JP2009097888A - Catalytic activity measuring method - Google Patents
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 67
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 9
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- ZGYRTJADPPDDMY-UHFFFAOYSA-N titanium;tetrahydrate Chemical compound O.O.O.O.[Ti] ZGYRTJADPPDDMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims 2
- 239000012488 sample solution Substances 0.000 claims 2
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 12
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 9
- 230000001877 deodorizing effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 5
- 239000012860 organic pigment Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 2
- 239000000975 dye Substances 0.000 description 93
- 239000003054 catalyst Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 22
- 238000004042 decolorization Methods 0.000 description 17
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000000691 measurement method Methods 0.000 description 7
- JFTBTTPUYRGXDG-UHFFFAOYSA-N methyl violet Chemical compound Cl.C1=CC(=NC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JFTBTTPUYRGXDG-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000002781 deodorant agent Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 229920002307 Dextran Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- -1 hydroxide ions Chemical class 0.000 description 3
- DXTCFKRAUYBHRC-UHFFFAOYSA-L iron(2+);dithiocyanate Chemical compound [Fe+2].[S-]C#N.[S-]C#N DXTCFKRAUYBHRC-UHFFFAOYSA-L 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
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Abstract
Description
本発明は消臭、抗菌効果を有する製剤の触媒活性を測定する方法に関する。 The present invention relates to a method for measuring the catalytic activity of a preparation having a deodorant and antibacterial effect.
消臭、抗菌効果を発揮する製剤が多く市販されている。それらの効果はラジカルの発生を利用している。特に、ヒドロキシルラジカル（以下、・ＯＨという）は酸素の２倍以上の酸化力を有しており、臭いの成分の分解や細菌類の細胞の分解を誘導することで、強い消臭、抗菌効果を発揮できると考えられる。 Many preparations that exhibit deodorant and antibacterial effects are commercially available. Their effect utilizes the generation of radicals. In particular, hydroxyl radical (hereinafter referred to as “OH”) has an oxidizing power more than twice that of oxygen, and it induces strong deodorant and antibacterial effects by inducing the decomposition of odor components and bacterial cells. It is thought that can be demonstrated.
たとえば、アミノ基を含む有機化合物が臭い成分である場合の消臭機構について説明する。すなわち、ヒドロキシルラジカルが有機化合物に作用すると、有機化合物は最終的に水、炭酸ガス、アンモニアなどに分解する。この有機化合物から発生するアンモニアは微量であり、かつ空気の比重より軽く、すぐに空気中に拡散するため、悪臭の原因とはならない。 For example, a deodorizing mechanism in the case where an organic compound containing an amino group is an odor component will be described. That is, when a hydroxyl radical acts on an organic compound, the organic compound is finally decomposed into water, carbon dioxide gas, ammonia and the like. Ammonia generated from this organic compound is a trace amount, lighter than the specific gravity of air, and quickly diffuses into the air, so it does not cause bad odor.
このようなヒドロキシルラジカルによる消臭効果を有する製剤（以下、空気触媒と称する）については、特許文献１に記載されている。特許文献１に記載されている空気触媒によるヒドロキシルラジカルの発生機構は以下の通りである。すなわち、空気触媒中には質量数４０のカリウム（以下、40Ｋという）が微量に含まれており、不安定な40Ｋが安定な元素に変換する際に放出する電子線、電磁波、および電子線が金属原子に衝突して放出される２次電磁波が、空気中の水分と反応してヒドロキシルラジカルを発生させる。このようにして発生した酸化力の強いヒドロキシルラジカルが消臭、抗菌作用を発揮するのである。このような消臭、抗菌作用有する製剤には、例えば、空気触媒セルフィール（Ｓｅｌｆｅｅｌ、ニチリンケミカル株式会社製）などがある。 A preparation having such a deodorizing effect due to hydroxyl radicals (hereinafter referred to as an air catalyst) is described in Patent Document 1. The generation mechanism of hydroxyl radicals by the air catalyst described in Patent Document 1 is as follows. That is, the air catalyst contains a small amount of potassium having a mass number of 40 (hereinafter referred to as 40 K), and the electron beam, electromagnetic waves, and electrons emitted when unstable 40 K is converted into a stable element. Secondary electromagnetic waves emitted when the line collides with metal atoms react with moisture in the air to generate hydroxyl radicals. The hydroxyl radicals with strong oxidizing power generated in this way exhibit deodorizing and antibacterial effects. Examples of such deodorant and antibacterial preparations include air catalyst self-feel (Selfeel, manufactured by Nichirin Chemical Co., Ltd.).
