JP2018049022A - Freshness marker and sensing system using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a freshness marker capable of detecting various types of biogenic amines with high sensitivity, and a freshness sensing system using the same.SOLUTION: Provided is a freshness marker for detecting amines. The freshness marker includes a plurality of detection bodies 2 having an agglomerated phosphor 3 which agglomerates by coexisting with the amines to change fluorescence properties, and a mixture which contains a solvent which solves the agglomerated phosphor. In the plurality of detection bodies, hydrophobicity of the solvent is different for each detection body.SELECTED DRAWING: Figure 2

Description

  The present embodiment relates to a freshness marker that can easily determine the freshness of food and a sensing system using the same.

  Amines produced by food spoilage (hereinafter referred to as “biological amines” or simply “amines”) are produced by decarboxylation of amino acids and are found in seafood and meat and are healthy for allergic diseases and food poisoning. This is a risk. Since biogenic amines are also generated during processing and storage of foods, the amount of biogenic amines is an indicator of the freshness of foods. In recent years, from the standpoint of preventing allergic diseases and food poisoning and reducing food waste, a highly sensitive and highly selective biogenic amine sensing method has been demanded.

  As a sensing method for biogenic amines, a method of performing instrumental analysis such as gas chromatography or liquid chromatography is known. However, such instrument analysis requires time for processing before measurement, and the apparatus to be used must always be managed and adjusted, resulting in high costs.

  On the other hand, a method using a tetraphenylethene fluorescent substance is known as a simple and rapid method for sensing biogenic amines. In this sensing method, tetraphenylethene phosphors are dissolved in a solution. As a first step, a biogenic amine is dissolved in the solution, and as a second step, the tetraphenylethenes phosphor and the biogenic amine react. Thus, an aggregate is formed. Tetraphenylethene phosphors have a weak fluorescence intensity when used alone, but are known to increase fluorescence intensity when aggregated. The increase in fluorescence intensity can detect the generation of biogenic amines. With the result, it is possible to sense the freshness deterioration of the food.

JP 2012-51816 A (Claims) Chem. Eur. J. 2011, 17, 5344-5349.

  There are many kinds of biogenic amines generated by food spoilage, and each has different hydrophobicity. For this reason, a biogenic amine that is compatible with the solvent used in the sensing method described above is detected, while a biogenic amine that is significantly different in hydrophobicity from the biogenic amine cannot be dissolved in the used solvent and is not detected. Since the type of biogenic amine varies depending on the food, it is uneconomical to change the solvent used for each target food when the above-described sensing method is used.

  This invention is made | formed in view of the said subject, and it aims at providing the freshness marker which can detect many types of biogenic amines with high sensitivity.

The freshness marker according to the present embodiment is a freshness marker for detecting an amine, and is a mixed liquid containing an aggregated phosphor that aggregates and changes fluorescence characteristics when coexisting with the amine, and a solvent that dissolves the aggregated phosphor The plurality of detection bodies are characterized in that the hydrophobicity of the solvent is different for each detection body.
Further, the freshness marker according to the present embodiment is a freshness marker for detecting an amine, and is an aggregated phosphor that aggregates and changes fluorescence characteristics when coexisting with the amine, and a solvent or a mixture that dissolves the aggregated phosphor It has a detector having a mixed liquid containing a solvent, and the difference in hydrophobic parameter Log P value between all or part of the amine and the solvent or mixed solvent is 1.53 or less.

FIG. 1 is a diagram showing the relationship between the hydrophobic parameter Log P value of a glycol solvent and a biogenic amine. FIG. 2 is a diagram illustrating an example of a biogenic amine detection process of a freshness marker according to the present embodiment. FIG. 3 is a schematic configuration diagram of a freshness marker according to the second embodiment. FIG. 4 is a schematic configuration diagram of a freshness marker according to the third embodiment. FIG. 5 is a diagram for explaining a method of creating a freshness marker sample. FIG. 6 is a diagram illustrating a method for evaluating a freshness marker sample. FIG. 7 is an image showing the fluorescence state of the freshness marker sample A. FIG. 8 is an image showing the fluorescence state of the freshness marker sample B. FIG. 9 is a fluorescence spectrum of the compound (1) immediately after the addition of spermidine. FIG. 10 is a fluorescence spectrum of the compound (1) after spermidine addition and after irradiation with black light for 14 hours. FIG. 11 is a fluorescence spectrum of the compound (1) after standing for 13 days at room temperature, room light, and open air conditions after the addition of spermidine.

