JP2021115507A - Water containing oxygen-containing nanoparticles - Google Patents
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 102
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 68
- 239000001301 oxygen Substances 0.000 title claims abstract description 68
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 6
- -1 iron ions Chemical class 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 229910052742 iron Inorganic materials 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 17
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 10
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 239000002101 nanobubble Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 230000005514 two-phase flow Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
Images
Abstract
Description
本発明は、酸素を含有するナノ粒子を含む水に関する。より詳細には、ナノ粒子が、気液界面を有する気泡（ナノバブル）とは異なる、水に関する。 The present invention relates to water containing nanoparticles containing oxygen. More specifically, the nanoparticles relate to water, which is different from bubbles having a gas-liquid interface (nano bubbles).
酸素を含有するナノバブルを含む水（酸素ナノバブル水）が、生物に対して酸素による生理活性効果を高める作用を有することは、例えば特許文献１から当業者によく知られており、本発明者の高橋によって見出された知見である。また、高橋は、特許文献１において、酸素ナノバブル水を製造する方法として、電解質イオンを混入した電気伝導度が３ｍＳ／ｃｍ以上の水溶液に、酸素を供給し、粒径が１０〜５０μｍであるマイクロバブルを発生させ、これに物理的刺激を加えて縮小させることによる方法を提案している。マイクロバブルは、微小な気泡の特性として、水中で縮小し、その際に表面の電荷を濃縮する。気泡の表面は、集まった水に由来する水酸化物イオン（ＯＨ−）により、マイナスに帯電している。気泡の縮小は、水中における効率的な気体の溶解と緩やかな上昇速度に起因している。マイクロバブルは、球形の気泡であり、二層流旋回方式や加圧溶解方式と呼ばれる方法によって発生させることができる。発生された気泡は水に取り囲まれた存在であり、その表面（気液界面）には表面張力が作用する。表面張力はその面積を小さくするように作用する力である。球形をしたマイクロバブルの場合、表面を小さくする力は結果的に内部の気体を圧縮する力となる。その結果、気泡の内部は加圧される。気体は圧力が高いほど、周りの水に効果的に溶解する。内部の気体が溶解することによりもともと小さなマイクロバブルはさらに縮小していき、ついには水の中で消滅する。しかしながら、マイクロバブルを発生させる水が、電解質イオンを混入することで所定の電気伝導度（例えば３００μｍ以上）を有する場合、気泡の縮小によって表面の電荷が濃縮されると、その対イオンとなる電解質イオンもあわせて濃縮される。その結果、濃縮された電解質イオンが、気泡を取り囲む殻のように働き、気泡の内部の気体が水に溶解することを抑制して気泡のさらなる縮小を阻害することで、気泡が長寿命化し、５０〜５００ｎｍ程度の大きさのナノバブルとして存在するようになる。 It is well known to those skilled in the art from Patent Document 1, for example, that water containing nanobubbles containing oxygen (oxygen nanobubble water) has an effect of enhancing the physiological activity effect of oxygen on living organisms, and the present inventor's This is the finding found by Takahashi. Further, in Patent Document 1, as a method for producing oxygen nanobubble water, Takahashi supplies oxygen to an aqueous solution having an electric conductivity of 3 mS / cm or more mixed with electrolyte ions, and has a microparticle size of 10 to 50 μm. We are proposing a method by generating bubbles and then applying physical stimulation to them to shrink them. Microbubbles, as a characteristic of microbubbles, shrink in water and concentrate the charge on the surface at that time. The surface of the bubbles is negatively charged by hydroxide ions (OH −) derived from the collected water. The shrinkage of bubbles is due to the efficient dissolution of gas in water and the slow rate of ascent. Microbubbles are spherical bubbles and can be generated by a method called a two-phase flow swirling method or a pressure melting method. The generated bubbles are surrounded by water, and surface tension acts on the surface (gas-liquid interface). Surface tension is a force that acts to reduce its area. In the case of spherical microbubbles, the force that makes the surface smaller results in the force that compresses the gas inside. As a result, the inside of the bubble is pressurized. The higher the pressure, the more effectively the gas dissolves in the surrounding water. As the gas inside dissolves, the originally small microbubbles shrink further and finally disappear in the water. However, when the water that generates microbubbles has a predetermined electrical conductivity (for example, 300 μm or more) by mixing electrolyte ions, when the charge on the surface is concentrated by the shrinkage of the bubbles, the electrolyte becomes the counter ion. Ions are also concentrated. As a result, the concentrated electrolyte ions act like a shell surrounding the bubbles, suppressing the dissolution of the gas inside the bubbles in water and hindering further shrinkage of the bubbles, thereby extending the life of the bubbles. It comes to exist as nanobubbles having a size of about 50 to 500 nm.