これらの消臭、抗菌効果を発揮する製剤の活性をモニターするには、ヒドロキシルラジカルの発生の有無を測定することが有効である。 In order to monitor the activity of these preparations exhibiting deodorant and antibacterial effects, it is effective to measure the presence or absence of the generation of hydroxyl radicals.
ヒドロキシルラジカルの一般的な測定方法は、スピントラップ法や電子スピン共鳴分光法などの直接測定法である。しかしながら、これらの直接測定法は、非常に高価な装置を必要とするうえに、短寿命のラジカルをトラップして測定するものであるため、測定には高度な技量が必要で一般的ではない。そこで、ヒドロキシルラジカルの簡便な測定方法が求められていた。 A general method for measuring hydroxyl radical is a direct measurement method such as a spin trap method or electron spin resonance spectroscopy. However, these direct measurement methods require a very expensive apparatus and trap and measure short-lived radicals. Therefore, the measurement requires a high level of skill and is not general. Therefore, a simple method for measuring hydroxyl radicals has been demanded.
また、ヒドロキシルラジカルによって分解される色素が知られているので、そのような色素の分解を利用して、色素の色調変化を検知することが考えられる。しかしながら、空気触媒セルフィールなどの消臭、抗菌効果を有する製剤は一度に多量のヒドロキシルラジカルを発生しない。そのため、色調変化を検出するには数日以上かかり実用的でないという欠点があった。 Moreover, since the pigment | dye decomposed | disassembled by a hydroxyl radical is known, it is possible to detect the color tone change of a pigment | dye using such decomposition | disassembly of a pigment | dye. However, preparations having a deodorizing and antibacterial effect such as air-catalyzed serfiel do not generate a large amount of hydroxyl radicals at once. For this reason, it takes several days or more to detect a change in color tone, which is not practical.
本発明は、このような消臭、抗菌効果を有する製剤の触媒活性を簡便かつ迅速に測定する測定方法を提供することを目的としている。 The object of the present invention is to provide a measuring method for simply and rapidly measuring the catalytic activity of a preparation having such deodorant and antibacterial effects.
すなわち本発明は、空気中の水を分解させてヒドロキシルラジカルを生成させる物質の触媒活性測定方法であって、過酸化水素と有機色素と物質とを含む検体水溶液を作製する工程と、過酸化水素と有機色素とを含む基準水溶液を作製する工程と、検体水溶液と基準水溶液の色調変化の差異を検出する工程とを含む触媒活性測定方法である。 That is, the present invention relates to a method for measuring the catalytic activity of a substance that decomposes water in the air to generate hydroxyl radicals, the step of preparing a sample aqueous solution containing hydrogen peroxide, an organic dye, and a substance; And a method for measuring catalytic activity comprising a step of preparing a reference aqueous solution containing an organic dye and a step of detecting a difference in color tone between the sample aqueous solution and the reference aqueous solution.
ヒドロキシルラジカルを生成させる物質（検体物質）が遷移金属を含有することが好ましい。 The substance (analyte substance) that generates hydroxyl radicals preferably contains a transition metal.
検体物質が、鉄、アルミニウム、およびカリウムを含む金属組成物またはさらに水を含む水性組成物であることが好ましい。 The specimen substance is preferably a metal composition containing iron, aluminum, and potassium or an aqueous composition further containing water.
金属組成物の水性組成物は、アルミニウムおよびカリウムを、鉄１００ｐｐｍに対してそれぞれ１００〜３００ｐｐｍおよび１〜２０ｐｐｍ含有している水性組成物であることが好ましい。 The aqueous composition of the metal composition is preferably an aqueous composition containing 100 to 300 ppm and 1 to 20 ppm of aluminum and potassium with respect to 100 ppm of iron, respectively.
金属組成物の水性組成物はさらに水酸化チタン（IV）塩酸塩を含有し、チタン含有量が、鉄１００ｐｐｍに対して０．２〜５０ｐｐｍであることが好ましい。 The aqueous composition of the metal composition further contains titanium (IV) hydroxide, and the titanium content is preferably 0.2 to 50 ppm with respect to 100 ppm of iron.
有機色素が、メチルバイオレット、メチレンブルー、イエロー４、グリーン、およびレッド３の群から選ばれる少なくとも一つの色素であることが好ましい。 The organic dye is preferably at least one dye selected from the group consisting of methyl violet, methylene blue, yellow 4, green, and red 3.