Hereinafter, the present embodiment will be described in detail with reference to the drawings.
In the present embodiment, an aggregated phosphor that aggregates and changes fluorescence characteristics by coexisting with a biogenic amine that is a detection target substance, a solvent that dissolves the aggregated phosphor, and the aggregated phosphor and the solvent are retained. It has a detection body composed of a medium, and the detection body is divided into two or more, and the hydrophobicity of the solvent is different for each of the fractionated detection bodies. According to the freshness marker according to the present embodiment, since the hydrophobicity of the solvent is different for each detector, many types of biogenic amines can be detected.

(Biogenic amine)
Generally, if food is left unattended, some change occurs in odor, appearance, texture, taste, etc. over time, and eventually it becomes unfit for consumption. Such an awkward change in food is called deterioration, deterioration, or alteration, and is commonly referred to as “food rots”. Deterioration of food is caused not only by microbial causes but also by insects, self-digestion, chemical causes (lipid oxidation, browning), or physical causes (damage such as wounds and crushing), but by the growth of microorganisms (rot bacteria) In many cases, it is altered and cannot be eaten.

  A process in which food proteins are decomposed by the action of microorganisms to produce harmful substances and foul odors, while carbohydrates and oils are decomposed by the action of microorganisms to deteriorate the flavor and make it unfit for consumption May be distinguished from corruption or alteration. The main component of the rot odor component is an amine component called various biological amines such as ammonia and trimethylamine.

  For this reason, it is useful to quantify this biogenic amine component in order to know the degree of spoilage of protein-rich foods such as meat and fish. As a method for quantitative analysis of biogenic amines, detection by liquid high-speed chromatography or the like is generally used, but it takes time for determination such as complicated pretreatment and measurement time of a sample, and costs are also increased.

  Nitrogen compounds in food are mainly proteins, which are hydrolyzed by microbial enzymes or food enzymes to become polypeptides, simple peptides or amino acids. Then, the amino acid is decomposed by deamination reaction, transamination, decarboxylation reaction or the like to produce a biogenic amine.

  Examples of biogenic amines generated from amino acids include 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, spermidine, spermine, histamine, Tryptamine etc. are mentioned.

(Aggregated phosphor)
The aggregated phosphor according to the present embodiment refers to a phosphor in which fluorescence characteristics such as a fluorescence spectrum, a shape and intensity of an excitation spectrum, and a fluorescence lifetime are changed by aggregation or crystal precipitation in the presence of an amine. Examples of such aggregated phosphors include aggregation-induced luminescent molecules described in JP 2012-51816 A, for example. Aggregation-inducing luminescent molecules do not emit fluorescence even when irradiated with excitation light in a state dissolved in a solvent, but emit fluorescence by aggregation. A specific example is a tetraarylethene derivative represented by the following general formula (I).

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently of each other, -COOM ₁ ,-(CH ₂ ) _m -COOM ₂ , -X- (CH ₂ ) _n -COOM ₃ , -Y _{- (CH2) o -Z- (CH} 2) p -COOM 4 ( _{wherein, M 1, M 2, M} 3, M 4 , independently of one another, represent a hydrogen atom or a cation, X, Y, Z Each independently represents —O—, —NH—, or —S—, and m, n, o, and p each independently represents an integer of 1 to 6), a hydrogen atom, a halogen atom , Hydroxyl group, nitro group, carbamoyl group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, alkenyl group having 2 to 6 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, 1 to 6 carbon atoms An alkyloxy group, an acyl group having 2 to 6 carbon atoms, an amino group, an alkylamino group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a heteroaryl group having 5 to 10 carbon atoms. Selected and at least _one of R ₁ , R ₂ , R ₃ , R ₄ Even two, independently of one _{another, -COOM 1, - (CH 2} ) m -COOM 2, -X- (CH 2) n -COOM 3, and _{-Y- (CH 2) o -Z- (} CH ₂ ) selected from the group consisting of _p- COOM ₄ (where M ₁ , M ₂ , M ₃ , M ₄ , X, Y, Z, m, n, o, and p are as described above) )

  The “cation” in the above formula is not particularly limited, and may be an organic cation or an inorganic cation. Examples of such cations include ammonium, alkali metal, alkaline earth metal, pyridinium, and the like. In addition, when two or more cations are present in one molecule, they may be different cations.

