WO2020036171A1

WO2020036171A1 - Sensor

Info

Publication number: WO2020036171A1
Application number: PCT/JP2019/031822
Authority: WO
Inventors: 幸治弘中
Original assignee: 富士フイルム株式会社
Priority date: 2018-08-17
Filing date: 2019-08-13
Publication date: 2020-02-20
Also published as: JP7106651B2; JPWO2020036171A1

Abstract

The present invention provides a sensor that has excellent sensitivity and selectivity with respect to a component to be detected, said component being contained at a low concentration in a system. A sensor according to the present invention is a resonance type or stress type sensor which has a receiving layer that contains a polymer having a repeating unit that has a partial structure represented by formula (1).

Description

Sensor

The present invention relates to a sensor.

There is an increasing demand for highly sensitive detection and monitoring of rare gases floating in the air. For example, it is known that a biological gas such as breath and skin gas contains a ketone compound, and it is considered that a result of detecting the ketone compound with a sensor may be used as an index for diagnosing a health condition. I have.
For example, Non-Patent Document 1 discloses the use of a resonance-type sensor (specifically, a quartz crystal microbalance sensor) having a receiving layer containing a porphyrin compound in order to detect biogas. .

The present inventor produced a resonance type and a stress type sensor having a receiving layer composed of a porphyrin compound disclosed in Non-Patent Document 1, and found that the detection target component contained in the system at a low concentration was highly sensitive and selective. Could not be detected. That is, in the form of Non-Patent Document 1, it is difficult to apply to low-concentration subjects such as breath and skin gas.

The object of the present invention is to provide a sensor having excellent sensitivity and selectivity to a detection target component (for example, a biological gas such as a ketone compound) contained in a system at a low concentration.

As a result of intensive studies on the above problems, the present inventors have found that a desired effect can be obtained by using a predetermined receiving layer, and have reached the present invention.
That is, it has been found that the above-mentioned problems can be solved by the following configuration.

(1) A resonance type or stress type sensor having a receptor layer containing a polymer having a repeating unit having a partial structure represented by the following formula (1).
(2) The sensor according to (1), wherein the partial structure represented by Expression (1) is a partial structure represented by Expression (2) described later.
(3) The sensor according to (1) or (2), wherein the partial structure represented by the formula (1) is a partial structure represented by the formulas (1-A) to (1-D).
(4) The sensor according to any one of (1) to (3), further comprising a receiving layer and another receiving layer.
(5) The sensor according to any one of (1) to (4), which is a resonance type.

According to the present invention, it is possible to provide a sensor having excellent sensitivity and selectivity for a detection target component contained in a system at a low concentration.

It is sectional drawing which shows an example of the resonance type sensor of this invention typically.

Hereinafter, the sensor of the present invention will be described.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present invention, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the present specification, the weight average molecular weight is defined as a value in terms of polystyrene measured by GPC (Gel Permeation Chromatography).
For example, GPC measurement uses HLC-8121GPC (manufactured by Tosoh), two columns of TSKgel GMH _HR- H (20) HT (manufactured by Tosoh, 7.8 mm ID × 30 cm) as columns, and 1,2,2,2 as eluents. Use 4-trichlorobenzene. The conditions are as follows: the sample concentration is 0.02% by mass, the flow rate is 1.0 ml / min, the sample injection amount is 300 μl, the measurement temperature is 160 ° C., and an IR (infrared) detector is used.
In the present specification, “ppm” means “parts-per-million (10 ⁻⁶ )” and “ppt” means “parts-per-trillion (10 ⁻¹² )”.

The bonding direction of the divalent linking group described in the present specification is not particularly limited. For example, when X ¹ is —CO—CR ⁹ R ¹⁰ —, —CO— may be bonded to the Y ¹ side, or —CR ⁹ R ¹⁰ — may be bonded to the Y ¹ side.