検体水溶液と基準水溶液のｐＨがｐＨ５〜７であることが好ましい。 The pH of the sample aqueous solution and the reference aqueous solution is preferably pH 5-7.
本発明の測定方法により、高価な装置を用いることなく、色素の色調変化をモニターすることを介して短時間で空気触媒の触媒活性を測定することができるため、空気触媒の品質管理指標を簡便に提供することができる。 With the measurement method of the present invention, the catalytic activity of the air catalyst can be measured in a short time through monitoring the change in the color tone of the dye without using an expensive apparatus. Can be provided.
鉄などの遷移元素が触媒量存在する系内に過酸化水素（Ｈ2Ｏ2）が入ると、遷移元素が触媒として作用することで・ＯＨと水酸イオン（ＯＨ-）が生成することが知られている。セルフィールなどの空気触媒には、遷移元素を含むものが多い。本発明は、本来それ自体、・ＯＨを発生することが知られており、かつ遷移元素を含有する空気触媒を、過酸化水素中に投入し、かつ、その系に色素を混在させたことを特徴とする触媒活性の検出方法である。過酸化水素と空気触媒との相乗効果により、ヒドロキシルラジカルが高濃度で発生し、混在する色素と化学反応することで色素の色調変化が促進される。色素の色調変化は色素を含む系全体の色変化として容易に検出することができる。 When hydrogen peroxide (H 2 O 2 ) enters a system in which a catalytic amount of a transition element such as iron is present, OH and hydroxide ions (OH − ) may be generated due to the transition element acting as a catalyst. Are known. Many air catalysts such as SELFEEL contain transition elements. The present invention itself is known to generate OH itself, and an air catalyst containing a transition element was introduced into hydrogen peroxide, and a dye was mixed in the system. This is a characteristic method for detecting catalytic activity. Due to the synergistic effect of hydrogen peroxide and the air catalyst, hydroxyl radicals are generated at a high concentration, and the color change of the dye is promoted by a chemical reaction with the mixed dye. The color tone change of the dye can be easily detected as a color change of the entire system including the dye.
本発明で検出対象となる物質は、空気中の水を分解させてヒドロキシルラジカルを生成させる物質である。そのような物質としては遷移金属を含むものが好ましい。例えば、鉄、アルミニウム、およびカリウムを含む金属組成物またはさらに水を含む水性組成物が挙げられる。前記水性組成物はさらに水酸化チタン（IV）塩酸塩を含有してもよい。好ましくは、前記水性組成物は、アルミニウムおよびカリウムを、鉄１００ｐｐｍに対してそれぞれ１００〜３００ｐｐｍおよび１〜２０ｐｐｍ含有している水性組成物である。このような検出対象物質として具体的には、先述のセルフィールが挙げられる。ただし、ヒドロキシルラジカルを発生し、過酸化水素存在下で色素の分解を加速させる物質であればよく、特に、遷移元素を含有するという条件を充たすのであれば、セルフィールに限定されるものではない。 The substance to be detected in the present invention is a substance that decomposes water in the air to generate hydroxyl radicals. As such a substance, a substance containing a transition metal is preferable. For example, a metal composition containing iron, aluminum, and potassium or an aqueous composition further containing water can be used. The aqueous composition may further contain titanium (IV) hydrochloride. Preferably, the aqueous composition is an aqueous composition containing 100 to 300 ppm and 1 to 20 ppm of aluminum and potassium with respect to 100 ppm of iron, respectively. Specific examples of such a substance to be detected include the above-mentioned selfie. However, any substance that generates hydroxyl radicals and accelerates the decomposition of the dye in the presence of hydrogen peroxide may be used. In particular, the substance is not limited to SELFIRE as long as the condition that it contains a transition element is satisfied. .
過酸化水素としては市販品（３５％）を適当に希釈して用いることができる。 As hydrogen peroxide, a commercially available product (35%) can be appropriately diluted and used.
本発明では色素の選定が重要である。用いることができる色素としては、過酸化水素のみによる脱色が大きくなく、かつ、空気触媒が混在する過酸化水素中では脱色速度が大きいことが好ましい。 In the present invention, the selection of the dye is important. As the dye that can be used, it is preferable that decolorization by hydrogen peroxide alone is not large and that the decolorization rate is high in hydrogen peroxide mixed with an air catalyst.
