JP2010132559A - Water-soluble metal phthalocyanine complex, sensor element and sensor comprising the same and manufacturing method of sensor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-soluble metal phthalocyanine complex, a sensor element, a sensor and a manufacturing method of the sensor element. <P>SOLUTION: The water-soluble metal phthalocyanine complex is represented by the formula (wherein A is an ionic hydrophilic group; M is a metal element; and n is an integer selected from among 1-8). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel water-soluble metal phthalocyanine complex, a sensor element, a sensor using them, and a method for producing the sensor element.

In the field of chemical sensors, MOS (Metal Oxide Sensor) type sensors using oxide semiconductors are generally used.
The MOS type sensor is based on a relatively small fine particle crystal or sintered body of a metal oxide made into a semiconductor, and usually comprises a ceramic structure having an electrode wire such as Pt inside. The MOS type sensor is used at a high temperature of about 300 ° C. Due to the catalytic reaction at a high temperature on the metal oxide surface, gas molecules such as alcohol are reduced on the surface, and electrons are taken into the depleted metal oxide and neutralized. This utilizes the principle that the potential barrier at the grain boundary is lowered and the resistance is lowered. This MOS sensor is used as a sensor for alcohol and propane gas, but it has insufficient sensitivity, lacks selectivity for gas, is difficult to integrate, and requires high-temperature sensing There are problems such as.

In recent years, research on increasing the sensitivity of chemical sensors that detect chemical substances such as gases, odors, and volatile organic compounds, and research on chemical sensors that match the chemical substances to be detected have been conducted. Various proposals have also been made.
For example, Patent Document 1 describes a sensor in which a sensitive film is formed of a rubber-based material having a double bond on the surface of a piezoelectric vibrator. Patent Document 2 describes an ion concentration measurement ion sensor that forms a porphyrin-sensitive film and measures hydrogen ion, hydrofluoric acid, metal ion concentration, and the like. Patent Document 3 describes that a chemical gas sensor material containing a thin-film crown ether condensed phthalocyanine-based compound is formed on a crystal resonator and detects gases such as NOx and SOx.

  However, when the detection target of the chemical sensor is “odor”, no sensitive material has been found at present. When the detection target is “odor”, there are various types of odor molecules such as hydrogen sulfide, thiol, disulfide, amine, ammonia, indole, skatole, and aldehydes. However, no such sensitive material has been found.

JP-A-11-108818 JP 2004-37430 A JP 7-43285 A

  The present invention has been made based on such a technical problem, and an object thereof is to provide a novel water-soluble metal phthalocyanine complex that selectively captures a specific target substance such as an odor molecule. Another object of the present invention is to provide a sensor element and a sensor having high sensitivity suitable for the water-soluble metal phthalocyanine complex according to the present invention. Furthermore, a method for manufacturing a novel sensor element is also proposed.

上記一般式［化１］中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は、ポリフェニレン、ポリチオフェン、ポリピロール、ポリピリジンから選択される置換基を表す。
Ａは、Ｒ１、Ｒ２、Ｒ３、Ｒ４の少なくとも一部を置換するイオン性親水性基を表す。
Ｍは、Ｃｏ、Ｚｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ｍｎ、Ａｌ、Ｍｏ、Ｖ＝Ｏ、Ｒｕ、Ｇａ、Ｏｓ、Ｒｈ、Ｐｄ、Ｐｔから選択される１種または２種以上の金属元素を表す。
ｎは、１〜８から選択される整数を表す。 Under such a purpose, the present inventors have conducted intensive studies focusing on the high catalytic activity of water-soluble phthalocyanine, and as a result, by modifying the periphery of water-soluble phthalocyanine with a rigid and bulky substituent, It has been found that the target substance can be selectively captured by preventing nano-stacking and constructing nanospace.
That is, the present invention is a water-soluble metal phthalocyanine complex represented by the general formula [Chemical Formula 1].

In the general formula [Chemical Formula 1], R 1, R 2, R 3, and R 4 represent a substituent selected from polyphenylene, polythiophene, polypyrrole, and polypyridine.
A represents an ionic hydrophilic group that substitutes at least a part of R1, R2, R3, and R4.
M represents one or more metal elements selected from Co, Zn, Fe, Ni, Cu, Mn, Al, Mo, V = O, Ru, Ga, Os, Rh, Pd, and Pt.
n represents an integer selected from 1 to 8.

R1, R2, R3 and R4 are preferably polyphenylene.
A is preferably a —SO ₃ ^— group.
M is preferably Co.

  In addition, the present inventors pay attention to the fact that there are many ionic odor molecules such as organic acids typified by ammonia, hydrogen sulfide, and acetic acid as odor molecules as target substances. In order to capture the sensitivity, it has been found that it is effective to attract odor molecules around the polymer brush by introducing a chargeable monomer as a modifying group into the polymer brush. Further, by supporting the water-soluble metal phthalocyanine complex of the present invention on a polymer brush having a chargeable monomer as a modifying group, the concentration of odor molecules around the polymer brush is increased, and the water-soluble metal phthalocyanine complex more reliably It has been found that odor molecules can be captured.

  That is, the sensor element of the present invention is a sensor element having a substrate, a self-assembled monomolecular film formed on the substrate, and a polymer film made of a polymer brush formed on the self-assembled monomolecular film. The polymer brush is a polymer brush having a chargeable monomer as a modifying group.

上記一般式［化２］中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は、ポリフェニレン、ポリチオフェン、ポリピロール、ポリピリジンから選択される置換基を表す。
Ａは、Ｒ１、Ｒ２、Ｒ３、Ｒ４の少なくとも一部を置換するイオン性親水性基を表す。
Ｍは、Ｃｏ、Ｚｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ｍｎ、Ａｌ、Ｍｏ、Ｖ＝Ｏ、Ｒｕ、Ｇａ、Ｏｓ、Ｒｈ、Ｐｄ、Ｐｔから選択される１種または２種以上の金属元素を表す。
ｎは、１〜８から選択される整数を表す。
また、荷電性モノマーは、２−（ジメチルアミノ）−アクリル酸エチル、メタクリル酸メチル、スチレンから選ばれる１種以上であることが好ましい。
本発明のセンサー素子においては、基板が、金からなる基板またはＳｉ系材料の表面に金薄膜を形成した基板であることが好ましい。
また、自己組織化単分子膜は、チオール基を含有することが好ましい。 In the sensor element of the present invention, it is preferable that a water-soluble metal phthalocyanine complex represented by the following general formula [Chemical Formula 2] is supported on a polymer brush having a chargeable monomer as a modifying group.