The sensor of the present invention has a receptor layer containing a polymer having a repeating unit having a partial structure represented by the following formula (1) (hereinafter, also referred to as “specific polymer”).
In the sensor according to the present invention, the detection target component is detected as a result of the detection target component adsorbing to the reception layer through some interaction between the specific polymer contained in the reception layer and the detection target component.
The sensor of the present invention has excellent sensitivity and selectivity to a detection target component (particularly, a ketone-based compound) contained at a low concentration in the system. Although the reason for this has not been clarified, the ability of the sensor to detect trace components and the ability to adsorb the target component of the specific polymer contained in the receptor layer act synergistically, and have not been found before. It is considered that the sensitivity and the potential of the molecular recognition ability of the specific polymer were exhibited.
Hereinafter, the sensor of the present invention will be described in detail. First, the specific polymer contained in the receiving layer will be described in detail.

[Specific polymer]
The specific polymer has a repeating unit having a partial structure represented by the formula (1).
Since the partial structure represented by the formula (1) is a rigid and bent structure, the specific polymer can form fine and random voids on the molecular level in the receiving layer. The void formed by the specific polymer can have a high sensitivity and a high selectivity for the detection target component, possibly due to some kind of molecular interaction different from the molecular sieving function.

In the formula (1), L ¹ and L ² each independently represent a divalent linking group.
Examples of the divalent linking group include —O—, —CO—, —COO—, —CONH—, —S—, —SO ₂ —, and —NR ^A — (R ^A is a hydrogen atom or an alkyl A divalent hydrocarbon group (eg, an alkylene group, an alkenylene group (eg, —CH ＝ CH—), an alkynylene group (eg, —C≡C—), and an arylene group), or A group obtained by combining these (for example, -O-divalent hydrocarbon group-) is exemplified.
The partial structure represented by the formula (2) is preferable as the partial structure represented by the formula (1) from the viewpoint that the sensitivity and / or the selectivity of the sensor are more excellent.

In the formula (2), X ¹ and X ² are each independently —CR ¹ R ² —, —CR ³ R ⁴ —CR ⁵ R ⁶ —, —CR ⁷ ＣＲCR ⁸ —, —CO—, —CO Represents —CR ⁹ R ¹⁰ — or —O—.
Y ¹ and Y ² each independently represent —CR ¹¹ R ¹² —, —O—, or a single bond.
R ¹ to R ¹² each independently represent a hydrogen atom or a substituent.
The type of the substituent is not particularly limited, and examples thereof include a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an aryl group. , Heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group) An acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, Sur Group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group , A phosphinylamino group, and a silyl group.
Among them, a hydrocarbon group is preferable as the substituent, and an alkyl group or an aryl group is preferable because the sensitivity and / or selectivity of the sensor are more excellent.
The carbon number of the alkyl group is not particularly limited, and is preferably from 1 to 5, more preferably from 1 to 3, and still more preferably 1, from the viewpoint that the sensitivity and / or selectivity of the sensor are more excellent.

R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² are independently bonded to each other to form a ring It may be.
The type of ring formed is not particularly limited, and may be an aromatic ring or a non-aromatic ring. Examples of the aromatic ring include an aromatic hydrocarbon ring (for example, a benzene ring and a fluorene ring) or an aromatic heterocyclic ring. Examples of the non-aromatic ring include an aliphatic hydrocarbon ring.

When Y ¹ is —O—, X ¹ represents —CR ³ R ⁴ —CR ⁵ R ⁶ —, and when Y ² is —O—, X ² represents —CR ³ R ⁴ —CR ^5. It is preferred to represent R ^6- . Also, if ^{Y 1} is a single bond, ^{X 1} is ^-CR 7 = CR ⁸ - represents, if ^{Y 2} is a single bond, ^{X 2} is ^-CR 7 = CR ⁸ - preferably represents a.