  The tetraarylethene derivative represented by the general formula (I) has a solubility in a solution due to a hydrogen bond or an electrostatic interaction (hereinafter also referred to as “reaction”) in which the carboxyl group in the molecule is an amine. Decreases and aggregates. When this aggregated tetraarylethene derivative is irradiated with excitation light such as ultraviolet rays, it emits fluorescence. In the present embodiment, the composition containing the aggregated phosphor and the solvent held in the medium is prepared so that the unreacted aggregated phosphor does not aggregate and precipitate, that is, does not become saturated.

(solvent)
The solvent according to the present embodiment uses a solvent that can dissolve the aggregated phosphor and has a difference in hydrophobic parameter Log P value of 1.53 or less from all or part of the biogenic amine to be detected. To do. If the difference in the hydrophobic parameter Log P value between the biogenic amine and the solvent to be detected exceeds 1.53, the compatibility between the biogenic amine and the solvent becomes poor, resulting in non-uniform aggregates and freshness. The sensitivity of the marker may be reduced.

  The hydrophobic parameter Log P value is a distribution coefficient of a substance in water and 1-octanol, and is a value calculated using software “Molecular modeling Pro. Plus version 7.0.4” of Norgwyn Montgomery Software. .

  Moreover, since the freshness marker detects freshness deterioration over time, the solvent according to the present embodiment is preferably a solvent that does not lose its volatility during a certain period in an atmosphere. Furthermore, the solvent according to the present embodiment is preferably a solvent that is highly safe for the human body because the freshness marker is attached to the food or used in the vicinity. Moreover, the solvent which concerns on this embodiment may mix and use 2 or more types as a mixed solvent.

  As such a solvent, a glycol solvent having a high boiling point and low toxicity is preferable. Specific examples of glycol solvents include polyethylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, polyethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol butyl methyl ether, and other ethylene glycol solvents, propylene glycol monomethyl ether, propylene Examples thereof include propylene glycol solvents such as glycol monobutyl ether and propylene glycol dimethyl ether.

  FIG. 1 shows an example of the correlation between the glycol solvent and the hydrophobic parameter Log P value, and the comparison with the hydrophobic parameter Log P value of biogenic amine.

  As shown in FIG. 1, the hydrophobic parameter Log P value of the glycol solvent greatly depends on the number of repeating units of the terminal substituent and the glycol unit. Specifically, the hydrophobicity parameter Log P value increases as the total number of carbon atoms of the terminal substituent increases, and decreases as the number of repeating units of the glycol unit increases.

The closer the hydrophobic parameter Log P value of the solvent and the biogenic amine is, the more easily the biogenic amine is dissolved, and the farther the hydrophobic parameter Log P value of the solvent and the biogenic amine is, the more difficult it is to dissolve. That is, substances having similar hydrophobic parameter Log P values have high compatibility. The fact that the log P values of the solvent and the detection target substance (septic substance) are close means that the solvent and the detection target substance are easily mixed uniformly.
Therefore, in the case of the glycol solvent exemplified in FIG. 1, for example, the following detectors are preferably arranged in order from the relationship with the hydrophobic parameter Log P value of the biogenic amine.
(1) When the solvent is monoethylene glycol or diethylene glycol, the total number of carbon atoms of the terminal substituent is 2, or the total number of carbon atoms of the terminal substituent of the triethylene glycol system is 2 to 3, or tetraethylene glycol A detector in which the total number of carbon atoms of the terminal substituents of the system is 2 to 5,
(2) The total number of carbon atoms of the monoethylene glycol-based terminal substituent is 3 to 4, or the total number of carbon atoms of the diethylene glycol-based terminal substituent is 3 to 6, and the triethylene glycol-based terminal substitution is the solvent. A detector in which the total number of carbon atoms of the group is 3 to 6, or the total number of carbon atoms of the tetraethylene glycol-based terminal substituent is 3 to 7,
(3) The total number of carbon atoms of the monoethylene glycol-based terminal substituent is 5 to 8, or the total number of carbon atoms of the diethylene glycol-based terminal substituent is 6 to 8, and the triethylene glycol-based terminal substitution is the solvent. A detector in which the total number of carbon atoms of the group is 7 to 8, or the total number of carbon atoms of the terminal substituents of tetraethylene glycols is 7 to 8.