In the above general formula [Chemical Formula 2], R 1, R 2, R 3 and R 4 represent a substituent selected from polyphenylene, polythiophene, polypyrrole and polypyridine.
A represents an ionic hydrophilic group that substitutes at least a part of R1, R2, R3, and R4.
M represents one or more metal elements selected from Co, Zn, Fe, Ni, Cu, Mn, Al, Mo, V = O, Ru, Ga, Os, Rh, Pd, and Pt.
n represents an integer selected from 1 to 8.
The chargeable monomer is preferably at least one selected from 2- (dimethylamino) -ethyl acrylate, methyl methacrylate, and styrene.
In the sensor element of the present invention, the substrate is preferably a substrate made of gold or a substrate in which a gold thin film is formed on the surface of a Si-based material.
Further, the self-assembled monolayer preferably contains a thiol group.

（上記一般式［化３］中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は、ポリフェニレン、ポリチオフェン、ポリピロール、ポリピリジンから選択される置換基を表す。
Ａは、Ｒ１、Ｒ２、Ｒ３、Ｒ４の少なくとも一部を置換するイオン性親水性基を表す。
Ｍは、Ｃｏ、Ｚｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ｍｎ、Ａｌ、Ｍｏ、Ｖ＝Ｏ、Ｒｕ、Ｇａ、Ｏｓ、Ｒｈ、Ｐｄ、Ｐｔから選択される１種または２種以上の金属元素を表す。
ｎは、１〜８から選択される整数を表す。）
からなるセンサー素子と、水溶性金属フタロシアニン錯体によりターゲット物質を捕捉し、捕捉したターゲット物質によるセンサー素子の物理的な変化を検出する検出手段と、を有することを特徴とする。
本発明のセンサーにおいては、検出手段が、センサー素子に捕捉されたターゲット物質による質量変化を振動型質量検出センサーの周波数変化として検出する検出手段であることが好ましい。 Furthermore, the sensor of the present invention is a polymer film comprising a substrate, a self-assembled monolayer formed on the substrate, and a polymer brush formed on the self-assembled monolayer and having a chargeable monomer as a modifying group. A water-soluble metal phthalocyanine complex represented by the following general formula [Chemical Formula 3] supported on a polymer brush;

(In the above general formula [Chemical Formula 3], R 1, R 2, R 3 and R 4 represent a substituent selected from polyphenylene, polythiophene, polypyrrole and polypyridine.
A represents an ionic hydrophilic group that substitutes at least a part of R1, R2, R3, and R4.
M represents one or more metal elements selected from Co, Zn, Fe, Ni, Cu, Mn, Al, Mo, V = O, Ru, Ga, Os, Rh, Pd, and Pt.
n represents an integer selected from 1 to 8. )
And a detection means for capturing a target substance with a water-soluble metal phthalocyanine complex and detecting a physical change of the sensor element due to the captured target substance.
In the sensor of the present invention, the detection means is preferably detection means for detecting a mass change due to the target material trapped by the sensor element as a frequency change of the vibration type mass detection sensor.

  Still further, the present invention provides a step of immobilizing a self-assembled monolayer in which a polymerization initiation point has been introduced in advance on a substrate, and a step of extending a polymer brush having a chargeable monomer as a modifying group based on the polymerization initiation point. And a method for manufacturing a sensor element.

  As described above, according to the present invention, a specific target substance such as an odor molecule can be selectively captured by a water-soluble metal phthalocyanine complex. Moreover, a sensor element and a sensor having high sensitivity suitable for the water-soluble metal phthalocyanine complex of the present invention can be obtained. Furthermore, the sensor element manufacturing method of the present invention can provide a sensor element in which a substrate, a self-assembled monolayer, and a polymer brush are chemically bonded.

Hereinafter, the present invention will be described in more detail.
<Water-soluble metal phthalocyanine complex>
The water-soluble metal phthalocyanine complex of the present invention has a structure of [Chemical Formula 1] [Chemical Formula 2] and [Chemical Formula 3], and has a feature that a target substance can be selectively captured. About this reason, this inventor has guessed as follows. This will be described with reference to FIGS. FIG. 1 (A) is a diagram schematically showing stacking of the phthalocyanine ring of the conventional water-soluble phthalocyanine shown in [Chemical Formula 5], and FIG. 1 (B) is the water-soluble metal of the present invention shown in [Chemical Formula 4]. It is a figure showing typically a phthalocyanine complex. Since water-soluble phthalocyanine 1 has a planar structure as shown in FIG. 1A, stacking is likely to occur between complexes. On the other hand, the water-soluble metal phthalocyanine complex of the present invention can prevent stacking of the phthalocyanine ring 2 by modifying the periphery of the phthalocyanine ring 2 with a rigid and bulky substituent 3 as shown in FIG. it can. Further, it is considered that the nanospace 4 can be constructed between the phthalocyanine ring 2 and the rigid and bulky substituent 3, and the target substance can be selectively captured in the nanospace 4.
Since the water-soluble metal phthalocyanine complex of the present invention can selectively capture a target substance, it can be used as a molecular recognition film of a chemical sensor.
In the present invention, capture of the target material means physical and chemical adsorption of the target material to the water-soluble metal phthalocyanine complex.

The substituent of the water-soluble metal phthalocyanine complex according to the present invention will be described.
R1, R2, R3, and R4 are substituents that modify the periphery of the phthalocyanine ring, and are selected from polyphenylene, polythiophene, polypyrrole, and polypyridine. Since these substituents have a rigid and bulky structure, an effect of preventing stacking of the phthalocyanine ring can be obtained.
R 1, R 2, R 3, and R 4 can be independently selected as a substituent so as to construct a nanospace in accordance with the target material to be captured, or can all be the same substituent.
R1, R2, R3, and R4 are preferably polyphenylene. The rigid structure of polyphenylene gives the water-soluble metal phthalocyanine complex of the present invention physical properties such as highly efficient electronic conductivity and photoconductivity.
As polyphenylene, pentaphenylbenzene and triphenylene are preferable.

A is an ionic hydrophilic group that substitutes a part of R1, R2, R3, and R4, and imparts water solubility to the water-soluble metal phthalocyanine complex of the present invention. As the ionic hydrophilic group, —SO ₃ ^— group, —COO ⁻ , —NH ₂ ⁺ , —O ⁻ , —CN ⁻ , —N (CH ₃ ) ³⁺ are preferable. The ionic hydrophilic group may be neutralized to form a salt.

N representing the number of substitutions of A is a number selected from an integer of 1 to 8, and is appropriately selected so that the water-soluble metal phthalocyanine complex becomes water-soluble in accordance with the substituents of R1, R2, R3, and R4. That's fine.
For example, when pentaphenylbenzene is used as R1 to R4 and —SO ₃ ^— group is used as A, a water-soluble metal phthalocyanine complex can be obtained by setting n to 5.