以上の通り、本発明者の高橋のこれまでの精力的な研究によって、酸素ナノバブル水の実態が解明されつつある。しかしながら、酸素ナノバブル水については未だ明らかでないことも多く、さらなる研究が必要な状況にあると言える。 As described above, the actual condition of oxygen nanobubble water is being elucidated by the vigorous research of the inventor Takahashi so far. However, there are still many unclear points about oxygen nanobubble water, and it can be said that further research is needed.
本発明は、酸素ナノバブル水とは異なる、酸素を含有するナノ粒子を含む水を提供することを目的とする。 An object of the present invention is to provide water containing oxygen-containing nanoparticles, which is different from oxygen nanobubble water.
本発明者は、酸素ナノバブル水を製造する新たな方法の研究過程において、酸素を含有するマイクロバブルを発生させる水に微量の２価の鉄イオン（Ｆｅ２＋）を存在させると、気液界面を有する気泡（ナノバブル）とは異なるナノ粒子を含む水が得られることを見出した。 In the process of researching a new method for producing oxygen nanobubble water, the present inventor presents a trace amount of divalent iron ion (Fe 2+ ) in water that generates oxygen-containing microbubbles to create a gas-liquid interface. It has been found that water containing nanoparticles different from the bubbles (nano bubbles) having it can be obtained.
以上の知見に基づいてなされた本発明は、請求項１記載の通り、原子間力顕微鏡による観察において表面の少なくとも一部に高さが２ｎｍ以下の凹凸構造を持つことが認められ、粒径が５０ｎｍ以下であり、酸素を含有する、ナノ粒子を含み、酸を添加すると水酸基ラジカルを発生させる、水である。
また、本発明は、請求項２記載の通り、電気伝導度が３００μＳ／ｃｍ未満である水に、２価の鉄イオンを濃度が１〜１００ｐｐｂとなるように添加した水中に、酸素を含む乃至からなる気体を供給し、粒径が５０μｍ以下であるマイクロバブルを発生させ、発生したマイクロバブルが縮小することによる、請求項１記載の水の製造方法である。
また、請求項３記載の製造方法は、請求項２記載の製造方法において、２価の鉄イオンを、塩化鉄（ＩＩ）、硫酸化鉄（ＩＩ）、硝酸鉄（ＩＩ）から選択される少なくとも１種の形態で添加する。
As described in claim 1, the present invention made based on the above findings is found to have an uneven structure having a height of 2 nm or less on at least a part of the surface when observed with an atomic force microscope, and the particle size is large. Water having a diameter of 50 nm or less, containing oxygen, containing nanoparticles, and generating hydroxyl radicals when an acid is added.
Further, as described in claim 2, the present invention contains oxygen in water in which divalent iron ions are added so as to have a concentration of 1 to 100 ppb in water having an electric conductivity of less than 300 μS / cm. The method for producing water according to claim 1, wherein a gas composed of the above is supplied, microbubbles having a particle size of 50 μm or less are generated, and the generated microbubbles are reduced.
Further, in the production method according to claim 3, at least the divalent iron ion is selected from iron (II) chloride, iron (II) sulfate, and iron (II) nitrate in the production method according to claim 2. It is added in one form.
本発明によれば、酸素ナノバブル水とは異なる、酸素を含有するナノ粒子を含む水を提供することができる。 According to the present invention, it is possible to provide water containing oxygen-containing nanoparticles, which is different from oxygen nanobubble water.
本発明が提供する、酸素ナノバブル水とは異なる、酸素を含有するナノ粒子を含む水は、原子間力顕微鏡による観察において表面の少なくとも一部に高さが２ｎｍ以下の凹凸構造を持つことが認められ、粒径が５０ｎｍ以下であり、酸素を含有する、ナノ粒子を含み、酸を添加すると水酸基ラジカルを発生させる、水である。 It was found that the water containing oxygen-containing nanoparticles, which is different from the oxygen nanobubble water provided by the present invention, has an uneven structure having a height of 2 nm or less on at least a part of the surface when observed with an atomic force microscope. Water having a particle size of 50 nm or less, containing oxygen, containing nanoparticles, and generating hydroxyl radicals when an acid is added.
本発明の酸素を含有するナノ粒子を含む水の最大の特徴は、酸素を含有するナノ粒子が、原子間力顕微鏡による観察において表面の少なくとも一部に高さが２ｎｍ以下の凹凸構造を持つことが認められることにある。表面が気液界面であるナノバブルはこのような表面構造を持ちえないので、このナノ粒子はナノバブルと一線を画すものであることから、本発明者はこのナノ粒子を「ナノキャビティ」と命名している（以下、このナノ粒子をナノキャビティと称することもある）。 The greatest feature of the water containing oxygen-containing nanoparticles of the present invention is that the oxygen-containing nanoparticles have an uneven structure having a height of 2 nm or less on at least a part of the surface when observed with an atomic force microscope. Is to be recognized. Since nanobubbles whose surface is a gas-liquid interface cannot have such a surface structure, these nanoparticles are different from nanobubbles, and therefore, the present inventor named these nanoparticles "nanocavities". (Hereinafter, these nanoparticles may be referred to as nanocavities).