また、用いることができる色素としては、弱酸性〜中性の水溶液を作製することが出来る有機色素が好ましい。なかでも、メチルバイオレット、メチレンブルー、イエロー４、グリーン、およびレッド３が好ましい。これらの色素をそれぞれ単独で用いてもよいし、二種以上の色素を混合して用いてもよい。 Moreover, as a pigment | dye which can be used, the organic pigment | dye which can produce weakly acidic-neutral aqueous solution is preferable. Of these, methyl violet, methylene blue, yellow 4, green, and red 3 are preferable. These pigments may be used alone or in combination of two or more pigments.
また、系中の色素濃度が高すぎると、色素分解による色調変化に時間がかかりすぎるし、一方で、系中の色素濃度が低すぎると、試験開始前と試験後の色調変化が小さいため、色調変化の検出が困難となる。用いる色素によって異なるものの、色素毎に適切な色素濃度の範囲が存在する。 Also, if the dye concentration in the system is too high, it takes too much time to change the color tone due to dye decomposition, while if the dye concentration in the system is too low, the change in color tone before and after the test is small, It becomes difficult to detect a change in color tone. Although depending on the dye used, there is a range of suitable dye concentrations for each dye.
以下、実施の形態により、本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to embodiments.
１．色素水溶液の調整
色素１．メチルバイオレット水溶液
メチルバイオレットをイオン交換水に溶解し、まず色素濃度１０ｍｇ／ｍｌ（色素１ａ）の水溶液を作製し、色素１ａを希釈することで色素濃度０．１ｍｇ／ｍｌ（色素１ｂ）、色素濃度０．０２ｍｇ／ｍｌ（色素１ｃ）の水溶液を調整した。
1. Preparation dye of dye aqueous solution Methyl violet aqueous solution Dissolve methyl violet in ion-exchanged water, first prepare an aqueous solution with a dye concentration of 10 mg / ml (dye 1a), and dilute dye 1a to obtain a dye concentration of 0.1 mg / ml (dye 1b). An aqueous solution of 0.02 mg / ml (Dye 1c) was prepared.
色素２．メチレンブルー水溶液
メチレンブルーをイオン交換水に溶解し、色素濃度１０ｍｇ／ｍｌ（色素２ａ）、色素濃度０．１ｍｇ／ｍｌ（色素２ｂ）、色素濃度０．０２ｍｇ／ｍｌ（色素２ｃ）の水溶液を調整した。
Dye 2. Methylene blue aqueous solution Methylene blue was dissolved in ion-exchanged water to prepare an aqueous solution having a dye concentration of 10 mg / ml (dye 2a), a dye concentration of 0.1 mg / ml (dye 2b), and a dye concentration of 0.02 mg / ml (dye 2c).
色素３．アリザリン水溶液
あらかじめ炭酸ナトリウムをイオン交換水に溶解し、濃度１０ｍｇ／ｍｌの炭酸ナトリウム水溶液（弱アルカリ性）を作製した。次に、アリザリンを上記炭酸ナトリウム水溶液に溶解し、色素濃度１０ｍｇ／ｍｌ（色素３ａ）、色素濃度０．１ｍｇ／ｍｌ（色素３ｂ）、色素濃度０．０２ｍｇ／ｍｌ（色素３ｃ）の水溶液を調整した。
Dye 3. Alizarin aqueous solution Sodium carbonate was previously dissolved in ion-exchanged water to prepare a sodium carbonate aqueous solution (weakly alkaline) with a concentration of 10 mg / ml. Next, alizarin is dissolved in the aqueous sodium carbonate solution to prepare an aqueous solution having a dye concentration of 10 mg / ml (dye 3a), a dye concentration of 0.1 mg / ml (dye 3b), and a dye concentration of 0.02 mg / ml (dye 3c). did.
色素４．イエロー４水溶液
イエロー４（Ｙｅｌｌｏｗ−４）とデキストランが重量比で１／９の混合物をイオン交換水に溶解し、色素濃度１ｍｇ／ｍｌ（色素４ａ）、色素濃度０．０２ｍｇ／ｍｌ（色素４ｂ）の水溶液を調整した。
Dye 4. Yellow 4 aqueous solution A mixture of yellow 4 (Yellow-4) and dextran in a weight ratio of 1/9 is dissolved in ion-exchanged water to obtain a dye concentration of 1 mg / ml (dye 4a) and a dye concentration of 0.02 mg / ml (dye 4b). An aqueous solution was prepared.