The water-soluble metal phthalocyanine complex of the present invention has selectivity for the target material due to the nanospace, but M also contributes to the selectivity for the target material.
M is one or more metal elements selected from Co, Zn, Fe, Ni, Cu, Mn, Al, Mo, V = O, Ru, Ga, Os, Rh, Pd, and Pt. A complex is composed of phthalocyanine and metal. V = O represents a double bond between V and O. Among M, Co (II) has a high catalytic ability in the oxidation reaction of thiols such as 2-mercaptoethanol.

Next, the synthesis of the water-soluble metal phthalocyanine complex of the present invention will be described.
A substituent such as polyphenylene and N, N-dimethylaminoethanol are put in a reaction vessel and degassed for 15 to 30 minutes, and then metal chloride is added and degassed for 15 to 30 minutes. Thereafter, the reaction is stirred and refluxed at a reaction temperature of 150 to 170 ° C. for a reaction time of 24 to 48 hours to allow the reaction to proceed. The obtained reaction solution is concentrated under reduced pressure, and a metal phthalocyanine complex can be synthesized by isolating and purifying by, for example, alumina column chromatography (dichloromethane). The reaction is preferably performed under a nitrogen stream.

Subsequently, a part of the substituents such as polyphenylene of the obtained metal phthalocyanine complex is substituted with an ionic hydrophilic group to obtain a water-soluble metal phthalocyanine complex. In order to take out the obtained water-soluble metal phthalocyanine complex as a solid, a salt obtained by neutralizing an ionic hydrophilic group may be used and dialyzed.
For example, when the substitution with an ionic hydrophilic group is sulfonation using concentrated sulfuric acid (H ₂ SO ₄ ), it is then neutralized with NaOH to form a sodium sulfonate salt. In order to take out the water-soluble metal phthalocyanine complex having the sulfonic acid sodium salt as a substituent as a solid, dialysis may be performed.

  In addition, it is preferable to add the metal which comprises a complex as a metal chloride, and it is preferable to use cobalt chloride, iron chloride, nickel chloride, copper chloride, etc.

<Sensor element>
The sensor element of the present invention will be described.

In the sensor element of the present invention, by introducing a modifying group having a chargeable monomer into the polymer brush, the functional group of the target substance is attracted and concentrated around the polymer brush, thereby improving the sensitivity as the sensor element.
In addition, by supporting the water-soluble metal phthalocyanine complex on the polymer brush into which the chargeable monomer is introduced, the target substance attracted to the polymer brush can be more reliably captured by the water-soluble metal phthalocyanine complex.
Furthermore, depending on the selection of the chargeable monomer, the polymer brush itself can capture the target substance, and in that case, it can be used as a sensitive material for the sensor without supporting a water-soluble metal phthalocyanine complex.

FIG. 2A is a schematic view of a substrate obtained by extending a polymer brush into which a chargeable monomer is introduced. The polymer brush 11 into which a chargeable monomer 12 is introduced is extended on a gold (Au) substrate 10. FIG. 2B is a schematic diagram illustrating a state where the water-soluble metal phthalocyanine complex 13 is supported on FIG. As shown in FIG. 2B, even when the target molecule 14 and other molecules 15 coexist, the charged monomer 12 attracts the target molecule 14 and promotes trapping in the water-soluble metal phthalocyanine complex 13.
A polymer brush refers to a molecule in which one end of a polymer is bonded to a material or the surface of a substrate and the other end is a free end. The polymer brush constructed on the surface of the substrate has a soft structure and can be extended by its own charge repulsion to form a three-dimensional functional group field on the surface. Furthermore, by controlling the length of the brush, the surface can be designed in accordance with the structure of the molecule to be fixed or the assembly, and a functional material can be produced at the molecular level.
In the present invention, the term “supporting” means that the charged group of the polymer brush is ionically bonded to the water-soluble group of the complex side chain. It also includes immobilization of the complex in the polymer brush by ionic bond, coordinate bond, hydrogen bond, etc. with the side chain of the polymer brush.

Since the sensor element is used by being arranged on an electrode substrate of a crystal resonator or an optical fiber substrate, the present invention also proposes a method for fixing a polymer brush to the substrate.
As the substrate, a substrate made of gold (Au) or a substrate in which a gold (Au) thin film is formed on the surface of a Si-based material is preferable. A substrate having a gold surface can be used as an electrode of a vibration-type mass detection sensor such as a crystal resonator.

A self-assembled monolayer (hereinafter referred to as SAMs) is formed on the substrate surface. By forming the SAMs on the substrate surface, the substrate and the SAMs, and the SAMs and the polymer brush are chemically bonded to each other.
SAMs are formed by combining thiol molecules having a thiol group (—SH) with gold. As a molecule having a thiol group, 2-Mercaptoethanol (2-mercaptoethanol), 3-Mercapto-1-propanol (3-mercapto-1-propanol), 11-Mercapto-1-undecanol (11-mercapto-1-undecanol) ), Cystine (cystine), 3,3′-Dithiodipropionic Acid (3,3′-dithiodipropionic acid), 4,4′-Dithiodibutyric Acid (4,4′-dithiodibutyric acid) and the like are preferable.

Next, in order to stretch the polymer brush on the gold substrate on which the SAMs are formed, first the polymerization start point of the polymer brush is introduced, and then the polymer brush is stretched.
The polymerization initiation point binds 2-brom-2-methylhl propionyl bromide (2-bromopropynyl bromide) or the like to the end opposite to the end of the thiol molecular chain that is bonded to thiol.
By introducing a chargeable monomer as a modifying group from the polymerization start point, the polymer expands due to the charge repulsion of the chargeable monomer itself, and (CH ₂ CHX) _m (where X represents a functional group, m is A polymer brush made of a polymer such as a polymer representing the degree of polymerization is obtained. By selecting a chargeable monomer having a charge opposite to that of the functional group of the target material, an effect of attracting the target material can be obtained. Examples of the chargeable monomer include 2- (dimethylamino) -ethyl acrylate, methyl methacrylate, styrene, trimethylvinylammonium bromide, vinyl sulfonate sodium salt, sodium allyl sulfonate, 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate) ), 4-Hydroxybutyryl acrylate (4-hydroxybutyl acrylate), 2-Cyanoethyl acrylate (2-cyanoethyl acrylate), Methacryloyl Chloride Chloride (methacryloylcholine chloride), 3-Sulfopropyl Methacrylate sulphopropyl methacrylate 4-vinylpyridine, 1, 2,2,6,6-Pentametyl-4-piperidyl methacrylate (1,2,2,6,6-pentamethyl-4-piperidyl methacrylate) is preferred. Further, when styrene is used as the chargeable monomer, the target material can be captured with a polymer brush.
What is necessary is just to set the polymerization degree of a polymer brush suitably according to the length of the desired polymer brush.

