, and 9 days.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. It is natural that such variations and modifications are included in the claims.

< Example >

Example  1: Preparation of solution composition for pore-forming sensor 1

A single molecule can be used to produce a film that responds to pore secretions, but a polymer can be added to prevent film peeling when the fingerprint is taken. Depending on the type of polymer, the efficiency with which the pattern of pore holes may be different may vary. Although various kinds of polymers can be used, PVP polymers were used in this study.

After dissolving the matrix polymer and a solvent capable of dissolving the monomer to be used, it is dissolved and spin-coated to produce a film. Specific examples of the solvent that can be used include alcohols such as alcohol, chloroform, dichloromethane, dimethylformamide, hexane, benzene, toluene, dioxane, N-methylpyrrolidone, acetonitrile, tetrahydrofuran, dimethylsulfoxide, And the like, but the present invention is not limited thereto. Depending on the monomolecular material to be used, the solvent may be different, and depending on the solvent used, the wt% of the polymer suitable for film formation may also be different, but about 15 wt% is preferably used.

First, dissolve about 10-20wt% of polyvinylpyrrolidone (PVP) polymer (based on total solution) in 8ml solvent, dissolve monomolecular substance to be used in 2ml of solvent, mix solution and solution So that it can be melted more uniformly.

Example  1-1: As a single molecule Lihart The dye (2,6-Diphenyl-4- (2,4,6- 트리 피닐 -1-pyridinio) phenolate, Reichardt 'S dye) for the detection of pore holes

The first solution was prepared by dissolving 1.66 g (15 wt% based on the total solution) of PVP in 8 ml of DMF solvent, dissolving 0.0550 g (10 mM based on the total solution) of Reichardt's dye in 2 ml of DMF solvent, Solution. Both the first solution and the second solution were mixed to prepare a solution composition for a pore-forming sensor.

Example  1-2: As a single molecule Rubrocurcumin  Preparation of Solution Composition for Pore Bore Detection Sensor Used

The first solution was prepared by dissolving 1.66 g (15 wt% based on the total solvent) of PVP in 8 ml of DMF solvent and dissolving 0.0466 g (10 mM based on total solution) of Rubrocurcumin in 2 ml of DMF solvent to prepare a second solution . Both the first solution and the second solution were mixed to prepare a solution composition for a pore-forming sensor.

Example  1-3: As a single molecule AIEE characteristics  A branch material 2Z, 2'Z ) -3,3 '- (1,4-phenylene) bis (2- (4-methoxyphenyl) acrylonitrile)

In CHCl 3 solvent for PVP 8ml, 0.9g (total solvent based 10wt%) CHCl 3 solvent for dissolving to prepare a first solution, and 2ml of (2Z, 2'Z) -3,3 '- (1,4- 0.0466 g (10 mM based on total solution) of bis (phenylene) bis (2- (4-methoxyphenyl) acrylonitrile) was dissolved to prepare a second solution. Both the first solution and the second solution were mixed to prepare a solution composition for a pore-forming sensor.

Example  1-4: As a single molecule  Fluorescein isothiocyanate ( Fluorescein  Preparation of Solution Composition for Pore Detection Sensor Using Isothiocyanate

The first solution was prepared by dissolving 1.66 g (15 wt% based on the total solution) of PVP in 8 ml of DMF solvent, and 0.0390 g (10 mM based on total solution) of fluorescein isothiocyanate was added to 2 ml of DMF solvent To prepare a second solution. Both the first solution and the second solution were mixed to prepare a solution composition for a pore-forming sensor.

Example  1-5: As a single molecule  Fluorescein ( Fluorescein ) To prepare a solution composition for a pore-forming sensor

The first solution was prepared by dissolving 1.66 g (15 wt% based on the total solution) of PVP in 8 ml of DMF solvent, and 0.0332 g of fluorescein (10 mM based on total solution) was dissolved in 2 ml of DMF solvent to prepare a second solution . Both the first solution and the second solution were mixed to prepare a solution composition for a pore-forming sensor. Fig. 1 (a) shows the fluorescence-increasing molecular structure mechanism after moisture was brought into contact with the prepared composition, and Fig. 1 (b) shows a fluorescence graph before and after moisture addition.