The partial structure represented by the formula (1) is preferably a partial structure represented by the formula (1-A) to the formula (1-D) from the viewpoint that the sensitivity and / or the selectivity of the sensor are more excellent.
In the partial structure represented by the formula (1-A), X ¹ and X ² in the formula (2) are —CR ¹ R ² —, and Y ¹ and Y ² are —CR ¹¹ R ¹² —. In a certain embodiment, the partial structure represented by the formula (1-B) is such that X ¹ and X ² in the formula (2) are —CR ⁷ ＣＲCR ⁸ —, and Y ¹ and Y ² are a single bond. In the partial structure represented by the formula (1-C), X ¹ and X ² in the formula (2) are —CR ³ R ⁴ —CR ⁵ R ⁶ —, and Y ¹ and The partial structure represented by the formula (1-D) corresponds to the embodiment in which Y ² is —O—, wherein X ¹ and X ² in the formula (2) are —O—, and Y ¹ and Y ² There ^-CR 11 ^{R 12} - corresponding to the is aspect.

The repeating unit having the partial structure represented by the formula (1) only needs to include the partial structure represented by the above formula (1) as the partial structure, but the sensor has higher sensitivity and / or selectivity. Thus, the repeating unit is preferably represented by the formula (3).

In the formula (3), the definition of ^{L 1} and ^{L 2} are the same as those defined ^{L 1} and ^{L 2} in Formula (1) described above.
Z ¹ to Z ⁴ each independently represent —O—, —S—, or —SO ₂ —.
A represents an aromatic ring or a non-aromatic ring which may have a substituent.
Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Examples of the hetero atom contained in the aromatic heterocyclic ring include an oxygen atom, a nitrogen atom, and a sulfur atom.
Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of the aromatic heterocycle include a pyridine ring, a pyrrole ring, and a thiophene ring.
The aromatic ring may be monocyclic or polycyclic. When the aromatic ring is polycyclic, it may be a condensed ring or a ring in which two aromatic rings are connected via a hetero atom.

Non-aromatic rings include aliphatic hydrocarbon rings and aliphatic heterocycles. The hetero atom contained in the aliphatic heterocyclic ring includes, for example, an oxygen atom, a nitrogen atom, and a sulfur atom.
Examples of the aliphatic hydrocarbon ring include a cyclohexane ring. Examples of the aliphatic heterocyclic ring include a tetrahydrofuran ring and a piperidine ring.
The non-aromatic ring may be monocyclic or polycyclic.

Examples of the substituent which the aromatic ring and the non-aromatic ring may have include the groups exemplified as the substituents represented by R ¹ to R ¹² described above.

As the repeating unit represented by the formula (3), a repeating unit represented by the formula (4) is preferable from the viewpoint that the sensitivity and / or selectivity of the sensor are more excellent.

In the formula ^(4), of X ^1, X 2, ^{Y 1} and ^{Y 2} definition is synonymous with ^X ^1, the X 2, ^{Y 1} and ^{Y 2} defined in the above Expression (2).
Definition in the formula ^{^{(4), Z 1 ~ Z}} 4 and A are the same as those defined ^Z 1 ~ ^{Z 4} and A in the above Expression (3).

Although the content of the repeating unit having the partial structure represented by the formula (1) is not particularly limited, the content is preferably 10 to 10 with respect to all the repeating units of the specific polymer, since the sensor is more excellent in sensitivity and / or selectivity. It is preferably 100% by mass, more preferably 40 to 100% by mass.
The weight average molecular weight of the specific polymer is preferably from 10,000 to 1,000,000, more preferably from 20,000 to 500,000, from the viewpoint that the sensitivity and / or selectivity of the sensor is more excellent.

具体 Specific examples of the repeating unit having the partial structure represented by the formula (1) are shown below.

The specific polymer can be produced by a known method.