A method for manufacturing a sensor element according to the present invention will be described with reference to the flowcharts shown in FIGS.
The manufacturing method of the sensor element shown in FIG. 6 includes a step of fixing SAMs to the substrate (S11), a step of introducing a polymerization start point (S12), and a step of extending a polymer brush (S13).
On the other hand, the method for producing the sensor element shown in FIG. 7 includes a step (S21) of immobilizing the self-assembled monolayers (SAMs) into which a polymerization initiation point has been introduced in advance on a substrate, and the polymerization initiation point as a base point. And a step (S22) of extending a polymer brush having a chargeable monomer as a modifying group.
Although any of the methods can produce the sensor element of the present invention, it is preferable to use the production method shown in FIG. 7 in the present invention. Since it is important to keep the substrate clean when performing operations in each process, the substrate is cleaned for each process. Although the method shown in FIG. 6 has three steps, the method shown in FIG. 7 has two steps and the number of steps is small, the number of times of substrate cleaning can be reduced, and stable manufacturing becomes possible.
For cleaning the substrate, the piranha solution is placed on the entire substrate or the surface on which the SAMs are immobilized, allowed to stand for 15 minutes, rinsed with distilled water, and dried with N ₂ or clean air. Further, it is preferable to perform the next step without leaving after washing and immobilization of SAMs.

  The support of the water-soluble metal phthalocyanine complex on the polymer brush can be obtained by immersing the substrate on which the polymer brush has been extended in a water-soluble metal phthalocyanine complex aqueous solution for 10 minutes to 24 hours, washing with distilled water, and drying. The concentration of the water-soluble metal phthalocyanine complex aqueous solution at this time is preferably 1 mM.

<Sensor>
The sensor according to the present invention preferably has detection means for detecting a physical change of the sensor element when the target substance is adsorbed on the sensor element of the present invention. As detection means, methods such as electrical detection, optical detection, chemical detection, and electrochemical detection can be applied. As a detection means applied to the sensor according to the present invention, it is preferable to detect a mass change due to adsorption / desorption of the target substance as a frequency change using a vibration type mass detection sensor. By arranging the sensor element of the present invention using the electrode on the vibration mass detection sensor as a substrate, a highly sensitive sensor is obtained. As the vibration type mass detection sensor, a sensor using a crystal resonator is preferable. Further, a vibration type mass detection sensor using a small vibrator using a MEMS (Micro Mechanical Electrical System) technique can be used. In this case, integration and integration with a circuit are easier than QCM.
For example, in a quartz crystal microbalance (QCM), when a substance is adsorbed on the surface of the crystal oscillator, the fundamental frequency of the crystal oscillator is proportional to the mass of the adsorbed substance according to the Sauerbrey equation (1) below. Change. Here, ΔF is a change in fundamental frequency, Δm is a change in weight, and K is a constant.
ΔF = −K × Δm (1)

As a water-soluble metal phthalocyanine complex according to the present invention, β-tetrakis [2,3,4,5-penta (2,3,4,5,6-sulfonyl) benzene] phthalocyanate cobalt represented by [Chemical Formula 4] ( II) was synthesized.
In the synthesis of sulfonated β-tetrakis (2,3,4,5-pentaphenylbenzene) phthalocyanate cobalt (II), first, (1) 3,4-dicyanohexaphenylbenzene was synthesized, and (2) obtained 3 Β-tetrakis (2,3,4,5-pentaphenylbenzene) phthalocyanate cobalt (II) was synthesized from 1,4-dicyanohexaphenylbenzene as a raw material, and (3) sulfonation and dialysis were performed.
The obtained β-tetrakis [2,3,4,5-penta (2,3,4,5,6-sulfonyl) benzene] phthalocyanate cobalt (II) was evaluated (4).
Hereinafter, the synthesis methods (1) to (3) and the evaluation (4) will be sequentially described.
(1) Synthesis of 3,4-dicyanohexaphenylbenzene 3,4-dicyanodiphenylacetylene 0.19 g (8.19 × 10 −4 mol), tetraphenylcyclopentadienone 0.38 g (9.83 × 10 −4 mol) ), 4 ml of diphenyl ether were placed in a flask and stirred and refluxed at 210 ° C. for 20 hours. After returning to room temperature, the reaction solution was purified by silica gel column chromatography (petroleum ether → petroleum ether / dichloromethane = 1) and dried under reduced pressure to obtain 3,4-dicyanohexaphenylbenzene.
The synthesis of 3,4-dicyanohexaphenylbenzene was performed under a nitrogen stream.

(2) Synthesis of β-tetrakis (2,3,4,5-pentaphenylbenzene) phthalocyanate cobalt (II) Next, using 3,4-dicyanohexaphenylbenzene as a raw material, β-tetrakis (2,3,4,5) -Pentaphenylbenzene) phthalocyanate cobalt (II) was synthesized.
0.30 g (5.13 × 10 −4 mol) of 3,4-dicyanohexaphenylbenzene and 3 ml of N, N-dimethylaminoethanol were placed in a flask, deaerated for 30 minutes, and then added with anhydrous cobalt (II) chloride (0.1). 033 g (2.57 × 10 −4 mol) was added, and deaeration was performed again for 30 minutes. Thereafter, the mixture was stirred and refluxed at 170 ° C. for 48 hours. After the reaction solution was concentrated under reduced pressure, purification was performed by applying alumina column chromatography (dichloromethane) twice, followed by drying under reduced pressure, and β-tetrakis (2,3,4,5-pentaphenylbenzene) phthalocyanate cobalt (II ) Was synthesized.
The synthesis of β-tetrakis (2,3,4,5-pentaphenylbenzene) phthalocyanate cobalt (II) was performed under a nitrogen stream.

(3) Sulfonation and dialysis of β-tetrakis (2,3,4,5-pentaphenylbenzene) phthalocyanate cobalt (II) β-tetrakis (2,3,4,5-pentaphenylbenzene) obtained in (2) ) 0.10 g (2.5 × 10 −5 mol) of phthalocyanate cobalt (II) and 2 ml of concentrated sulfuric acid were placed in a flask and stirred and refluxed at 100 ° C. for 1 hour. The reaction solution was quenched, neutralized with sodium hydroxide, dialyzed using a 0.2 ml / cm dialysis tube, dried under reduced pressure, and β-tetrakis [2,3,4,5-penta (2, 3,4,5,6-sulfonyl) benzene] phthalocyanate cobalt (II) was obtained.