本発明の酸素を含有するナノ粒子を含む水は、電気伝導度が３００μＳ／ｃｍ未満である水に、２価の鉄イオンを濃度が１〜１００ｐｐｂとなるように添加した水中に、酸素を含む乃至からなる気体を供給し、粒径が５０μｍ以下であるマイクロバブルを発生させ、発生したマイクロバブルが縮小することによって製造することができる。 The water containing oxygen-containing nanoparticles of the present invention contains oxygen in water having an electric conductivity of less than 300 μS / cm and divalent iron ions added so as to have a concentration of 1 to 100 ppb. It can be produced by supplying a gas composed of or to generate microbubbles having a particle size of 50 μm or less, and the generated microbubbles shrink.
電気伝導度が３００μＳ／ｃｍ未満である水としては、例えば電気伝導度が３μＳ／ｃｍ以下である純水を好適に用いることができるが、水道水や地下水を用いてもよい。水のｐＨは、後述する２価の鉄イオンの添加の前後を通して調整してもしなくてもよく、例えば６〜８であってよいが、７〜８が望ましい。 As the water having an electric conductivity of less than 300 μS / cm, for example, pure water having an electric conductivity of 3 μS / cm or less can be preferably used, but tap water or groundwater may also be used. The pH of water may or may not be adjusted before and after the addition of divalent iron ions, which will be described later, and may be, for example, 6 to 8, but 7 to 8 is preferable.
２価の鉄イオンは、塩化鉄（ＩＩ）、硫酸化鉄（ＩＩ）、硝酸鉄（ＩＩ）などの形態で添加することができる。 The divalent iron ion can be added in the form of iron (II) chloride, iron (II) sulfate, iron (II) nitrate and the like.
酸素を含む気体としては、例えば酸素濃度が約２０％である空気を用いることができ、酸素からなる気体としては、例えば純酸素を用いることができる。 As the gas containing oxygen, for example, air having an oxygen concentration of about 20% can be used, and as the gas composed of oxygen, for example, pure oxygen can be used.
水中に粒径が５０μｍ以下である酸素を含有するマイクロバブルを発生させる方法は、公知の方法であってよく、例えば、自体公知の二相流旋回方式や加圧溶解方式によるマイクロバブル発生装置を利用して発生させることができる。二相流旋回方式を採用する場合、回転子などを利用して半径が１０ｃｍ以下の渦流を強制的に生じせしめ、壁面などの障害物や相対速度の異なる流体に酸素を含んだ気液混合物を打ち当てることにより、渦流中に獲得した酸素を含んだ気体成分を渦の消失とともに分散させることで、所望の酸素を含有するマイクロバブルを大量に発生させることができる。また、加圧溶解方式を採用する場合、２気圧以上の高圧下で酸素を含んだ気体を水中に溶解させた後、これを大気圧に開放することにより生じた酸素を含んだ溶解気体の過飽和条件から酸素を含んだ気泡を発生させることができる。この場合、圧力の開放部位において、水流と障害物を利用して半径が１ｍｍ以下の渦を多数発生させ、渦流の中心域における水の分子揺動を起因として多量の気相の核（気泡核）を形成させるとともに、過飽和条件に伴ってこれらの気泡核に向かって水中の酸素を含んだ気体成分を拡散させ、気泡核を成長させることにより、所望の酸素を含有するマイクロバブルを大量に発生させることができる。こうして発生させたマイクロバブルは、粒径が５０μｍ以下で、レーザー光遮断方式の液中パーティクルカウンターによる計測において５〜１５μｍに粒径のピークを有しており、そのピークの領域におけるマイクロバブルの個数は１０００個／ｍＬ以上である（必要であれば特開２０００−５１１０７号公報や特開２００３−２６５９３８号公報などを参照のこと）。 The method for generating oxygen-containing microbubbles having a particle size of 50 μm or less in water may be a known method. It can be generated by using it. When adopting the two-phase flow swirling method, a vortex flow with a radius of 10 cm or less is forcibly generated using a rotor, etc., and a gas-liquid mixture containing oxygen in obstacles such as walls and fluids with different relative velocities is formed. By striking, a large amount of microbubbles containing desired oxygen can be generated by dispersing the oxygen-containing gas component acquired in the vortex flow with the disappearance of the vortex. Further, when the pressure dissolution method is adopted, the oxygen-containing dissolved gas is hypersaturated by dissolving the oxygen-containing gas in water under a high pressure of 2 atm or more and then releasing the gas to atmospheric pressure. Bubbles containing oxygen can be generated depending on the conditions. In this case, a large number of vortices with a radius of 1 mm or less are generated by using the water flow and obstacles at the pressure release site, and a large amount of gas phase nuclei (bubble nuclei) are generated due to the molecular fluctuation of water in the central region of the vortex. ) Is formed, and the oxygen-containing gas component in the water is diffused toward these bubble nuclei under hypersaturation conditions to grow the bubble nuclei, thereby generating a large amount of desired oxygen-containing microbubbles. Can be made to. The microbubbles generated in this way have a particle size of 50 μm or less, and have a particle size peak of 5 to 15 μm as measured by a laser light blocking type submerged particle counter, and the number of microbubbles in the peak region. Is 1000 pieces / mL or more (see JP-A-2000-51107, JP-A-2003-265938, etc., if necessary).