色素５．グリーン水溶液
グリーン（Ｇｒｅｅｎ）とデキストランが重量比で５／９５の混合物をイオン交換水に溶解し、色素濃度１ｍｇ／ｍｌ（色素５ａ）、色素濃度０．０２ｍｇ／ｍｌ（色素５ｂ）の水溶液を調整した。
Dye 5. Green aqueous solution A mixture of green and dextran in a weight ratio of 5/95 is dissolved in ion-exchanged water to prepare an aqueous solution having a dye concentration of 1 mg / ml (dye 5a) and a dye concentration of 0.02 mg / ml (dye 5b). did.
色素６．レッド３水溶液
レッド３（ＲＥＤ−３）とデキストランが重量比で５／９５の混合物をイオン交換水に溶解し、色素濃度０．１ｍｇ／ｍｌ（色素６ａ）、色素濃度０．０５ｍｇ／ｍｌ（色素６ｂ）、色素濃度０．０２ｍｇ／ｍｌ（色素６ｃ）の水溶液を調整した。
Dye 6. Red 3 aqueous solution A mixture of Red 3 (RED-3) and dextran in a weight ratio of 5/95 is dissolved in ion-exchanged water, and the dye concentration is 0.1 mg / ml (dye 6a), the dye concentration is 0.05 mg / ml (dye 6b), an aqueous solution having a dye concentration of 0.02 mg / ml (dye 6c) was prepared.
色素７．チオシアン酸鉄イオン水溶液
硫酸第二鉄とチオシアン酸カリウムとをイオン交換水に溶解し、チオシアン酸濃度１０ｍｇ／ｍｌ（色素７ａ）、色素濃度０．２ｍｇ／ｍｌ（色素７ｂ）の水溶液を調整した。
Dye 7 Iron thiocyanate ion aqueous solution Ferric sulfate and potassium thiocyanate were dissolved in ion-exchanged water to prepare an aqueous solution having a thiocyanate concentration of 10 mg / ml (dye 7a) and a dye concentration of 0.2 mg / ml (dye 7b).
２．触媒活性の測定実験
２−１．測定試料の調整
調整した上記の各色素水溶液、空気触媒溶液、および過酸化水素（１７．５重量％水溶液）を準備した。ここで、空気触媒が固体の場合にはイオン交換水の０．０１ｇ／ｍｌ水溶液とした。
2. 2. Experiment for measuring catalytic activity 2-1. Preparation of measurement sample The prepared dye aqueous solutions, air catalyst solution, and hydrogen peroxide (17.5 wt% aqueous solution) were prepared. Here, when the air catalyst was solid, it was made into 0.01g / ml aqueous solution of ion-exchange water.
上記３種類の溶液を表１に示すように組み合わせて、４種類の試験管試料を作製した。 The above three types of solutions were combined as shown in Table 1 to prepare four types of test tube samples.
ここで試験管試料１〜４を作製した目的について説明する。
（試験管試料１）色素単独での脱色速度の確認用である。色素単独で急速に脱色するようだと本発明の目的である空気触媒活性のモニター用としては不適用と判断する。
（試験管試料２）空気触媒のみによる脱色速度の測定用である。
（試験管試料３）色素の過酸化水素による脱色速度の測定用試料であって、基準水溶液と称する。
（試験管試料４）本発明の測定方法に必要な要素がすべて揃った試験管であって、検体水溶液と称する。検体水溶液と基準水溶液とは、色調を整合させるため同一の過酸化水素濃度および同一の色素濃度を有する。
Here, the purpose of producing the test tube samples 1 to 4 will be described.
(Test tube sample 1) This is for confirming the decolorization rate of the dye alone. If the dye alone seems to rapidly decolorize, it is judged that it is not applicable for monitoring the air catalyst activity which is the object of the present invention.
(Test tube sample 2) This is for measuring the decolorization rate using only the air catalyst.
(Test tube sample 3) A sample for measuring the decolorization rate of the dye by hydrogen peroxide, which is referred to as a reference aqueous solution.
(Test tube sample 4) A test tube in which all the elements necessary for the measurement method of the present invention are prepared, and is referred to as a sample aqueous solution. The sample aqueous solution and the reference aqueous solution have the same hydrogen peroxide concentration and the same dye concentration in order to match the color tone.
検体水溶液（試験管試料４）が基準水溶液（試験管試料３）より速く脱色するのであれば、空気触媒による色素の脱色速度の増分を検知できる。 If the sample aqueous solution (test tube sample 4) decolors faster than the reference aqueous solution (test tube sample 3), the increase in the decoloration rate of the dye by the air catalyst can be detected.