[Sensor form]
<Receiving layer>
The sensor of the present invention has a receiving layer containing a specific polymer. The configuration of the sensor of the present invention is not particularly limited as long as it has a predetermined receiving layer, but it has at least a sensor body (for example, a resonance sensor body or a stress sensor body) and a receiving layer containing a specific polymer. Is preferred. Note that the sensor of the present invention may have a predetermined receiving layer and other members other than the sensor main body.
Although the content of the specific polymer in the receiving layer varies depending on the form of the sensor, it is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, and more preferably 50 to 100% by mass based on the total mass of the receiving layer. % Is more preferable, 75 to 100% by mass is particularly preferable, and 90 to 100% by mass is most preferable.
The method for forming the specific polymer-containing receptor layer is not particularly limited. For example, a composition obtained by dissolving a specific polymer in a solvent (such as tetrahydrofuran) is coated on the surface on which the specific polymer-containing receptor layer is to be formed. A method of coating and drying the obtained coating film to form a film may be mentioned. Examples of the application method include an ink-jet method, a dipping method, and a spray method.
The thickness of the receptor layer containing the specific polymer varies depending on the form of the sensor, but is preferably from 10 nm to 100 μm, more preferably from 50 nm to 50 μm, even more preferably from 100 nm to 10 μm.

In addition, it is preferable that the sensor of the present invention further has another receiving layer in addition to the receiving layer containing the specific polymer. When the sensor of the present invention has another receiving layer having a different property, for example, there is an advantage that it is possible to detect other components or to improve the measurement accuracy for a composite gas. The receiving layer containing the specific polymer and the other receiving layer may be separately arranged or may be laminated.
Specific examples of the other receiving layer include a receiving layer obtained by using a hydrophobic compound (for example, poly (1-trimethylsilyl-1-propyne)). Thereby, since the sensor of the present invention has the hydrophilic receiving layer containing the specific polymer and the hydrophobic receiving layer, it is possible to detect various components.

<Resonant sensor>
The resonance type sensor of the present invention adsorbs a specific kind of gas molecules contained in air on the surface and determines whether or not the adsorbed gas molecules are adsorbed or the amount of the adsorbed gas molecules by changing the resonance frequency of a dielectric material (piezoelectric material) that is resonantly driven (specifically, Specifically, the target gas is detected. That is, the resonance type sensor is a sensor using a mass micro-balancing method.
FIG. 1 is a cross-sectional view schematically showing an example of a laminated structure in a resonance type sensor of the present invention. The resonance type sensor shown in FIG. 1 has a laminated structure in which a first electrode 1, a dielectric material 2, a second electrode 3, and a receiving layer 4 containing a specific polymer are sequentially provided. Further, a substrate for supporting the resonance type sensor may be provided on the surface of the first electrode 1 opposite to the side in contact with the dielectric material 2. If the dielectric material is self-oscillating, the substrate is not essential. On the other hand, when the dielectric material is a ceramic piezoelectric element or the like, a substrate is required to drive the element resonantly.

In sensing by the mass micro-balancing method, a voltage is applied to a fine dielectric material (piezoelectric material) to vibrate the dielectric material at a constant frequency (resonance frequency), and the mass increase due to gas adsorption on the surface of the dielectric material resonates. The change is detected as a change in frequency (specifically, a decrease). As a typical example of a resonance type sensor using the mass micro-balancing method, a sensor using a QCM (Quartz Crystal Mass micro-balancing; a quartz oscillator micro-balancing) method using quartz as a dielectric material to be driven for resonance (hereinafter, referred to as a quartz resonator micro balance) , "QCM sensor") are known.
In a QCM sensor, electrodes are usually provided on both surfaces of a crystal thin film cut at a specific angle (AT-cut), and a voltage is applied to cause shear vibration in a horizontal direction with respect to the crystal surface at a resonance frequency. Since this resonance frequency decreases in accordance with the mass of the gas adsorbed on the electrode, a change in mass of the substance on the electrode can be detected. The QCM sensor itself having a quartz oscillator composed of quartz and an electrode sandwiching the quartz is known, and can be prepared by an ordinary method, or a commercially available product may be used.
A QCM sensor as one mode of the resonance type sensor of the present invention includes a specific polymer for adsorbing a detection target component on one electrode surface of a pair of electrodes provided with a dielectric material interposed therebetween. It is preferred to have a receiving layer. That is, as the resonance type sensor of the present invention, a QCM sensor having a quartz oscillator and a receiving layer disposed on the quartz oscillator is preferable. The mass of the detection target component adsorbed on the receiving layer containing the specific polymer is detected as a change (specifically, a decrease) in the resonance frequency of the quartz oscillator driven in resonance.