(4) Evaluation In order to evaluate whether or not odor molecules can be selectively captured, the β-tetrakis [2,3,4,5-penta (2,3,4,5) obtained in (3) is used using a DO meter. 5,6-sulfonyl) benzene] phthalocyanate cobalt (II) concentration of 6.0 × 10 ⁻⁶ mol / l was mixed with 2-mercaptoethanol, and dissolved oxygen was measured. The maximum reaction rate Vmax was It was 1.8 × 10 ⁻⁴ mol / l · min, and the catalyst rotation speed k ₅ was 30 min ⁻¹ .
For comparison, 2-mercaptoethanol was mixed in an aqueous solution of 8.8 × 10 ⁻⁶ mol / l of β-tetrakis (sulfonyl) phthalocyanate cobalt (II) represented by the general formula [Chemical Formula 6] and dissolved. It was subjected to measurement of oxygen, the maximum reaction rate Vmax is ^{3.75 × 10 -4 mol / l ·} min, the catalyst turnover number _{k 5} was 426min ^-1.

The β-tetrakis [2,3,4,5-penta (2,3,4,5,6-sulfonyl) benzene] phthalocyanate cobalt (II) obtained in (3) has a high catalytic ability. Was confirmed.
Incidentally, _{k 5,} the maximum reaction rate Vmax (unit mol / l · min) (the unit mol / l) solution concentration of the complex is determined from the values divided by.

Here, the measuring method of the catalytic ability by the oxidation reaction of 2-mercaptoethanol will be described.
The oxidation reaction of 2-mercaptoethanol (sometimes referred to as 2HOCH ₂ CH ₂ SH: RSH) at pH 7.0 and 25 ° C. proceeds as follows.
_{2HOCH 2 CH 2 SH + O 2} → 2HOCH 2 CH 2 S-SCH 2 CHOH + H 2 O + 1 / 2O 2
The reaction rate in the thiol oxidation reaction was calculated from the oxygen consumption rate, and the number of revolutions of the catalyst cycle was determined.

(5) Gas adsorption evaluation The β-tetrakis [2,3,4,5-penta (2,3,4,5,6-sulfonyl) benzene] phthalocyanate cobalt (II) of the present invention obtained in (3) is used. A film was formed on the sensor element using a cast method, and acetone, ethanol, and toluene were adsorbed as odor molecules, and a frequency change by a quartz crystal microbalance sensor (hereinafter referred to as a QCM sensor) was measured. Further, for comparison, acetone, ethanol, and toluene were adsorbed using a sensor element that was not formed into a film, and the frequency change by the QCM sensor was measured.
Film formation by the cast method was performed on a 0.05 wt% β-tetrakis [2,3,4,5-penta (2,3,4) on a sensor element having a quartz base plate size of 8.7 mm and a gold electrode diameter of 5.0 mm. , 5,6-sulfonyl) benzene] phthalocyanate cobalt (II) aqueous solution 8 μl was applied and vacuum dried.

Measurement of frequency change by the QCM sensor was performed in the same manner as in Example 4 described later. The results of measuring the frequency change are shown in FIGS. 8, 9, and 10. FIG. 8 shows the frequency change ΔF when acetone 4000 ppm is introduced, FIG. 9 shows the frequency change ΔF when ethanol 4000 ppm is introduced, and FIG. This is a frequency change ΔF when 4000 ppm of toluene is introduced. 8 to 10, no film is a sensor element that does not form a film, and Pc—SO ₃ Na is β-tetrakis [2,3,4,5-penta (2,3,4,5,6-sulfonyl) benzene] phthalo. This is a sensor element in which cyanate cobalt (II) is formed.
Referring to FIGS. 8, 9, and 10, by using β-tetrakis [2,3,4,5-penta (2,3,4,5,6-sulfonyl) benzene] phthalocyanate cobalt (II), It was confirmed that when any gas such as acetone, ethanol, and toluene was introduced, the frequency decreased and the gas could be adsorbed, and the frequency change pattern varied depending on the gas type.

A sensor element having β-tetrakis [2,3,4,5-penta (2,3,4,5,6-sulfonyl) benzene] phthalocyanate cobalt (II) obtained in Example 1 supported on a polymer brush was produced. did.
The sensor element uses a substrate in which a gold (Au) thin film is formed on the surface of a Si-based material, and (1) self-assembled monolayers (SAMs) are formed on the surface of the gold thin film, and (2) atom transfer living radical polymerization. A polymer brush was elongated by (ATRP), and (3) a water-soluble metal phthalocyanine complex was supported on the polymer brush, and (4) evaluated. Hereinafter, (1) and (2) will be described with reference to FIG. FIG. 3 is a diagram for explaining a process for forming a polymer brush on the gold (Au) surface of the substrate.

(1) Formation of self-assembled monolayers (SAMs) As shown in FIG. 3, the substrate 100 having a gold surface is reacted with 11-Mercapto-1-undecanol (11-mercapto-1-undecanol) (tinol treatment). ) To obtain the substrate 101 on which the SAMs are formed.
The gold surface of the substrate 100 was cleaned in advance. The cleaning was performed by washing the gold surface with 1% sodium dodecyl sulfate solution and sulfuric acid: 30% hydrogen peroxide solution = 4: 1 Piranha solution, and then thoroughly rinsing with distilled water.
Next, a 1 mM (0.7 mg / ml) ethanol solution of 11-Mercapto-1-undecanol was placed on the gold surface of the cleaned substrate and allowed to stand for 24 hours. Ethanol was degassed with nitrogen. After standing, the gold surface was washed with ethanol and dried to obtain a substrate 101 on which SAMs were formed.

(2) Extension of polymer brush by atom transfer living radical polymerization (ATRP) First, a treatment for introducing a polymerization start point of a polymer brush is performed. As shown in FIG. 3, a polymer brush polymerization start point is introduced into a substrate 101 having a gold surface on which SAMs are formed, and a substrate 102 is obtained.
In an ice bath, put SAMs substrate 101, triethylamine (hereinafter sometimes referred to as TEA) 0.07 ml (5.4 × 10 ⁻⁴ mol) in a flask, and tetrahydrofuran (hereinafter referred to as THF). It was dissolved in 1 ml. After the inside of the flask was degassed for 30 minutes, 0.07 ml (5.4 × 10 ⁻⁴ mol) of 2-bromopropionyl bromide was dissolved in 5 ml of THF and slowly added into the flask using a dropping funnel. It returned to room temperature and left to stand under nitrogen atmosphere for 12 hours. After standing, the substrate taken out from the flask was washed with THF and dried to obtain a substrate 102 into which a polymerization initiation point was introduced.