なお、試験管試料３，４のｐＨについては、特に規定しないが、弱酸性〜中性の条件が好ましい。特にｐＨ５〜７の範囲が好ましい。試験管試料がアルカリ性であると、過酸化水素の分解が過度に促進されるので好ましくない。 In addition, although it does not prescribe | regulate especially about the pH of the test tube samples 3 and 4, the conditions of weak acidity-neutrality are preferable. The range of pH 5-7 is particularly preferable. It is not preferable that the test tube sample is alkaline because decomposition of hydrogen peroxide is excessively accelerated.
また、試験管の温度条件についても特に規定しないが、室温付近、好ましくは１５〜２３℃前後が好ましい。なお、０℃近傍でも測定は可能である。ただし、高温にすると、過酸化水素の分解が過度に促進されるので好ましくない。 Moreover, although it does not prescribe | regulate especially about the temperature conditions of a test tube, Room temperature vicinity, Preferably around 15-23 degreeC is preferable. Note that measurement is possible even in the vicinity of 0 ° C. However, a high temperature is not preferable because decomposition of hydrogen peroxide is excessively accelerated.
さらに、過酸化水素濃度の適当な範囲を検討した。メチルバイオレットを色素として用い、本発明の測定方法を空気触媒セルフィールに適用した場合を例に、過酸化水素濃度が３５重量％である水溶液、１７．５重量％の水溶液、８重量％の水溶液、および４重量％の水溶液のそれぞれについて実験した。その結果、過酸化水素が８重量％以上の濃度にすると脱色が好適に進むので、本発明の目的に適していることがわかった。以下の実施例では、取り扱い性を考慮し、過酸化水素１７．５重量％を採用した。 Furthermore, an appropriate range of the hydrogen peroxide concentration was examined. Using methyl violet as a dye and applying the measurement method of the present invention to air catalyst self-feel, an aqueous solution having a hydrogen peroxide concentration of 35% by weight, an aqueous solution of 17.5% by weight, an aqueous solution of 8% by weight , And 4% by weight aqueous solutions, respectively. As a result, it was found that when the concentration of hydrogen peroxide is 8% by weight or more, decolorization proceeds favorably, which is suitable for the purpose of the present invention. In the following examples, 17.5% by weight of hydrogen peroxide was employed in consideration of handleability.
２−２．色素対比実験
空気触媒としてセルフィール、過酸化水素、および予め調整しておいた各色素水溶液とを用いて、色素ごとに、表１に示す４種類の試験管試料を作製した。作製した試験管試料について、所定時間経過後の色調変化をモニターした。観察した時間は、試験管試料作製直後（０分）、１５分、３０分、６０分、１日、３日、５日、１０日、１５日、３０日とした。ただし、迅速な測定の実現を目的とする本発明の趣旨に照らして、実験データとしては１日後のデータまでを記載した。なお、下記の表では、脱色が顕著になった時間に「脱色」と記載した。つまり、「脱色」と記載した時間以前にも色調変化が生じているが、目視で確実に脱色が確認できた状態を「脱色」と記載した。また、脱色までは到っていないものの目視での色調変化が確認できる状態を「変化あり」とした。
2-2. Dye contrast experiment Four types of test tube samples shown in Table 1 were prepared for each dye by using SELFEEL, hydrogen peroxide, and each dye aqueous solution prepared in advance as an air catalyst. About the produced test tube sample, the color tone change after progress for a predetermined time was monitored. The observed time was immediately after preparation of the test tube sample (0 minute), 15 minutes, 30 minutes, 60 minutes, 1 day, 3 days, 5 days, 10 days, 15 days, and 30 days. However, in light of the gist of the present invention for the purpose of realizing rapid measurement, the data up to one day later was described as experimental data. In the table below, “decolorization” is described as the time when decolorization becomes significant. That is, although the color tone change occurred before the time described as “decolorization”, the state where decoloration was confirmed by visual observation was described as “decolorization”. In addition, a state in which a change in color tone with the naked eye can be confirmed although it has not reached decoloration was defined as “changed”.
各実験例の水溶液のｐＨは、アリザリンを用いた比較例１が弱アルカリ性である以外は、ｐＨ５〜７に調整した。また、各試料の放置温度は１５〜２３℃とした。 The pH of the aqueous solution of each experimental example was adjusted to pH 5 to 7 except that Comparative Example 1 using alizarin was weakly alkaline. Moreover, the leaving temperature of each sample was 15-23 degreeC.