電極 There is no particular limitation on the electrodes used for the resonance sensor, and metal materials and the like usually used for the electrodes can be used.

として In addition to the QCM sensor as the resonance type sensor, a resonance type sensor using a ceramic dielectric (piezoelectric material) without using quartz or quartz as a dielectric material can be adopted. Such sensors include cantilever sensors and surface acoustic wave (SAW) sensors. Since a ceramic dielectric material can be formed on a substrate using a sputtering method, a vacuum evaporation method, or the like, there is an advantage that the ceramic dielectric material can be applied to the production of a sensor using a MEMS (Micro Electro Mechanical Systems) technique. Such ceramic dielectric materials include, for example, lead zirconate titanate (PZT), lead zirconate titanate doped with niobium (PZTN), zinc oxide (ZnO), and aluminum nitride (AIN).

In the cantilever sensor, electrodes are arranged on both surfaces of a film formed of the ceramic dielectric material, and a specific voltage is applied between the electrodes to drive the ceramic dielectric material in resonance. When a resonance sensor using a ceramic dielectric material is used as the resonance sensor of the present invention, a detection target component is adsorbed on one electrode surface of a pair of electrodes provided with the dielectric material interposed therebetween. It is preferable to dispose a receiving layer containing the specific polymer of (1). The mass of the detection target component adsorbed on the receiving layer containing the specific polymer is detected as a change (specifically, a decrease) in the resonance frequency of the ceramic dielectric material driven in resonance.

<Stress sensor>
Examples of the type of the stress sensor of the present invention include a film-type surface stress sensor and a cantilever sensor.

[Use]
The use of the sensor of the present invention is not particularly limited, and includes, for example, for inspection of breath or skin gas, for quantitative measurement of odor, for inspection of gas leak, and for environmental investigation.
The sensor of the present invention can detect a detection target component contained in a system at a low concentration with high sensitivity and high selectivity. Therefore, the sensor of the present invention is particularly suitable for the inspection of the breath gas or the skin gas containing the detection target component at a low concentration. Here, the skin gas in the present invention is a general term for volatile substances emitted from the body surface.
Further, as a specific example of the case where the detection target component is contained in the system at a low concentration, there is a case where the gas of the detection target component is present in the system in the range of 1 volume ppm to 100 ppm by volume. The sensor of the present invention more preferably detects the detection target component contained in the system with high sensitivity and selectively in the lower concentration range of 1 vol. Ppt to 10 vol ppm, and more preferably 1 vol. It is further preferable that the detection target component contained in the system is selectively detected with high sensitivity in the range of ppt to 1 ppm by volume.

[Detection target component]
The detection target component of the sensor of the present invention is preferably a hydrophilic compound, since it can be detected with higher sensitivity and higher selectivity when it is contained in the system at a low concentration.
In the present specification, a hydrophilic compound refers to, for example, a compound having an SP (Solubility Parameter) value of 9 to 17 (cal / cm ³ ) ^1/2 , and specifically, acetone (10.0) , Ethanol (12.7), acetonitrile (11.9), and acetic acid (12.6).
Here, the SP value (solubility parameter) is defined by the theory of Hildebrand's regular solution, and more specifically, the molar evaporation heat of a compound is ΔH, the molar volume is V, the gas constant is R, and the absolute temperature is Let T be an amount (cal / cm ³ ) ^1/2 defined by ((ΔH-RT) / V) ^1/2 .

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this. In addition, the compounding quantity of each component shows a mass reference | standard, unless there is particular notice.

[Example 1]
Polymer-1 was synthesized with reference to the method described in Chemical Communications, 2004, 230-231.

Polymer-1 (10 mg) was dissolved in THF (tetrahydrofuran, manufactured by Wako Pure Chemical Industries, Ltd.) (8 g). The obtained solution was dropped on one surface of a quartz oscillator in a QCM sensor (Quartz Crystal Microbalance, manufactured by Tama Device), and further dried at 80 ° C. to form a film made of Polymer-1 as a receiving layer.
The obtained QCM sensor having a receiving layer was put into a flow cell, and 1 mL of saturated vapor of each of the following test gases was passed therethrough to evaluate the sensitivity and selectivity of the QCM sensor having the receiving layer to a component to be detected. Table 1 shows the results.