Next, a polymerization process is performed, and as shown in FIG. 3, a polymer brush is extended on the substrate 102 into which the polymerization start point is introduced.
Substrate 102 with a polymerization initiation point introduced into the reaction vessel, 2- (dimethylaminoethyl) acrylate [2- (dimethylamino) -ethyl acrylate] 3.037 ml (0.02 mol), Fe (II) Br 0.014 g (0 0.067 mmol), Triphenylphosphine (triphenylphosphine) 0.05 g (0.2 mmol), ethyl-II-Bromoisobutyrate (ethyl-2-bromoisobutyrate) 0.009 ml (0.067 mmol), frozen, degassed, After dissolution, the mixture was reacted in an oil bath at 60 ° C. for 3 hours. After the reaction, the gold surface of the substrate was washed with methanol and then immersed in dichloromethane for 24 hours to remove the polymer not immobilized on the gold surface, thereby obtaining a substrate 103 with an extended polymer brush.

(3) Support of water-soluble metal phthalocyanine complex on polymer brush The substrate 103 with the polymer brush extended is immersed in a 1 mM (4.438 mg / ml) water-soluble metal phthalocyanine complex aqueous solution for 10 minutes, washed with distilled water, dry.
By observation with an AFM (atomic force microscope), mass measurement by QCM, and identification of the RAS spectrum of the substrate 103, it was confirmed that the water-soluble metal phthalocyanine complex was supported on the polymer brush.

(4) Evaluation A polymer brush having a positive charge adsorbs acidic gases such as hydrogen sulfide, methyl mercaptan, and acetic acid. In contrast, a negatively charged polymer brush adsorbs basic gases such as ammonia, dimethylamine, and pyridine. Furthermore, when the water-soluble metal phthalocyanine complex of the present invention is supported in a polymer brush, the selectivity is improved with respect to gases such as hydrogen sulfide, methyl mercaptan, ammonia and pyridine that can be coordinated to the central metal of the metal phthalocyanine complex.

  In Example 2, after forming SAMs, a substrate on which a polymer brush was formed was obtained by using a method of introducing a polymerization starting point and extending the polymer brush. In Example 3, a method of forming SAMs into which a polymerization start point has been introduced in advance on a substrate and extending a polymer brush will be described with reference to FIG. FIG. 4 is a diagram for explaining a process for forming a polymer brush on the gold (Au) surface of the substrate.

(1) Formation of self-assembled monolayers (SAMs) As shown in FIG. 4, 13, 13′-dithio-bis- (2-bromo-3-tridecanone) [13, 13] is formed on a substrate 200 having a gold surface. '-Dithio-bis- (2-bromo-3-tridecanone)] is reacted to obtain a substrate 201 having a gold surface on which SAMs into which a polymerization initiation point has been introduced are formed.
The gold surface of the substrate 200 was cleaned in advance. The cleaning was performed by washing the gold surface of the substrate 200 using a 1% sodium dodecyl sulfate solution and a Piranha solution of sulfuric acid: 30% hydrogen peroxide = 4: 1, and then thoroughly rinsing with distilled water.
Next, a 1 mM (0.7 mg / ml) dry toluene solution of 13,13′-dithio-bis- (2-bromo-3-tridecanone) was prepared, and the substrate 200 was immersed vertically in a Teflon plate at 60 ° C. The SAMs were immobilized by leaving still in an oil bath for 24 hours. Thereafter, the substrate was rinsed with toluene and ethanol, and nitrogen was blown and dried to obtain a substrate 201 on which SAMs into which a polymerization start point was introduced were formed.

In addition, 13,13′-dithio-bis- (2-brom-3-tridecanone) is a compound in which a polymerization starting point is introduced using 11-Mercapto-1-undecanol as a raw material. A method for synthesizing 13,13′-dithio-bis- (2-bromo-3-tridecanone) is shown in FIG. The operation is performed under a nitrogen stream. In an ice bath, 11-mercapto-1-undecanol 0.5 g (2.246 × 10 ⁻³ mol), 2 ml of 10% KHCO ₃ aqueous solution and 10 ml of dryCH ₂ Cl ₂ are placed in the flask and thoroughly deaerated. Thereafter, bromine was added little by little until white, extracted with water and dichloromethane, dehydrated with anhydrous sodium sulfate, and purified by silica gel column chromatography (dichloromethane).

(2) Extension of polymer brush by atom transfer living radical polymerization (ATRP) The substrate 201 on which the SAMs into which the polymerization initiation point has been introduced is formed using 2- (dimethylamino) -ethyl acrylate as a chargeable monomer. Then, a substrate 202 was produced by extending the polymer brush shown in FIG.
Substrate 201 on which SAMs having a polymerization initiation point introduced are formed in a reaction vessel, 2- (Dimethylaminoethyl) acrylate [2- (dimethylamino) -ethyl acrylate] 3.037 ml (0.02 mol), Fe (II) Br0 .014 g (0.067 mmol), Triphenylphosphine (triphenylphosphine) 0.05 g (0.2 mmol), ethyl-II-bromoisobutyrate (ethyl-2-bromoisobutyrate) 0.009 ml (0.067 mmol) After deaeration and dissolution, the mixture was reacted in an oil bath at 60 ° C. for 3 hours. After the reaction, the gold surface of the substrate was washed with methanol, and then immersed in dichloromethane for 24 hours to remove the polymer not immobilized on the gold surface, thereby obtaining a substrate 202 with an extended polymer brush.

  A sensor element in which a polymer brush was extended using three kinds of chargeable monomers was manufactured, and gas change was performed by a QCM sensor to measure a frequency change. For comparison, frequency changes were also measured for sensor elements not forming SAMs or polymer brushes.

Here, the QCM sensor will be described with reference to FIGS. FIG. 11 is a schematic diagram of the QCM sensor 21, and the oscillator 23 and the sensor element 24 placed on the oscillator 23 are installed in the chamber 22 and connected to the frequency detection counter 25 outside the chamber 22. . The chamber 22 includes a gas introduction valve 27, a nitrogen introduction valve 30, and an exhaust valve 28, and the inside of the chamber 22 can be controlled to a desired atmosphere. Further, the gas introduction valve 27 is provided with a heater 29 so that the gas introduced into the chamber 22 can be heated as necessary. A hygrometer (not shown) may be installed in the chamber 22.
When gas is introduced into the chamber 22 through the gas introduction valve 27, the sensor element 24 adsorbs the gas and changes its mass. Since the frequency changes with the mass change, the frequency change is measured by the frequency detection counter 25, and the frequency change is output by the computer 26 connected to the frequency detection counter 25. As the frequency detection counter 25, an Agilent 53131A universal frequency counter was used.