実施例１．メチルバイオレット水溶液（濃度０．０２ｍｇ／ｍｌ）
実施例２．メチレンブルー水溶液（濃度０．０２ｍｇ／ｍｌ）
実施例３．イエロー４水溶液（濃度０．０２ｍｇ／ｍｌ）
実施例４．グリーン水溶液（濃度０．０２ｍｇ／ｍｌ）
実施例５．レッド３水溶液（濃度０．１ｍｇ／ｍｌ）
比較例１．アリザリン水溶液（濃度０．１ｍｇ／ｍｌ）
比較例２．チオシアン酸鉄イオン水溶液（濃度０．２ｍｇ／ｍｌ）
３．各色素の触媒活性の評価
実験例１〜５（表２〜６）の結果から、メチルバイオレット、メチレンブルー、イエロー４、グリーン、およびレッド３は、いずれも本発明の目的である触媒活性のモニター用途に適した色素であることがわかった。すなわち、空気触媒を添加することにより、過酸化水素の存在下における色素の脱色（検体水溶液）が、過酸化水素単独の場合（基準水溶液）の脱色よりも早いことを示した。また、上記の色素を用いた場合には、６０分以内に検体水溶液（試験管試料４）の脱色が確認でき、簡便かつスピーディーな触媒活性測定方法が実現できることがわかった。
3. Evaluation of Catalytic Activity of Each Dye From the results of Experimental Examples 1 to 5 (Tables 2 to 6), methyl violet, methylene blue, yellow 4, green, and red 3 are all used for monitoring the catalytic activity that is the object of the present invention. It was found that the dye was suitable for That is, it was shown that by adding an air catalyst, the decolorization of the dye in the presence of hydrogen peroxide (analyte aqueous solution) was faster than the decolorization in the case of hydrogen peroxide alone (reference aqueous solution). In addition, when the above dye was used, decolorization of the sample aqueous solution (test tube sample 4) could be confirmed within 60 minutes, and it was found that a simple and speedy method for measuring catalytic activity could be realized.
一方、比較例１（表７）のアリザリン水溶液は弱アルカリ性であり、過酸化水素の混合直後に脱色するため、本発明に用いる色素としては適当ではないものと考えられる。弱アルカリ性では過酸化水素の分解が促進されるためである。 On the other hand, the alizarin aqueous solution of Comparative Example 1 (Table 7) is weakly alkaline and decolorizes immediately after mixing with hydrogen peroxide, so it is considered that it is not suitable as a dye used in the present invention. This is because the weak alkalinity promotes the decomposition of hydrogen peroxide.
また、比較例２（表８）に示すように、無機色素であるチオシアン酸鉄イオン水溶液は、過酸化水素単独の場合（試験管試料３）に対して、過酸化水素と空気触媒とが混在する場合に脱色の加速性が認められない。したがって、チオシアン酸鉄イオンに代表される無機色素は本発明に用いる色素としては適当ではないものと考えられる。 Further, as shown in Comparative Example 2 (Table 8), the aqueous iron thiocyanate ion solution, which is an inorganic dye, contains a mixture of hydrogen peroxide and an air catalyst as compared with hydrogen peroxide alone (test tube sample 3). Acceleration of decolorization is not observed when Therefore, it is considered that inorganic dyes represented by iron thiocyanate ions are not suitable as the dyes used in the present invention.
以上の結果から、本発明の触媒活性測定方法は、有機色素を用い、かつ酸性から中性の水溶液中で行うことが好ましいことがわかる。 From the above results, it can be seen that the method for measuring catalytic activity of the present invention is preferably performed using an organic dye and in an acidic to neutral aqueous solution.