Example  2: Preparation of solution composition for pore-forming sensor 2

Polymers can be added to prevent the peeling of the thin film when the fingerprint is taken, although only a single molecule can be used to produce a film that reacts with the secretion of pores. Depending on the type of polymer, the efficiency with which the pattern of pore holes may be different may vary. Although various kinds of polymers can be used, PVP polymers were used in this study.

After dissolving the matrix polymer and a solvent capable of dissolving the monomer to be used, it is dissolved and spin-coated to produce a film. Examples of usable solvents include alcohols such as alcohol, chloroform, dichloromethane, dimethylformamide, hexane, benzene, toluene, dioxane, N-methylpyrrolidone, acetonitrile, tetrahydrofuran, dimethylsulfoxide, acetone, Water, and the like, but the present invention is not limited thereto. Depending on the monomolecular material to be used, the solvent may be different, and depending on the solvent used, the wt% of the polymer suitable for film formation may also be different, but about 15 wt% is preferably used.

First, dissolve about 10-20wt% of polyvinylpyrrolidone (PVP) polymer in 8ml solvent and dissolve monomolecular substance to be used in 2ml of solvent. So that it can be melted more uniformly.

The monomolecular substance can be used as the substance itself, but the hydrogen ion of the carboxyl group can be substituted with an alkali ion. The alkali ion which may be substituted is lithium, sodium, potassium, rubidium or cesium ion.

Example  2-1: As a single molecule  Fluorescein ( Fluorescein ) To prepare a solution composition for a pore-forming sensor

Fluorescein-Cs can be synthesized by mixing fluorescein (1 equivalent) and CsOH (1 equivalent). The first solution was prepared by dissolving 1.66 g (15 wt% based on the total solution) of PVP in 8 ml of DMF solvent, dissolving 0.0322 g of Fluorescein (10 mM in total solution) in 1.8 ml of DMF, ml water solution of CsOH, 0.0150 g (10 mM based on total solution) was dissolved to prepare a third solution. The first solution, the second solution and the third solution were mixed together to prepare a solution composition for a pore-forming sensor.

Example  2-2: As a single molecule Calcein  Preparation of Solution Composition for Pore Bore Detection Sensor Used

 Calcein-4Cs can be synthesized by mixing calcine (1 equivalent) and CsOH (4 equivalents). A first solution was prepared by dissolving 0.9 g (10 wt% based on the total solvent) of PVP in 8 ml of water and 0.0622 g of Calcein (10 mM based on the total solvent) was dissolved in 1.8 ml of water to prepare a second solution, 0.0600 g (40 mM based on the total solution) of CsOH was dissolved in the water solvent. The first solution, the second solution and the third solution were mixed together to prepare a solution composition for a pore-forming sensor.

Example  2-3: As a single molecule Carl Saine - Blue (Calcein-blue)  Preparation of Solution Composition for Pore Bore Detection Sensor Used

Calcein-2Cs can be synthesized by mixing Calcein-blue (1 equivalent) and CsOH (2 equivalents). A first solution was prepared by dissolving 0.9 g (10 wt% based on the total solvent) of PVP in 8 ml of water, 0.0321 g of Calcein-blue (10 mM based on total solution) was dissolved in 1.8 ml of water, A third solution was prepared by dissolving CsOH, 0.0300 g (20 mM based on total solution) in 0.2 ml of water. The first solution, the second solution and the third solution were mixed together to prepare a solution composition for a pore-forming sensor.