(Medium)
The medium according to the present embodiment is not particularly limited as long as it can hold the composition (mixed liquid) containing the aggregated phosphor and the solvent. However, in consideration of the retention of the composition (mixed liquid), the porosity is low. A certain amount or more is preferable, and examples thereof include a porous substrate and a network structure.

  Examples of such a medium include cellulose fiber, paper, cloth, filter, sponge and the like. In particular, a membrane filter made of a cellulose acetate material is preferable because it can increase the fluorescence intensity.

  Further, it is preferable to select a medium that is as close as possible to the refractive index of the solvent used in this embodiment. By approximating the refractive index of the medium to be used and the solvent, the fluorescence generated inside the medium is not disturbed, so that a larger fluorescence intensity can be obtained, which is advantageous for freshness determination.

(Base material)
Moreover, you may use the base material which supports a detection body as needed. The substrate to be used has a solvent resistance to the solvent that dissolves the aggregated phosphor, and it is preferable to select a substrate that does not emit fluorescence. When the aggregated phosphor emits fluorescence The material is not particularly limited as long as it is made of a material that does not approximate the fluorescence wavelength.

  Examples of such base materials include Teflon (registered trademark) sheets, polyimide sheets, polyester films, polyacetal sheets, nylon sheets, polycarbonate sheets, polypropylene sheets, polyethylene sheets, PET films, vinyl chloride sheets and other plastic sheets, glass plates Etc.

  FIG. 2 is a diagram showing an example of a biogenic amine detection process of a freshness marker according to the present embodiment. As shown in FIG. 2 (a), in the freshness marker 10 according to the present embodiment, a detection body 2 divided into detection bodies 2a, 2b, and 2c is supported on a base material 1. The detectors 2a, 2b, and 2c hold the aggregate phosphor 3 and solvents 4a, 4b, and 4c having different hydrophobicities, respectively. As shown in FIG. 2 (b), biogenic amines 5a, 5b, and 5c generated from foods are aggregated fluorescence in the detectors 2a, 2b, and 2c in which the solvents 4a, 4b, and 4c that are easy to dissolve are retained, respectively. Form body 3 and aggregates 6a, 6b and 6c.

(Judgment method)
As described above, the freshness marker according to the present embodiment detects the freshness state of food by detecting the fluorescence characteristics changed by the reaction between the aggregated phosphor and the amine held on the medium. The freshness marker according to the present embodiment is irradiated with ultraviolet light by the ultraviolet light source unit, and the emitted fluorescence is confirmed using the light emission detection unit to determine the freshness state of the food.

  That is, the sensing system according to the present embodiment includes a freshness marker according to the present embodiment, an ultraviolet light source unit that irradiates the freshness marker with ultraviolet light, and a light emission detection unit that detects an image pattern that appears on the freshness marker by ultraviolet irradiation. The detection target substance is detected by an image pattern that appears on the freshness marker by ultraviolet irradiation, and the freshness state of the food is determined. Here, the light emission detection unit refers to an imaging device such as visual observation with the naked eye, a digital camera, or the like.

  In this embodiment, when the freshness state of food is visually determined as the light emission detection unit, it is preferable to be in the dark, avoiding under visible light as much as possible. Further, by using a fluorometer, it is possible to determine the freshness state with higher accuracy. Furthermore, it is possible to make a determination with higher accuracy by checking an image (image pattern) imaged through a CCD image sensor such as a digital camera or a CMOS image sensor.