４．レッド３の濃度確認実験
本発明の測定方法に用いる色素の一例としてレッド３を選定し、レッド３の濃度を変えて、表１に示す４種類の試験管試料を作製した。作製した試験管試料について、所定時間経過後の色調変化をモニターした結果を表９に示す。観察した時間は、試験管試料作製直後（０分）、５分、１０分、１５分、２０分、３０分、６０分とした。なお、表９では、脱色が顕著になった時間に「脱色」と記載した。「脱色」と記載した時間以前にも色調変化が生じているが、目視で確実に脱色が確認できた期間の欄に「脱色」と記載した。測定した水溶液のｐＨをｐＨ５〜７に調整し、放置時の温度は１５〜２３℃とした。
4). Red 3 Concentration Confirmation Experiment Red 3 was selected as an example of the dye used in the measurement method of the present invention, and the concentration of red 3 was changed to prepare four types of test tube samples shown in Table 1. Table 9 shows the results of monitoring the color tone change after the lapse of a predetermined time for the prepared test tube sample. The observed time was immediately after preparation of the test tube sample (0 minutes), 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, and 60 minutes. In Table 9, “decolorization” is described at the time when decolorization becomes significant. Although a change in color tone occurred before the time described as “decolorization”, “decoloration” was described in the column of the period during which decoloration could be confirmed by visual observation. The pH of the measured aqueous solution was adjusted to pH 5-7, and the temperature at the time of standing was 15-23 degreeC.
実施例６．レッド３水溶液
表９には、空気触媒、色素および過酸化水素を含む検体水溶液（試験管試料４）についての観察結果を示した。
Example 6 Table 3 shows the observation results for the sample aqueous solution (test tube sample 4) containing an air catalyst, a dye, and hydrogen peroxide.
４−１．レッド３の濃度の影響
レッド３の濃度が、０．０２ｍｇ／ｍｌの場合には、色素による水溶液の着色自体が薄いため、経時的な色調変化を明瞭に把握することがやや困難になる傾向があった。一方、レッド３の濃度が０．１ｍｇ／ｍｌの場合、水溶液の着色が顕著という点は好ましいが、色調変化がやや遅くなるという傾向が見られた。したがって、レッド３を用いる場合には、水溶液中の色素濃度は０．０２〜０．１ｍｇ／ｍｌの範囲が好ましく、０．０５ｍｇ／ｍｌ前後の色素濃度が特に好ましい。
4-1. Effect of the concentration of red 3 When the concentration of red 3 is 0.02 mg / ml, the coloring of the aqueous solution with the dye itself is thin, so it is somewhat difficult to clearly grasp the color tone change over time. there were. On the other hand, when the concentration of Red 3 is 0.1 mg / ml, it is preferable that the coloration of the aqueous solution is remarkable, but there is a tendency that the color tone change is slightly delayed. Therefore, when Red 3 is used, the dye concentration in the aqueous solution is preferably in the range of 0.02 to 0.1 mg / ml, and a dye concentration of around 0.05 mg / ml is particularly preferred.
なお、本発明では、検体水溶液と基準水溶液との色調の差異を目視で判断することで、より簡便な測定方法が提供できるが、分光光度計などの光学計測器を用いて、色調変化をより高精度に測定してもよい。 In the present invention, it is possible to provide a simpler measurement method by visually determining the difference in color tone between the sample aqueous solution and the reference aqueous solution, but the change in color tone can be further reduced by using an optical measuring instrument such as a spectrophotometer. You may measure with high precision.
以上説明したように、本発明は、空気触媒の触媒活性の簡便な測定方法を提供するものである。すなわち、本来それ自体、ヒドロキシルラジカルを発生することが知られており、かつ遷移元素を含有する空気触媒を過酸化水素中に投入し、かつ、その系に色素を混在させ、色素分解に伴う色調変化を観察することにより、空気触媒の触媒活性の検出を簡便に行うことができる方法を提供するものである。 As described above, the present invention provides a simple method for measuring the catalytic activity of an air catalyst. That is, it is originally known to generate hydroxyl radicals, and an air catalyst containing a transition element is introduced into hydrogen peroxide, and a dye is mixed in the system, so that the color tone accompanying the dye decomposition is increased. By observing the change, a method for easily detecting the catalytic activity of the air catalyst is provided.
Claims (8)
過酸化水素と有機色素と前記物質とを含む検体水溶液を作製する工程と、
前記検体水溶液と同じ濃度の過酸化水素および前記有機色素を含む基準水溶液を作製する工程と、
前記検体水溶液と前記基準水溶液の色調変化の差異を検出する工程とを含む触媒活性測定方法。 A method for measuring the catalytic activity of a substance that decomposes water in the air to generate hydroxyl radicals,
Producing an aqueous sample solution containing hydrogen peroxide, an organic dye, and the substance;
Producing a reference aqueous solution containing hydrogen peroxide having the same concentration as the sample aqueous solution and the organic dye;
A method for measuring catalytic activity, comprising a step of detecting a difference in color tone between the aqueous sample solution and the reference aqueous solution.
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