Example  3: For pore detection sensor using spin coating technique Thin film  Produce

The slide glass was cut with a suitable size (2.5 cm x 2.5 cm) for fingerprinting and cleaned with methanol, chloroform, and acetone. An appropriate amount (0.25 ml) of the solution composition in which the above-mentioned monomolecular substance was dissolved was spin-coated on the prepared glass plate. It is dried in a 70 degree oven for 5 minutes to 30 minutes in order to blow the solvent sufficiently to form a film film. Especially when solvents with low volatility such as DMSO and DMF are used, they are dried for 20 minutes or more. In order to produce a multi-layer film, the solution was again spin-coated on the dried film, and then dried again to obtain a film. Thin films of Examples 3-1 to 3-8 were prepared using the solution compositions of Examples 1-1 to 1-5 and 2-1 to 2-3 (see Table 1, Fig. 2). In Table 1, the thin film described on the right was prepared using the solution composition shown on the left. 2 (a) is a thin film according to Example 3-1, (b) is a thin film according to Example 3-2, and (c) is a thin film according to Example 3-3.

Solution composition Thin film Example 1-1 Example 3-1 Examples 1-2 Example 3-2 Example 1-3 Example 3-3 Examples 1-4 Example 3-4 Examples 1-5 Example 3-5 Example 2-1 Examples 3-6 Example 2-2 Examples 3-7 Example 2-3 Examples 3-8

Experimental Example  1: Fingerprint analysis using fluorescence microscope

A fingerprint was taken on a thin film for a pore detection sensor manufactured according to Example 2, and a fluorescence microscope was analyzed. The results are shown in FIG. 3 to FIG. The pore position and the pattern can be easily confirmed as shown in Figs. 3 to 6. Figure 7 compares the image obtained above (Figure 4) with the image obtained by the Ninhydrin detection method used at the actual crime scene. As a result of comparing the two images using the matching program, it can be seen that the same pattern is confirmed when the same person takes a fingerprint.

8 (a) shows the image of the pores of the entire fingerprint observed with a fluorescence microscope after the fingerprint was taken on the film produced according to Example 3-5, and FIG. 8 (b) And images obtained by comparing patterns produced by the film. In FIG. 8 (b), the red circular display portion indicates pores in which perspiration does not occur. As a result, it can be seen that there is no problem in fingerprint recognition even if a part of the portion is not detected. FIG. 9 is an image showing the result of matching with the image analyzed by Ninhydrin in the image of FIG. 8 (a).

The optical image and fluorescence image after the film was prepared according to Example 3-5 and the fingerprint was taken on the film are shown in FIG. An optical image and a fluorescence image obtained by the same method as in Example 3-5 except that a film using PAA was prepared in place of the PVP polymer were also shown in FIG. Similar results were obtained when PAA polymer was used instead of PVP polymer.

The sensor film according to the present invention may have reversibility and can be applied to a security device because it can repeatedly use the punched fingerprint detection function. When the reversibility of the film is used, fluorescence can be shown by touching a finger on the sensor film, and after the finger is removed from the film surface, the fluorescence disappears. When this characteristic is used, it is possible to use it repeatedly several times . A flowchart of one form of this order of use is shown in Fig.

Experimental Example  2: Single molecule  Identification of reversible properties of water-based thin film

12 (1)) was produced using the solution composition prepared in Example 2-2, the reversible characteristics were analyzed by moisture, and the results are shown in FIG. 12 Respectively. First, the water was sucked using a capillary, and then the thin film according to Example 3-7 was photographed with the capillary, and the color change of the thin film was observed (see (2) in FIG. 12). Secondly, a drop of water was dropped on the thin film according to Example 3-7 using a dropper, and then the color change of the thin film was observed (see (3) in FIG. 12). Finally, the thin film dropped one drop of water was heated under a temperature range in which the characteristics of the monomolecular or polymer were not changed to evaporate the water, and the color change of the thin film was observed (see (4) in FIG. 12). Optical characteristics and various fluorescence properties in each of the above steps were confirmed by fluorescence microscopy in order to confirm reversible characteristics by moisture. As shown in FIG. 12, it can be confirmed that when the moisture is applied, the color change is exhibited and when it is dried again, it returns to the color change before the color change.