  An electronically processed image such as a digital camera can convert a weak fluorescent image into an image with greater contrast, and when it is desired to determine a subtle difference in fluorescence intensity, that is, generation of biogenic amines This is a more effective method for discriminating slight differences in quantity. Furthermore, by providing a colorimetric function by image processing to a smartphone with a camera or the like, freshness determination with an automatic determination function can be performed.

(Other forms of freshness marker)
FIG. 3 shows a freshness marker 20 according to the second embodiment. As shown in FIG. 3, in the freshness marker 20, a plurality of detectors 2 are two-dimensionally arranged on the substrate 1, and the hydrophobic parameter Log P value of the solvent and the concentration of the aggregated phosphor are continuously changed. A matrix composed of a plurality of detectors 2 is formed. Many types of biogenic amines can be detected by continuously changing the hydrophobic parameter Log P value of the solvent, and the sensitivity to detect biogenic amines can be increased by continuously changing the concentration of the aggregated phosphor. be able to.

  FIG. 4 is a diagram illustrating a schematic configuration of the freshness marker 30 according to the third embodiment. As shown in FIG. 4, in the freshness marker 30, detectors 2 (2a to 2g) are arranged so that biogenic amines generated in accordance with the degree of progress of corruption can be sequentially detected, and a gradual freshness is arranged along this arrangement. Display 7 (7a-7g) is displayed. This facilitates visual freshness determination. By using a display (symbol 7d in the figure) in which the scale located at the boundary between edible and non-edible is emphasized, visual freshness determination is easier. In FIG. 4, the overall shape of the detection body 2 is triangular, but the shape of the detection body 2 is not particularly limited.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited to the following Example.

[Biogenic amine dependence of freshness marker]
Preparation of fluorescent solution (composition):
As the aggregated phosphor, the compound (1) in which R ₁ and R ₃ are carboxyl groups and R ₂ and R ₄ are hydrogen atoms in the above general formula (I), 0.02 wt. It was made to make fluorescent solution A and B by dissolving so that it might become a% solution.

Fluorescent liquid A
Polyethylene glycol dimethyl ether 99.98wt%
(Hisolv MPM, manufactured by Toho Chemical Industries)
Compound (1) 0.02wt%
Fluorescent liquid B
Triethylene glycol monobutyl ether 99.98wt%
(BTG, made by Nippon Emulsifier)
Compound (1) 0.02wt%

Preparation of freshness marker sample:
FIG. 5 is a diagram illustrating a method for creating a freshness marker sample for evaluation.
First, as shown in FIG. 5 (a), two membrane filters 102 (CELLULOSE ACETATE C020A013A manufactured by Advantech Co., Ltd.) are installed on the glass plate 101, and then, as shown in FIG. 5 (b), each membrane filter is installed. A screen ridge 103 (manufactured by Murakami Co., Ltd., thread diameter: 34 μm, thickness: 52 μm) was covered on 102, and both ends thereof were fixed with polyimide adhesive tape 104.

  Thereafter, as shown in FIG. 5 (c), about 10 μL of the fluorescent solution 106 is dropped onto the membrane filter 102 from above the screen ridge 103 using a pipette 105, and the membrane filter 102 is impregnated to form a detector for evaluation. A freshness marker sample 100 was prepared. A sample in which fluorescent solution A was dropped as fluorescent solution 106 was defined as freshness marker sample A, and a sample in which fluorescent solution B was dropped was defined as freshness marker sample B.

Evaluation of freshness marker samples:
As shown in FIG. 6, the freshness marker samples A and B prepared by the above method are placed so that the detection body does not come into contact with the glass container G with a lid containing raw food P (kamaboko). After setting the freshness marker sample, the lid was closed and stored in an environment at room temperature, and the fluorescence state of the freshness marker sample was observed over time.

  The fluorescence state was observed based on an image obtained by taking a freshness marker sample from the glass container G, irradiating it with ultraviolet rays in an appropriate dark room state, and photographing the fluorescence state with a digital camera. A handy type black light was used for ultraviolet irradiation.

  FIG. 7 is an image obtained by photographing the fluorescence state at the initial stage of installation of the freshness marker sample A using the fluorescent solution A, about 1 hour, about 6 hours, and 1 day. Fig. 7 (a) is an image of freshness marker sample A installed in a glass container G containing raw food P (kamaboko), and Fig. 7 (b) is an empty glass container G into which food P is not added. It is an image of freshness marker sample A installed in.