  FIG. 12 shows an enlarged schematic diagram of the sensor element 24. The sensor element 24 includes a substrate 31 and a sensitive film 32 formed on the substrate 31, and includes a terminal 33. As the substrate 31, a substrate having a frequency of 9 MHz, a crystal base plate size of φ8.7 mm, a gold electrode diameter of φ5.0 mm, and a chromium / gold (thickness 500 angstrom) electrode deposited on both sides of an AT-Cut crystal plate is used (Tama Device made) When 1 ng substance adheres to the electrode surface, the frequency decreases by 1 Hz. As the sensitive film 32, a polymer film made of the water-soluble metal phthalocyanine complex of the present invention or a polymer brush is formed.

In the measurement of the frequency change by the QCM sensor 21 shown in FIG. 11, first, the exhaust valve 28 is opened and the inside of the chamber 22 is evacuated, then the exhaust valve 28 is closed, the nitrogen introduction valve 30 is opened, and the inside of the apparatus is made a nitrogen atmosphere. . A state where the nitrogen introduction valve 30 was closed and the frequency was stabilized was taken as a baseline. Next, the gas introduction valve 27 was opened to introduce gas (referred to as gas in in FIGS. 13 to 16). The gas was introduced for 1 minute. Thereafter, the gas introduction valve 27 is closed, the apparatus is sealed, and the frequency change is measured. When the frequency change accompanying the gas introduction becomes constant, the exhaust valve 28 is opened (denoted as open in FIGS. 13 to 16). The gas in the apparatus was exhausted, and the nitrogen introduction valve 30 was opened and replaced with nitrogen to return the frequency to the baseline. The frequency change was measured at room temperature.
Hereinafter, four types of sensor element manufacturing methods and gas adsorption evaluation using them will be described.

(1) Formation of self-assembled monolayers (SAMs) Four sensor elements having a quartz base plate size of 8.7 mm and a gold electrode diameter of 5.0 mm were prepared, and the washing operation was repeated twice. The washing operation was carried out by placing a Piranha solution (concentrated sulfuric acid: 30% hydrogen peroxide solution = 3: 1) only on the gold electrode portion, allowing to stand for 15 minutes, rinsing with distilled water, and drying with N ₂ or clean air. For sensor elements that do not form SAMs or polymer brushes, frequency changes were measured after two washing operations.
Next, a 1 mM (0.7 mg / ml) dry toluene solution of 13,13′-dithio-bis- (2-bromo-3-tridecanone) was made, and the sensor elements were immersed vertically in a Teflon plate at 60 ° C. The SAMs were immobilized by leaving still in an oil bath for 24 hours. Thereafter, the sensor element was rinsed with toluene and ethanol, and dried by spraying nitrogen to obtain three sensor elements formed with SAMs into which a polymerization initiation point was introduced.
The synthesis of 13,13′-dithio-bis- (2-bromo-3-tridecanone) was performed in the same manner as in Example 3.

(2) Extension of polymer brush by atom transfer living radical polymerization (ATRP) Three types of 2- (dimethylamino) -ethyl acrylate, methyl methacrylate, and styrene are prepared as chargeable monomers and each has a modification group. A sensor element in which a polymer brush was formed was produced.

<2- (Dimethylamino) -ethyl acrylate>
In a molar ratio, 2- (dimethylamino) -ethyl acrylate: Triphenylphosphine: FeBr ₂ : ethyl-II-bromoisobutyrate = 1: 0.01: 0.003: 0.003 into a reaction vessel, and N ₂ Dissolved with replacement. Sensor elements on which SAMs having a polymerization initiation point were formed were immersed vertically in a Teflon plate, and after freezing and drying were repeated three times, they were reacted in an oil bath at 60 ° C. for 3 hours. After the reaction, the gold electrode surface of the sensor element is rinsed with dichloromethane and methanol, allowed to stand in dichloromethane at room temperature for 24 hours, dried with N ₂ , and a polymer having 2- (dimethylamino) -ethyl acrylate as a modifying group A sensor element with an extended brush was obtained.

<Methyl methacrylate>
In a molar ratio, methyl methacrylate: Triphenylphosphine: Fe (II) Br: ethyl-II-Bromoisobutyrate = 1: 0.01: 0.003: 0.003 into a reaction vessel and dissolved while substituting with N ₂ did. Sensor elements on which SAMs having a polymerization initiation point were formed were immersed vertically in a Teflon plate, and after freezing and drying were repeated three times, they were reacted in an oil bath at 60 ° C. for 3 hours. After the reaction, the surface of the gold electrode of the sensor element was rinsed with dichloromethane and methanol, allowed to stand in dichloromethane for 24 hours at room temperature, dried with N ₂ , and a sensor element with a polymer brush having methyl methacrylate as a modifying group extended. Obtained.

<Styrene>
In a molar ratio, styrene: Triphenylphosphine: Fe (II) Br: ethyl-II-Bromoisobutyrate = 1: 0.01: 0.003: 0.003 was placed in a reaction vessel and dissolved while substituting with N ₂ . Sensor elements on which SAMs having a polymerization initiation point were formed were immersed vertically in a Teflon plate, and after freezing and drying were repeated three times, they were reacted in an oil bath at 60 ° C. for 3 hours. After the reaction, the gold electrode surface of the sensor element was rinsed with dichloromethane and methanol, allowed to stand at room temperature in dichloromethane for 24 hours, and then dried with N ₂ to obtain a sensor element in which a polymer brush having styrene as a modifying group was elongated. .

(3) Gas adsorption evaluation In the case where 4000 ppm each of acetone, ethanol, and toluene is introduced using a sensor element obtained by extending the three types of polymer brushes prepared in (2) and a sensor element that does not form SAMs and polymer brushes. Frequency change was measured with a QCM sensor. FIG. 13 shows the frequency change ΔF for acetone, FIG. 14 shows the frequency change ΔF for ethanol, and FIG. 15 shows the frequency change ΔF for toluene. 13 to 15, amine is 2- (dimethylamino) -ethyl acrylate, MMA is methyl methacrylate, stylene is frequency change when styrene is used as a chargeable monomer, no film is SAMs, polymer brush The frequency change when not forming is shown.

  It can be seen from FIGS. 13 to 15 that each sensor element shows a different frequency change for each gas type. Further, when attention is paid to the frequency change of stylene, it can be confirmed that all of acetone, ethanol, and toluene have a decreased frequency and an increased weight. From this, it can be seen that the sensor element in which the polymer brush having styrene as the modifying group is formed has a function of capturing the target substance in addition to the improvement of the sensitivity of the sensor element. MMA has little frequency change with respect to acetone, ethanol, and toluene, and when these are used as target substances, it has little function of capturing, but since the functional group of MMA attracts the target substance, it has sensitivity as a sensor element. Contributes to improvement. In the case of amine, when toluene is adsorbed, the frequency decreases and the weight increases, whereas in FIGS. 13 and 14 where acetone and ethanol are adsorbed, the frequency increases and the weight decreases. This is because tertiary amine, which is a functional group of 2- (dimethylamino) -ethyl acrylate, captures water in the air in advance and is captured when a hydrophilic gas such as acetone or ethanol is introduced. It is thought that the moisture that had been introduced was introduced with the gas.