Experimental Example  3: Confirmation of reproducibility of reversible characteristics by moisture of film

After the thin film according to Example 3-7 was produced using the solution composition prepared in Example 2-2, the film was exposed to moisture using a humidifier , The thin film was heated under a temperature range in which the properties of the monomolecular or polymer were not changed to evaporate the water. Exposure to water and evaporation were repeated several times to confirm that reversible characteristics were repeated. As shown in FIG. 13, it can be seen that the phenomenon in which the color change reversibly appears according to the process of exposing to moisture and evaporating is repeated. 13 (a) is a state in which moisture is not exposed to moisture or water is evaporated, and (b) is in a state exposed to moisture.

Experimental Example  4: Stability test of sensor film

(1) Immediate measurement (2) Measurement after 1 day (3) Measurement after 3 days (4) After 5 days using a fluorescence microscope after taking a fingerprint on a thin film for pore detection sensor manufactured according to Example 3-5 Measurement (5) Measurement after 7 days (6) Measurement after 9 days. All of the fluorescence intensity was not significantly decreased, and the pore patterns were successfully obtained. The results are shown in Fig. Even after the passage of time, there was no significant change in the fluorescence color expressed by the sweat, and the stability as a pore mapping sensor was confirmed.

As described above, according to the present invention, a fingerprint is taken with a finger of a person who wants to obtain a map of the pores on the thin film, and then observed with a fluorescence microscope to obtain a pore pattern map of the person who took the fingerprint. According to the present invention, it is possible to easily map the pores without using expensive equipment or a high-quality fingerprint detection method or the like using existing fingerprint recognition equipment.

Further, in the case of a thin film using a compound having a reversible property to moisture, a pattern of pore holes appears for a while when the fingerprint is taken, and the property returns to the initial state due to the reversible characteristic over time. Therefore, when such a thin film is used, a pore pattern can be repeatedly obtained instead of a one-time pattern.

In addition, according to the present invention, color and fluorescence are changed by reacting with moisture when the finger fingerprint and the sensor film come into contact with each other. When the finger is released, moisture is evaporated and the color and fluorescence of the sensor film return to their original state, . Also, the method can be repeatedly used by turning the used sensor film into a normal state by heating, solvent exposure, rubbing, press, or the like. And can be used for a door sensor or a security device for identifying the user's identity.

According to the present invention, not only clearly fingerprints but also finely imprinted fingerprints or a partial pore distribution can be further subdivided and imaged in an amplified fluorescence pattern, thereby increasing the fingerprint recognition rate by nearly 100%. That is, since the distribution obtained from the specific pore map has a characteristic unique to each person, it is possible to judge whether or not the pore is true or false even with only a partial pore distribution.

In addition, the composition of sweat coming from the sweat glands of the finger surface is mostly composed of 98% moisture, amino acid, ion component, etc. Therefore, according to the present invention, by detecting moisture, amino acid, ion component, The amount of secretion of perspiration or the composition of the secretion which is generated when an abnormality occurs in the body can be used to analyze the condition of the body health as a result.

Claims (22)

delete A compound that exhibits color or fluorescence change in response to sweat gland secretion,
The compound which reacts with the glandular secretion and exhibits color or fluorescence change,
A composition for a pore-forming sensor, characterized in that it is at least one monomolecular compound contained in the following formula (1) or (2)
[Chemical Formula 1]
Figure 112017014824595-pat00003

(2)
Figure 112017014824595-pat00004

In the above formula (2), the hydrogen ion in the carboxyl group may be substituted with a cesium ion or may not be substituted.
delete A composition for a porthole detection sensor,
From 0.05 to 2% by weight of a compound which reacts with glandular secretion to exhibit color or fluorescence change;
0.1 to 20% by weight of a matrix polymer; And
75 to 99.5% by weight of a solvent,
Wherein the compound exhibiting color or fluorescence change by reacting with the glandular secretion is at least one monomolecular compound included in the following formula 1 or 2:
[Chemical Formula 1]
Figure 112017014824595-pat00005