  From the image shown in FIG. 7 (a), it can be seen that the fluorescence of the freshness marker sample A increases with time. On the other hand, as can be seen from the image shown in FIG. 7B, the freshness marker sample A in the empty glass bottle shows almost no change in fluorescence intensity.

  FIG. 8 is an image obtained by photographing the fluorescence state at the initial stage, 1 day, 2 days, and 3 days after the installation of the freshness marker sample B using the fluorescent solution B. Fig. 8 (a) is an image of freshness marker sample B installed in a glass container G containing raw food (kamaboko), and Fig. 8 (b) is installed in an empty glass container G where no food is added. It is the image of the freshness marker sample B made.

The change in the fluorescence intensity of freshness marker sample B is the same as that of freshness marker sample A using fluorescent solution A when placed in a glass container containing raw food P (kamaboko) and when placed in an empty glass container. It can be seen that it is small in comparison. In addition, there is no tendency for the fluorescence intensity to increase even after 3 days.
That is, in the foodstuff (kamaboko) used in this test, the more sensitive freshness marker for capturing the change in the freshness state can be said to be the freshness marker sample A using the fluorescent solution A in which the solvent is polyethylene glycol dimethyl ether. .

  From the above evaluation results, it can be seen that preparation of a fluorescent solution suitable for each food material is necessary to create a freshness marker suitable for various food materials.

[Solvent dependence of fluorescence spectrum]
Using the biological amine spermidine as a detection target substance, the solvent dependence of the fluorescence spectrum of compound (1) was evaluated. Table 1 shows various parameters of the solvent and spermidine used. As the hydrophobic parameter Log P value, Molecular modeling Pro. Plus Version 7.0.4 of Norgwyn Montgomery Software, Inc. was used. First, the structure was optimized by molecular mechanics calculation (MM2) and then calculated by three-dimensional structure-activity relationship (Three-D QSAR terms).

[Remarks]
* 1; Triethylene glycol butyl methyl ether * 2; Diethylene glycol dibutyl ether * 3; Triethylene glycol dimethyl ether * 4; Diethylene glycol monobutyl ether * 5; Difference between the log P value of the solvent and the log P value of spermidine

  FIG. 9 to FIG. 11 show fluorescence spectra after addition of 8 molar equivalents (500 μmol) of spermidine in each solvent of compound (1). Fig. 9 shows the fluorescence spectrum immediately after spermidine addition, Fig. 10 shows the fluorescence spectrum after irradiation with black light for 14 hours after spermidine addition, and Fig. 11 shows the room temperature, room light, and open to air conditions for 13 days after spermidine addition. It is a fluorescence spectrum. The parentheses in the figure are the magnification of the fluorescence intensity based on the fluorescence intensity at the maximum wavelength in the case of compound (1) alone.

  From the fluorescence spectra shown in FIG. 9 to FIG. 11, it can be seen that a significant increase in fluorescence intensity is observed immediately after the addition of spermidine except for diethylene glycol monobutyl ether (No. 4). Moreover, it can be seen from these fluorescence spectra that diethylene glycol monobutyl ether (No. 4) takes a long time to observe aggregated fluorescence. Such a solvent can be utilized in preparing a mixed solvent with another solvent for the purpose of enhancing aggregation stability.

As a comparative example using spermidine as a detection target, the fluorescence spectrum of compound (1) when dibutyl maleate with a Log P value of 2.13 was used as a solvent (ΔLog P = 1.91) was evaluated. The fluorescence intensity was significantly attenuated by irradiation for 14 hours.
However, when the detection target substance was phenethylamine (Log P = 1.84, ΔLog P <0.29 with dibutyl maleate) having a hydrophobic parameter Log P larger than that of spermidine, the fluorescence intensity was not significantly attenuated.

  From the above evaluation results, if the difference in the Log P value of the solvent used for the detection target substance and the freshness marker detector exceeds 1.53, the detection target substance does not disperse in the form of molecules in the solvent and forms minute droplets. As a result, it is considered that the aggregate formed from the substance to be detected and the aggregated phosphor becomes non-uniform, and the ability to maintain the fluorescence intensity decreases.