本発明の酸素を含有するナノ粒子を含む水を製造するに際しての要点は、電気伝導度が３００μＳ／ｃｍ未満である水への２価の鉄イオンの添加は、１〜１００ｐｐｂという極めて低濃度になるように行わなければならないところにある。２価の鉄イオンの添加がこれよりも少なくても多くても、目的とするナノキャビティが形成されて水中で安定に維持されない。その理由を、本発明者は次のように考えている。上述したように、ナノキャビティは、ナノバブルが持ちえない、表面の少なくとも一部に高さが２ｎｍ以下の凹凸構造を持つが、この特異な表面は、２価の鉄イオンが、酸素を含有するマイクロバブルが縮小する際に酸素から生成するオゾンによって酸化されて生成した３価の鉄イオンの水酸化物（Ｆｅ（ＯＨ）３）を主体とする固相からなり、この固相が、その内側に内包ガスとして存在する酸素を取り囲む殻として働くことで、ナノキャビティが形成されていると推察される。それを裏付ける事実としては、酸を加えると、この固相が溶解して消失することで、気泡の縮小が進行し、やがて水の中で消滅する際、マイクロバブルの消滅時と同様に、水酸基ラジカルを発生させることや、供給する酸素にオゾンを加えると、２価の鉄イオンの３価の鉄イオンへの酸化が促進されて、形成されるナノキャビティが増加することで、水酸基ラジカルの発生量も増加することが挙げられる。この固相は、マイクロバブルの縮小とともに徐々に形作られ、粒径が５０ｎｍ以下で堅固なものとなり、ナノキャビティを安定化させる。２価の鉄イオンの添加量が、その濃度が１ｐｐｂになる量よりも少ないと、この固相が十分に形作られるに足る３価の鉄イオンが供給されず、その濃度が１００ｐｐｂになる量よりも多いと、３価の鉄イオンの水酸化物が過剰に生成されることで、ナノキャビティが形成されても形成されたナノキャビティが集塊して沈殿物となってしまい、水中に存在しなくなる（従ってナノキャビティが形成されて水中で安定に維持されるためには他の電解質イオンが多量に存在することも望ましくないので２価の鉄イオンを添加する水の電気伝導度を３００μＳ／ｃｍ未満としている）。 The main point in producing water containing oxygen-containing nanoparticles of the present invention is that the addition of divalent iron ions to water having an electrical conductivity of less than 300 μS / cm results in an extremely low concentration of 1 to 100 ppb. It is where you have to do it. Even if the addition of divalent iron ions is less or more than this, the desired nanocavities are formed and are not stably maintained in water. The present inventor considers the reason as follows. As described above, the nanocavity has an uneven structure having a height of 2 nm or less on at least a part of the surface, which nanobubbles cannot have, but this peculiar surface contains oxygen by divalent iron ions. It consists of a solid phase mainly composed of a hydroxide of trivalent iron ions (Fe (OH) 3 ) generated by being oxidized by ozone generated from oxygen when microbubbles shrink, and this solid phase is inside. It is inferred that nanocavities are formed by acting as a shell surrounding oxygen, which exists as an contained gas. The fact that this is supported is that when an acid is added, this solid phase dissolves and disappears, causing the bubbles to shrink, and when they eventually disappear in water, the hydroxyl groups are the same as when the microbubbles disappear. When ozone is added to the generated oxygen or supplied oxygen, the oxidation of divalent iron ions to trivalent iron ions is promoted, and the number of nanocavities formed increases, resulting in the generation of hydroxyl radicals. The amount can also be increased. This solid phase is gradually formed as the microbubbles shrink and becomes solid with a particle size of 50 nm or less, stabilizing the nanocavities. If the amount of divalent iron ions added is less than the amount at which the concentration becomes 1 ppb, trivalent iron ions sufficient to form this solid phase are not supplied, and the concentration becomes 100 ppb. If there are too many, the hydroxide of trivalent iron ions is excessively generated, and even if the nanocavities are formed, the formed nanocavities are agglomerated and become a precipitate, which exists in water. (Therefore, in order for nanocavities to be formed and maintained stable in water, it is not desirable that a large amount of other electrolyte ions are present, so the electrical conductivity of water to which divalent iron ions are added is 300 μS / cm. Less than).