(2)
Figure 112017014824595-pat00006

In the above formula (2), the hydrogen ion in the carboxyl group may be substituted with a cesium ion or may not be substituted.
The method of claim 4,
Wherein the matrix polymer comprises at least one member selected from the group consisting of an acrylic polymer, a vinyl polymer, a cellulose derivative, an alkylene polymer, a glycol polymer, a urea polymer, a melamine polymer and an epoxy polymer Composition for detection sensor.
delete Preparing a first solution by dissolving the matrix polymer in a solvent (step a);
Preparing a second solution by dissolving a compound exhibiting color or fluorescence change in a solvent in reaction with glandular secretion (step b); And
Mixing the first solution and the second solution (step c)
Wherein the compound exhibiting a change in color or fluorescence upon reaction with the glandular secretion comprises at least one monomolecular compound represented by the following formula 1 or 2:
[Chemical Formula 1]
Figure 112017014824595-pat00007

(2)
Figure 112017014824595-pat00008

In the above formula (2), the hydrogen ion in the carboxyl group may be substituted with a cesium ion or may not be substituted.
The method of claim 7,
Wherein the matrix polymer comprises at least one member selected from the group consisting of an acrylic polymer, a vinyl polymer, a cellulose derivative, an alkylene polymer, a glycol polymer, a urea polymer, a melamine polymer and an epoxy polymer A method for preparing a composition for a detection sensor.
delete Thin film base material; And
And a coating layer formed on the thin film base material,
Wherein the coating layer comprises a compound which reacts with glandular secretion to exhibit color or fluorescence change,
The compound which reacts with the glandular secretion and exhibits color or fluorescence change,
A thin film for a porthole detection sensor, characterized in that it is at least one monomolecular compound contained in the following formula (1) or (2).
[Chemical Formula 1]
Figure 112017014824595-pat00009

(2)
Figure 112017014824595-pat00010

In the above formula (2), the hydrogen ion in the carboxyl group may be substituted with a cesium ion or may not be substituted.
The method of claim 10,
Wherein the thin film base material is selected from the group consisting of a glass plate, a plastic substrate, a paper and a metal substrate.
The method of claim 10,
Wherein the coating layer further comprises a matrix polymer.
The method of claim 12,
Wherein the matrix polymer comprises at least one member selected from the group consisting of an acrylic polymer, a vinyl polymer, a cellulose derivative, an alkylene polymer, a glycol polymer, a urea polymer, a melamine polymer and an epoxy polymer Thin film for detection sensor.
The method of claim 10,
The thin film for a porthole detection sensor according to claim 1,
delete Preparing a first solution by dissolving the matrix polymer in a solvent (step a);
Preparing a second solution by dissolving a compound exhibiting color or fluorescence change in a solvent in reaction with glandular secretion (step b);
Mixing the first solution and the second solution to produce a third solution (step c); And
(Step d) coating the third solution on the base material,
The compound which reacts with the glandular secretion and exhibits color or fluorescence change,
Wherein the compound is at least one monomolecular compound included in the following formula (1) or (2).
[Chemical Formula 1]
Figure 112017014824595-pat00011

(2)
Figure 112017014824595-pat00012

In the above formula (2), the hydrogen ion in the carboxyl group may be substituted with a cesium ion or may not be substituted.
18. The method of claim 16,
Wherein the matrix polymer comprises at least one member selected from the group consisting of an acrylic polymer, a vinyl polymer, a cellulose derivative, an alkylene polymer, a glycol polymer, a urea polymer, a melamine polymer and an epoxy polymer Method for manufacturing thin film for detection sensor.
delete A compound that exhibits color or fluorescence change in response to sweat gland secretion,
The compound which reacts with the glandular secretion and exhibits color or fluorescence change,
Wherein the biomolecule is one or more monomolecular compounds contained in the following formula (1) or (2).
[Chemical Formula 1]
Figure 112017014824595-pat00013

(2)
Figure 112017014824595-pat00014

In the above formula (2), the hydrogen ion in the carboxyl group may be substituted with a cesium ion or may not be substituted.
The method of claim 19,
Wherein the biometric information recognition sensor comprises:
And a sensor for mapping the pelvis.
The method of claim 19,
Wherein the sensor for biometric information recognition is a reversible sensor capable of repeated use.
23. The method of claim 21,
Wherein the sensor is for a security device.
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