  On the other hand, when the difference in Log P value is 1.53 or less, an aggregate in which the aggregated phosphor and the detection target substance form a network uniformly is easily constructed, and such an aggregate is excellent in durability. On the other hand, a solvent having an OH group at the end, such as the solvent of No. 4, forms a hydrogen bond with the COOH group of the phosphor, so that it is considered that the interaction with the spoilage substance is limited. Such a solvent is useful for adding as a part of the mixed solvent to adjust the sensitivity of the freshness marker (sensitivity adjustment is necessary depending on the food), but the whole solvent is a No.4 type solvent. In some cases, the rate at which aggregates are formed decreases.

[Fluorescence lifetime]
Compound (1) alone in solvent Nos. 1 to 4 above, immediately after addition of spermidine, 10 hours after black light irradiation, 14 hours after black light irradiation, and room temperature / room light / air as durability test The fluorescence lifetime after 13 days was left open. The evaluation results are shown in Table 2. The fluorescence lifetime in Table 2 was obtained by approximating the fluorescence decay function with two types of X-potential functions, and the parenthesis in each column is the χ2 coefficient.

  Table 2 shows experimentally how the fluorescence lifetime of compound (1) alone changes with the addition of spermidine, a detection target substance (septic substance), and how it changes after each durability test. It is a result.

As shown in Table 2, in the case of No. 1, No. 2, and No. 3 in which the fluorescence intensity increases with the addition of spermidine, the main fluorescence lifetime decreases with the addition of spermidine. On the other hand, in No. 4 in which the fluorescence intensity does not increase, the main fluorescence lifetime does not decrease. This is linked to an increase in the interaction between the compound (1) and spermidine, that is, the generation of aggregates.
The fluorescence intensity decreases with UV irradiation, but the fluorescence lifetime increases correspondingly. This is probably because the interaction between compound (1) and spermidine was weakened. On the other hand, the fluorescence lifetime in the rightmost column where the fluorescence intensity did not decrease by the durability test does not increase. From this result, it can be seen that the fluorescence lifetime can be utilized for freshness determination.

  As mentioned above, although embodiment of this invention was described, this embodiment is shown as an example and is not intending limiting the range of invention. The novel embodiment can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. This embodiment and its modifications are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

2; Detection body 3; Aggregated phosphor 4; Solvent 5; Detection target substance (biological amine)
6; Aggregate composed of phosphor and substance to be detected 7; Scale freshness display

The freshness marker according to the present embodiment is a freshness marker for detecting a detection target substance due to food spoilage, and the aggregated phosphor that aggregates and changes the fluorescence characteristics when coexisting with the detection target substance, and the aggregation It has a detector having a mixed solution containing a solvent or mixed solvent that dissolves the phosphor, and the difference in the hydrophobic parameter Log P value between all or part of the detection target substance and the solvent or mixed solvent is It is characterized by being 1.53 or less.

Claims (5)

A freshness marker for detecting amines,
Comprising a plurality of detectors having a mixed liquid containing an aggregated phosphor that aggregates and changes fluorescent properties by coexisting with the amine and a solvent that dissolves the aggregated phosphor,
The freshness marker, wherein the plurality of detection bodies have different hydrophobicity of the solvent for each detection body. A freshness marker for detecting amines,
An agglomerated phosphor that aggregates and changes in fluorescence characteristics by coexisting with the amine, and a detector having a solvent or a mixed solution containing the solvent that dissolves the agglomerated phosphor,
A freshness marker, wherein a difference in hydrophobic parameter Log P value between all or part of the amine and the solvent or mixed solvent is 1.53 or less.   The freshness marker according to claim 1 or 2, wherein the aggregated phosphor is tetraarylethene.   The freshness marker according to any one of claims 1 to 3, wherein the solvent contains a glycol system. The freshness marker according to claim 1, an ultraviolet light source unit, and a light emission detection unit,
A sensing system, wherein the light emission detection unit detects a substance to be detected based on an image pattern that appears on the freshness marker by ultraviolet irradiation by the ultraviolet light source unit.