なお、２価の鉄イオンを添加する電気伝導度が３００μＳ／ｃｍ未満である水に、アミノ酸、カルボン酸、アミンなどの有機化合物を加えてもよい。こうした有機化合物を、例えば濃度が０．１〜１００μＭとなるように加えることで、２価の鉄イオンの３価の鉄イオンへの酸化が促進され、形成されるナノキャビティを増加させることができる。 An organic compound such as an amino acid, a carboxylic acid, or an amine may be added to water having an electric conductivity of less than 300 μS / cm to which a divalent iron ion is added. By adding such an organic compound so as to have a concentration of, for example, 0.1 to 100 μM, the oxidation of divalent iron ions to trivalent iron ions is promoted, and the number of nanocavities formed can be increased. ..
本発明の酸素を含有するナノ粒子を含む水は、酸素ナノバブル水が有する生物に対して酸素による生理活性効果を高める作用と同様の作用を有することに加え、ナノ粒子が表面の少なくとも一部に高さが２ｎｍ以下の凹凸構造を持つことで、酸素ナノバブル水が持ちえない作用として、有機物（それは組織や細胞を含めた生物や微生物であっても分子レベルでの物質などであってもよい）に対する求核的な作用を有することが期待できる。こうしたサブナノサイズの構造においては、原子核に近い電子による遮蔽効果（電子遮蔽効果）が強まる傾向にあるため、固相の表面付近に存在する電子は、原子核からの束縛から解放されて比較的に自由に挙動することができるので、求電子性を有する有機物に対して求核的に作用することが考えられる。 The water containing oxygen-containing nanoparticles of the present invention has an action similar to the action of enhancing the physiological activity effect of oxygen on living organisms of oxygen nanobubble water, and in addition, the nanoparticles are formed on at least a part of the surface. By having an uneven structure with a height of 2 nm or less, as an action that oxygen nanobubble water cannot have, it may be an organic substance (it may be an organism or microorganism including tissues and cells, or a substance at the molecular level). ) Can be expected to have a nucleophilic effect. In such a sub-nano size structure, the shielding effect (electron shielding effect) by electrons close to the atomic nucleus tends to be strengthened, so that the electrons existing near the surface of the solid phase are released from the binding from the atomic nucleus and are relatively free. Since it can behave like this, it is considered that it acts nucleophilically on an organic substance having electrophilicity.
以下、本発明を実施例によって詳細に説明するが、本発明は以下の記載に限定して解釈されるものではない。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not construed as being limited to the following description.
実施例１：
容積が１５Ｌのガラス製容器に、電気伝導度が０．０６μＳ／ｃｍである超純水を１０Ｌ入れ、そこに塩化鉄（ＩＩ）を濃度が０．５μＭ（２価の鉄イオンとして約２５ｐｐｂ）となるように添加した。この液中に、加圧溶解型のマイクロバブル発生装置を用い、粒径が１５〜５０μｍのマイクロバブルを１０分間発生させた。装置は内部の水を循環させながら駆動させた。装置には純酸素を約１．０Ｌ／分で供給した。装置の駆動を停止し、一昼夜、室内環境下で自然放置することでマイクロバブルを縮小させた後、１．２μｍのメンブレンフィルターでろ過処理を行い、本発明の酸素を含有するナノ粒子を含む水（ｐＨ：約７）を得た。
Example 1:
In a glass container having a volume of 15 L, 10 L of ultrapure water having an electric conductivity of 0.06 μS / cm is placed, and iron (II) chloride having a concentration of 0.5 μM (about 25 ppb as divalent iron ions) is placed therein. It was added so as to be. In this liquid, microbubbles having a particle size of 15 to 50 μm were generated for 10 minutes using a pressure-dissolving type microbubble generator. The device was driven while circulating the water inside. Pure oxygen was supplied to the device at about 1.0 L / min. After stopping the drive of the device and letting it stand naturally in an indoor environment for a whole day and night to shrink the microbubbles, it is filtered with a 1.2 μm membrane filter to contain water containing nanoparticles containing oxygen of the present invention. (PH: about 7) was obtained.