[Examples 2 to 4]
The following Polymer-2 to Polymer-4 were respectively synthesized, and a QCM sensor having a receiving layer containing each polymer was formed according to the same procedure as in Example 1 by using each polymer instead of Polymer-1. An evaluation was performed.

[Comparative Example 1]
In the same manner as in Example 1, except that Polymer-1 was changed to a tetrakis (butoxyphenyl) porphyrin copper complex described in Non-Patent Document 1 (Sensors and Actuators B 173 (2012) 555-561). A QCM sensor having a receiving layer composed of a phenyl) porphyrin copper complex was obtained.
The sensitivity and selectivity of the QCM sensor having the receiving layer to the detection target component were evaluated in the same manner as in Example 1. Table 1 shows the results.

[Comparative Example 2]
A QCM sensor having a receiving layer made of polyisobutylene was obtained in the same manner as in Example 1 except that Polymer-1 was changed to polyisobutylene.
The sensitivity and selectivity of the QCM sensor having the receiving layer to the detection target component were evaluated in the same manner as in Example 1. Table 1 shows the results.

[Evaluation]
<Sensitivity>
Based on the absolute value of the frequency change generated in the QCM sensor having the receiving layer when 1 mL of saturated steam containing acetone was flown, the sensitivity was evaluated based on the following criteria. Here, the larger the absolute value of the frequency change, the better the sensitivity of the QCM sensor.
5: 100 Hz or higher 4: 70 Hz or higher but lower than 100 Hz 3: 40 Hz or higher but lower than 70 Hz 2: 10 Hz or higher but lower than 40 Hz 1: 1 Hz or lower

<Selectivity>
Absolute value of the frequency change of the QCM sensor when 1 mL of saturated vapor of n-hexane flows (RA [Hz]), and the absolute value of the change in frequency of QCM when 1 mL of saturated vapor of acetone flows (RN [Hz]) ) Was calculated, and the selectivity of the QCM sensor to acetone was evaluated according to the following criteria. The higher the value of the ratio, the better the selectivity of the QCM sensor.
5:20 or more 4:13 or more and less than 20 3: 6 or more and less than 13 2: 2 or more and less than 6 1: 2 or less

Table 1 shows the results of the above evaluation tests.

As shown in Table 1, the QCM sensors having the receiving layer containing the specific polymer (Examples 1 to 4) were different from the QCM sensors having the receiving layer containing other polymers (Comparative Examples 1 and 2) in It was shown that acetone contained in the system at a low concentration can be detected with high sensitivity and high selectivity.

1 first electrode 2 dielectric material (piezoelectric material)
3 second electrode 4 receiving layer containing specific polymer

Claims

A resonance-type or stress-type sensor having a receptor layer containing a polymer having a repeating unit having a partial structure represented by the formula (1).

In the formula (1), L 1 and L 2 each independently represent a divalent linking group.
The sensor according to claim 1, wherein the partial structure represented by the formula (1) is a partial structure represented by the formula (2).

In the formula (2), X 1 and X 2 are each independently —CR 1 R 2 —, —CR 3 R 4 —CR 5 R 6 —, —CR 7 ＣＲCR 8 —, —CO—, —CO Represents —CR 9 R 10 — or —O—. Y 1 and Y 2 each independently represent —CR 11 R 12 —, —O—, or a single bond.
R 1 to R 12 represent a hydrogen atom or a substituent. R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 9 and R 10 , and R 11 and R 12 are independently bonded to each other to form a ring It may be.
3. The sensor according to claim 1, wherein the partial structure represented by the formula (1) is a partial structure represented by the formulas (1-A) to (1-D).
(4) The sensor according to any one of (1) to (3), further comprising the receiving layer and another receiving layer.
The sensor according to any one of claims 1 to 4, wherein the sensor is a resonance type.