  FIG. 16 shows the result of measuring the frequency change by the QCM sensor after introducing water as a gas, together with the humidity change in the chamber of the QCM sensor. When FIG. 16 was seen, since a frequency fell with the increase in humidity and a frequency increased with the decrease in humidity, it was confirmed that 2- (dimethylamino) -ethyl acrylate is sensitive to water.

It is a schematic diagram for demonstrating the stacking control by the (A) conventional phthalocyanine complex and the (B) water-soluble metal phthalocyanine complex of this invention. (A) is a schematic diagram of the board | substrate which extended | stretched the polymer brush which introduce | transduced the chargeable monomer, (B) is a schematic diagram showing the state which carry | supported the water-soluble metal phthalocyanine complex in (A). It is a figure for demonstrating the preparation methods of the polymer brush concerning this invention. It is a figure for demonstrating the preparation methods of the polymer brush concerning this invention. It is a figure which shows the synthesis | combining method of 13,13'-dithio-bis- (2-bromo-3-tridecanone). It is a flowchart which shows the manufacturing process of a sensor element. It is a flowchart which shows the manufacturing process of a sensor element. It is a figure showing the frequency change at the time of adsorb | sucking acetone to the water-soluble phthalocyanine complex of this invention. It is a figure showing the frequency change at the time of adsorb | sucking ethanol to the water-soluble phthalocyanine complex of this invention. It is a figure showing the frequency change at the time of adsorb | sucking toluene in the water-soluble phthalocyanine complex of this invention. It is a schematic diagram of a QCM sensor. It is an expansion schematic diagram of a sensor element. It is a figure showing the frequency change at the time of adsorb | sucking acetone to a sensor element. It is a figure showing the frequency change at the time of adsorb | sucking ethanol to a sensor element. It is a figure showing a frequency change at the time of adsorbing toluene on a sensor element. It is a figure showing the frequency change and humidity change at the time of adsorb | sucking water to a sensor element.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Water-soluble phthalocyanine, 2 ... Phthalocyanine ring, 3 ... Rigid and bulky substituent, 4 ... Nanospace, 10 ... Gold substrate, 11 ... Polymer brush, 12 ... Chargeable monomer, 13 ... Water-soluble metal phthalocyanine complex, 14 ... target molecule, 15 ... other molecules, 21 ... QCM sensor, 23 ... oscillator, 24 ... sensor element, 25 ... frequency detection counter, 100 ... substrate, 101 ... substrate on which SAMs are formed, 102 ... polymerization start point is introduced Substrate, 103 ... Substrate obtained by extending a polymer brush, 200 ... Substrate, 201 ... Substrate on which SAMs having a polymerization start point are introduced, 202 ... Substrate obtained by extending a polymer brush

Claims (12)

A water-soluble metal phthalocyanine complex represented by the following general formula [Chemical Formula 1].

In the general formula [Chemical Formula 1], R 1, R 2, R 3, and R 4 represent a substituent selected from polyphenylene, polythiophene, polypyrrole, and polypyridine.
A represents an ionic hydrophilic group that substitutes at least a part of R1, R2, R3, and R4.
M represents one or more metal elements selected from Co, Zn, Fe, Ni, Cu, Mn, Al, Mo, V = O, Ru, Ga, Os, Rh, Pd, and Pt.
n represents an integer selected from 1 to 8.   The water-soluble metal phthalocyanine complex according to claim 1, wherein R1, R2, R3, and R4 are polyphenylene. The water-soluble metal phthalocyanine complex according to claim 1, wherein A is a —SO ₃ ^— group.   The water-soluble metal phthalocyanine complex according to any one of claims 1 to 3, wherein M is Co. A substrate,
A self-assembled monolayer formed on the substrate;
A polymer film comprising a polymer brush formed on the self-assembled monolayer;
A sensor element comprising:
A sensor element, wherein the polymer brush is a polymer brush having a chargeable monomer as a modifying group. To the polymer brush,
The sensor element according to claim 5, wherein a water-soluble metal phthalocyanine complex represented by the following general formula [Chemical Formula 2] is supported.

In the above general formula [Chemical Formula 2], R 1, R 2, R 3 and R 4 represent a substituent selected from polyphenylene, polythiophene, polypyrrole and polypyridine.
A represents an ionic hydrophilic group that substitutes at least a part of R1, R2, R3, and R4.
M represents one or more metal elements selected from Co, Zn, Fe, Ni, Cu, Mn, Al, Mo, V = O, Ru, Ga, Os, Rh, Pd, and Pt.
n represents an integer selected from 1 to 8.   The sensor element according to claim 5, wherein the chargeable monomer is at least one selected from 2- (dimethylamino) -ethyl acrylate, methyl methacrylate, and styrene.   8. The sensor element according to claim 5, wherein the substrate is a substrate made of gold or a substrate in which a gold thin film is formed on the surface of a Si-based material.   The sensor element according to claim 5, wherein the self-assembled monolayer contains a thiol group. A substrate,
A self-assembled monolayer formed on the substrate;
A polymer film formed on the self-assembled monolayer film and made of a polymer brush having a chargeable monomer as a modifying group;
A water-soluble metal phthalocyanine complex represented by the following general formula [Chemical Formula 3] supported on the polymer brush;

(In the above general formula [Chemical Formula 3], R 1, R 2, R 3 and R 4 represent a substituent selected from polyphenylene, polythiophene, polypyrrole and polypyridine.
A represents an ionic hydrophilic group that substitutes at least a part of R1, R2, R3, and R4.
M represents one or more metal elements selected from Co, Zn, Fe, Ni, Cu, Mn, Al, Mo, V = O, Ru, Ga, Os, Rh, Pd, and Pt.
n represents an integer selected from 1 to 8. )
A sensor element comprising:
A detection means for capturing a target substance with the water-soluble metal phthalocyanine complex, and detecting a physical change of the sensor element due to the captured target substance;
A sensor characterized by comprising:   The sensor according to claim 10, wherein the detection unit is a detection unit that detects a mass change due to the captured target material as a frequency change of a vibration type mass detection sensor. A step of immobilizing a self-assembled monolayer into which a polymerization initiation point is introduced in advance on a substrate;
A step of extending a polymer brush having a chargeable monomer as a modifying group based on the polymerization initiation point;
A method for producing a sensor element, comprising:

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