ろ過後の水２μＬを、プラスに帯電させた３−アミノプロピルトリエトキシシランで表面コートしたマイカ基板上に滴下し、原子間力顕微鏡（ＡＦＭ）で観察した。結果を図１に示す。図１から明らかなように、水中に、粒径が最大で３０ｎｍ程度の粒子（ナノキャビティ）が、基板に吸着するように集積して存在することを確認することができた。よって、このナノキャビティは、ｐＨが約７の水中で、ナノバブルと同様に、マイナスに帯電していることがわかった。また、原子間力顕微鏡による観察において、このナノキャビティは、表面の少なくとも一部に高さが２ｎｍ以下の凹凸構造を持つことが認められた（高さが１ｎｍ以下の凹凸構造も多数存在した）。このナノキャビティが表面に有する高さが２ｎｍ以下の凹凸構造は、このナノキャビティの断面解析（Ｚ軸方向）からも確認することができた（図２）。なお、原子間力顕微鏡による観察条件は次の通りとした。
（観察条件）
装置 ：高速原子間力顕微鏡ＮａｎｏＥｘｐｌｏｒｅｒ（生体分子計測研究所社）
観察環境 ：室温（２１℃）
カンチレバー：ＢＬ−ＡＣ１０ＤＳ−Ａ２（オリンパス社）
解像度 ：２００×２００ピクセル
観察イメージ：液中ＡＣモード形状像
2 μL of filtered water was dropped onto a mica substrate surface-coated with positively charged 3-aminopropyltriethoxysilane and observed with an atomic force microscope (AFM). The results are shown in FIG. As is clear from FIG. 1, it was confirmed that particles (nanocavities) having a maximum particle size of about 30 nm are accumulated and exist in water so as to be adsorbed on the substrate. Therefore, it was found that the nanocavities were negatively charged in water having a pH of about 7, similar to nanobubbles. Further, in observation with an atomic force microscope, it was found that this nanocavity had a concavo-convex structure having a height of 2 nm or less on at least a part of the surface (there were many concavo-convex structures having a height of 1 nm or less). .. The uneven structure having a height of 2 nm or less on the surface of the nanocavity could be confirmed from the cross-sectional analysis (Z-axis direction) of the nanocavity (FIG. 2). The observation conditions by the atomic force microscope were as follows.
(Observation conditions)
Equipment: High-speed atomic force microscope NanoExplorer (Biomolecule Measurement Laboratory)
Observation environment: Room temperature (21 ° C)
Cantilever: BL-AC10DS-A2 (Olympus)
Resolution: 200 x 200 pixels Observation image: Submerged AC mode shape image
ろ過後の水から１ｍＬをサンプリングし、これにエチレンジアミン四酢酸（ＥＤＴＡ）を濃度が２０ｍＭになるように加えた後、５，５−ジメチル−１−ピロリン Ｎ−オキシド（ＤＭＰＯ）を濃度が２００ｍＭになるように加え、さらに塩酸を濃度が５００ｍＭになるように加えた。得られた混合液を石英セルに吸引し、電子スピン共鳴装置（ＥＳＲ）で測定したところ、１：２：２：１のピークパターンを持つ顕著なＤＭＰＯ−ＯＨの信号を確認することができた。塩酸を加える前に、メタノールを０．２ｍＬ加え、同様の測定を行ったところ、１：２：２：１のピークパターンを持つ信号を確認することができたが、そのピーク長は１／３以下になった。メタノールは、水酸基ラジカルを捕捉して失活させてしまうスカベンジャーとして作用するので、以上の結果から、本発明の酸素を含有するナノ粒子を含む水は、酸を添加すると水酸基ラジカルを発生させることがわかった。また、ろ過後の水をペットボトルに入れて冷暗所で保管し、３か月後に同様の測定を行ったところ、１：２：２：１のピークパターンを持つ信号を確認することができ、そのピーク長は、製造直後のピーク長の９０％以上であったことから、本発明の酸素を含有するナノ粒子を含む水の優れた保存安定性を確認することができた。 1 mL is sampled from the filtered water, ethylenediaminetetraacetic acid (EDTA) is added to the sample to a concentration of 20 mM, and then 5,5-dimethyl-1-pyrroline N-oxide (DMPO) is added to a concentration of 200 mM. Further, hydrochloric acid was added so as to have a concentration of 500 mM. When the obtained mixed solution was sucked into a quartz cell and measured by an electron spin resonator (ESR), a remarkable DMPO-OH signal having a peak pattern of 1: 2: 2: 1 could be confirmed. .. When 0.2 mL of methanol was added before adding hydrochloric acid and the same measurement was performed, a signal with a peak pattern of 1: 2: 2: 1 could be confirmed, but the peak length was 1/3. It became the following. Methanol acts as a scavenger that captures and deactivates hydroxyl radicals. From the above results, water containing oxygen-containing nanoparticles of the present invention may generate hydroxyl radicals when an acid is added. all right. In addition, when the filtered water was placed in a PET bottle and stored in a cool and dark place, and the same measurement was performed 3 months later, a signal having a peak pattern of 1: 2: 2: 1 could be confirmed. Since the peak length was 90% or more of the peak length immediately after production, it was possible to confirm the excellent storage stability of water containing oxygen-containing nanoparticles of the present invention.
実施例２：
塩化鉄（ＩＩ）を濃度が０．０２μＭ（２価の鉄イオンとして約１ｐｐｂ）となるように添加すること以外は実施例１と同様の操作を行うことで、本発明の酸素を含有するナノ粒子を含む水を得た。ろ過後の水について電子スピン共鳴装置による測定を行ったところ、ＤＭＰＯ−ＯＨのピークを確認することができ、そのピーク長は、実施例１のろ過後の水のピーク長の約１／５倍であった。
Example 2:
By performing the same operation as in Example 1 except that iron (II) chloride is added so as to have a concentration of 0.02 μM (about 1 ppb as a divalent iron ion), the nano-containing oxygen of the present invention. Water containing particles was obtained. When the filtered water was measured by an electron spin resonator, the peak of DMPO-OH could be confirmed, and the peak length was about 1/5 of the peak length of the filtered water of Example 1. Met.
実施例３：
塩化鉄（ＩＩ）を濃度が２μＭ（２価の鉄イオンとして約１００ｐｐｂ）となるように添加すること以外は実施例１と同様の操作を行うことで、本発明の酸素を含有するナノ粒子を含む水を得た。ろ過後の水について電子スピン共鳴装置による測定を行ったところ、ＤＭＰＯ−ＯＨのピークを確認することができ、そのピーク長は、実施例１のろ過後の水のピーク長の約１／５倍であった。
Example 3:
By performing the same operation as in Example 1 except that iron (II) chloride is added so as to have a concentration of 2 μM (about 100 ppb as a divalent iron ion), the nanoparticles containing oxygen of the present invention can be obtained. Obtained water containing. When the filtered water was measured by an electron spin resonator, the peak of DMPO-OH could be confirmed, and the peak length was about 1/5 of the peak length of the filtered water of Example 1. Met.
比較例１：
塩化鉄（ＩＩ）を濃度が０．０１μＭ（２価の鉄イオンとして約０．５ｐｐｂ）となるように添加すること以外は実施例１と同様の操作を行うことで、本発明の酸素を含有するナノ粒子を含む水を得ようとしたが、得ることはできなかった（ろ過後の水についての電子スピン共鳴装置による測定においてＤＭＰＯ−ＯＨのピークを確認することができなかった）。
Comparative Example 1:
The oxygen of the present invention is contained by performing the same operation as in Example 1 except that iron (II) chloride is added so as to have a concentration of 0.01 μM (about 0.5 ppb as a divalent iron ion). I tried to obtain water containing nanoparticles, but I could not obtain it (the peak of DMPO-OH could not be confirmed by the measurement of the filtered water with an electron spin resonance device).
比較例２：
塩化鉄（ＩＩ）を濃度が６μＭ（２価の鉄イオンとして約３００ｐｐｂ）となるように添加すること以外は実施例１と同様の操作を行うことで、本発明の酸素を含有するナノ粒子を含む水を得ようとしたが、得ることはできなかった（ガラス容器の底部に水酸化鉄（Ｆｅ（ＯＨ）３）を主体とする茶色の沈殿物が顕著に認められ、この沈殿物をろ過した後の水についての電子スピン共鳴装置による測定においてＤＭＰＯ−ＯＨのピークを確認することができなかった）。
Comparative Example 2:
By performing the same operation as in Example 1 except that iron (II) chloride is added so as to have a concentration of 6 μM (about 300 ppb as a divalent iron ion), the oxygen-containing nanoparticles of the present invention can be obtained. An attempt was made to obtain water containing it, but it could not be obtained ( a brown precipitate mainly composed of iron hydroxide (Fe (OH) 3 ) was prominently observed at the bottom of the glass container, and this precipitate was filtered. The peak of DMPO-OH could not be confirmed in the measurement of water after this with an electron spin resonator).
実施例４：
マイクロバブル発生装置に供給する純酸素を、無声放電によるオゾン発生装置を介してから供給すること以外は実施例１と同様の操作を行うことで、本発明の酸素を含有するナノ粒子を含む水を得た。ろ過後の水について電子スピン共鳴装置による測定を行ったところ、ＤＭＰＯ−ＯＨのピークを確認することができ、そのピーク長は、実施例１のろ過後の水のピーク長の約１．５倍であった。
Example 4:
By performing the same operation as in Example 1 except that the pure oxygen supplied to the microbubble generator is supplied after passing through the ozone generator by silent discharge, water containing nanoparticles containing oxygen of the present invention is performed. Got When the filtered water was measured by an electron spin resonator, the peak of DMPO-OH could be confirmed, and the peak length was about 1.5 times the peak length of the filtered water of Example 1. Met.
実施例５：
マイクロバブル発生装置に供給する純酸素を空気に変更すること以外は実施例１と同様の操作を行うことで、本発明の酸素を含有するナノ粒子を含む水を得た。ろ過後の水について電子スピン共鳴装置による測定を行ったところ、ＤＭＰＯ−ＯＨのピークを確認することができ、そのピーク長は、実施例１のろ過後の水のピーク長の約１／５倍であった。
Example 5:
Water containing nanoparticles containing oxygen of the present invention was obtained by performing the same operation as in Example 1 except that the pure oxygen supplied to the microbubble generator was changed to air. When the filtered water was measured by an electron spin resonator, the peak of DMPO-OH could be confirmed, and the peak length was about 1/5 of the peak length of the filtered water of Example 1. Met.
実施例６：
塩化鉄（ＩＩ）にかわりに硫酸鉄（ＩＩ）を添加すること以外は実施例１と同様の操作を行うことで、本発明の酸素を含有するナノ粒子を含む水を得た。ろ過後の水について電子スピン共鳴装置による測定を行ったところ、ＤＭＰＯ−ＯＨのピークを確認することができ、そのピーク長は、実施例１のろ過後の水のピーク長とほぼ同じであった。
Example 6:
By performing the same operation as in Example 1 except that iron (II) sulfate was added instead of iron (II) chloride, water containing the oxygen-containing nanoparticles of the present invention was obtained. When the filtered water was measured by an electron spin resonator, a peak of DMPO-OH could be confirmed, and the peak length was almost the same as the peak length of the filtered water of Example 1. ..
実施例７：
塩化鉄（ＩＩ）にかわりに硝酸鉄（ＩＩ）を添加すること以外は実施例１と同様の操作を行うことで、本発明の酸素を含有するナノ粒子を含む水を得た。ろ過後の水について電子スピン共鳴装置による測定を行ったところ、ＤＭＰＯ−ＯＨのピークを確認することができ、そのピーク長は、実施例１のろ過後の水のピーク長とほぼ同じであった。
Example 7:
By performing the same operation as in Example 1 except that iron (II) nitrate was added instead of iron (II) chloride, water containing nanoparticles containing oxygen of the present invention was obtained. When the filtered water was measured by an electron spin resonator, a peak of DMPO-OH could be confirmed, and the peak length was almost the same as the peak length of the filtered water of Example 1. ..
実施例８：
超純水に予めグリシンを濃度が１０μＭとなるように加えておくこと以外は実施例５と同様の操作を行うことで、本発明の酸素を含有するナノ粒子を含む水を得た。ろ過後の水について電子スピン共鳴装置による測定を行ったところ、ＤＭＰＯ−ＯＨのピークを確認することができ、そのピーク長は、実施例５のろ過後の水のピーク長の約３倍であった。
Example 8:
Water containing the oxygen-containing nanoparticles of the present invention was obtained by performing the same operation as in Example 5 except that glycine was added to ultrapure water in advance so as to have a concentration of 10 μM. When the filtered water was measured by an electron spin resonator, the peak of DMPO-OH could be confirmed, and the peak length was about 3 times the peak length of the filtered water of Example 5. rice field.
実施例９：
超純水のかわりに電気伝導度が約１００μＳ／ｃｍの水道水を用いること以外は実施例１と同様の操作を行うことで、本発明の酸素を含有するナノ粒子を含む水を得た。ろ過後の水について電子スピン共鳴装置による測定を行ったところ、ＤＭＰＯ−ＯＨのピークを確認することができ、そのピーク長は、実施例１のろ過後の水のピーク長の約２／３倍であった。
Example 9:
By performing the same operation as in Example 1 except that tap water having an electric conductivity of about 100 μS / cm was used instead of ultrapure water, water containing nanoparticles containing oxygen of the present invention was obtained. When the filtered water was measured by an electron spin resonator, the peak of DMPO-OH could be confirmed, and the peak length was about 2/3 times the peak length of the filtered water of Example 1. Met.
実施例１０：
超純水のかわりに電気伝導度が約２５０μＳ／ｃｍの地下水（全有機炭素量（ＴＯＣ）が約０．５ｍｇ／Ｌで２価の鉄イオンの濃度が約５０ｐｐｂ）を用いることと、塩化鉄（ＩＩ）を添加しないこと以外は実施例１と同様の操作を行うことで、本発明の酸素を含有するナノ粒子を含む水を得た。ろ過後の水について電子スピン共鳴装置による測定を行ったところ、ＤＭＰＯ−ＯＨのピークを確認することができ、そのピーク長は、実施例１のろ過後の水のピーク長の約１／５倍であった。
Example 10:
Instead of ultrapure water, use groundwater with an electrical conductivity of about 250 μS / cm (total organic carbon (TOC) of about 0.5 mg / L and divalent iron ion concentration of about 50 ppb) and iron chloride. By performing the same operation as in Example 1 except that (II) was not added, water containing the oxygen-containing nanoparticles of the present invention was obtained. When the filtered water was measured by an electron spin resonator, the peak of DMPO-OH could be confirmed, and the peak length was about 1/5 of the peak length of the filtered water of Example 1. Met.
本発明は、酸素ナノバブル水とは異なる、酸素を含有するナノ粒子を含む水を提供することができる点において産業上の利用可能性を有する。 The present invention has industrial applicability in that it can provide water containing oxygen-containing nanoparticles, which is different from oxygen nanobubble water.
Claims (3)
The production method according to claim 2, wherein divalent iron ions are added in at least one form selected from iron (II) chloride, iron (II) sulfate, and iron (II) nitrate.
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| JP2020009559A JP7475025B2 (en) | 2020-01-23 | Water containing oxygen-containing nanoparticles |
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| JP2020009559A JP7475025B2 (en) | 2020-01-23 | Water containing oxygen-containing nanoparticles |
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| JP7475025B2 JP7475025B2 (en) | 2024-04-26 |
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