JP7475025B2 - Water containing oxygen-containing nanoparticles - Google Patents
Water containing oxygen-containing nanoparticles Download PDFInfo
- Publication number
- JP7475025B2 JP7475025B2 JP2020009559A JP2020009559A JP7475025B2 JP 7475025 B2 JP7475025 B2 JP 7475025B2 JP 2020009559 A JP2020009559 A JP 2020009559A JP 2020009559 A JP2020009559 A JP 2020009559A JP 7475025 B2 JP7475025 B2 JP 7475025B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- oxygen
- less
- added
- nanoparticles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 97
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 66
- 229910052760 oxygen Inorganic materials 0.000 title claims description 66
- 239000001301 oxygen Substances 0.000 title claims description 66
- 239000002105 nanoparticle Substances 0.000 title claims description 36
- -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 20
- 239000002245 particle Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 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
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- 239000002101 nanobubble Substances 0.000 description 18
- 238000004435 EPR spectroscopy Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 239000003792 electrolyte Substances 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
- 238000005259 measurement Methods 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
- 238000004090 dissolution Methods 0.000 description 3
- 238000011978 dissolution method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002244 precipitate 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
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000005416 organic matter Substances 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
- 239000004471 Glycine Substances 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 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
- 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
- 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
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
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 oxygen-containing nanoparticles. More specifically, the invention relates to water in which the nanoparticles are different from air bubbles (nanobubbles) having an air-liquid interface.
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, for example, Patent Document 1 that water containing nanobubbles containing oxygen (oxygen nanobubble water) has the effect of enhancing the physiological activity effect of oxygen on living organisms, and this knowledge was discovered by the inventor Takahashi. In Patent Document 1, Takahashi also proposes a method for producing oxygen nanobubble water by supplying oxygen to an aqueous solution containing electrolyte ions and having an electrical conductivity of 3 mS/cm or more, generating microbubbles with a particle size of 10 to 50 μm, and applying a physical stimulus to the microbubbles to shrink them. As a characteristic of microbubbles, they shrink in water, concentrating the charge on their surface. The surface of the bubbles is negatively charged by hydroxide ions (OH − ) derived from the collected water. The shrinkage of the bubbles is due to the efficient dissolution of gas in water and the gradual rate of ascent. Microbubbles are spherical bubbles, and can be generated by a method called a two-layer flow swirling method or a pressurized dissolution method. The generated bubbles are surrounded by water, and surface tension acts on their surface (gas-liquid interface). Surface tension is a force that acts to reduce the area. In the case of spherical microbubbles, the force that reduces the surface area ultimately 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 eventually disappear in the water. However, when the water that generates the microbubbles has a certain 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 ions that serve as counter 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 the water and inhibiting further shrinkage of the bubbles, which extends the life of the bubbles and makes them exist as nanobubbles with 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 inventor Takahashi's tireless research to date is helping to clarify the true nature of oxygen nanobubble water. However, there are still many things that are unclear about oxygen nanobubble water, and 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。 The present invention aims to provide water that contains 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 course of researching new methods for producing oxygen nanobubble water, the present inventors discovered that when trace amounts of divalent iron ions (Fe 2+ ) are added to water that generates oxygen-containing microbubbles, water containing nanoparticles that are different from bubbles that have a gas-liquid interface (nanobubbles) 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、内包ガスとして酸素を含有する、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、酸素を含む気体または酸素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。
The present invention, which has been made based on the above findings, is water, as described in claim 1, which contains nanoparticles that have an uneven structure with a height of 2 nm or less on at least a part of their surface when observed with an atomic force microscope, have a particle size of 50 nm or less, and contain oxygen as an encapsulated gas , and which generates hydroxyl radicals when acid is added.
The present invention relates to a method for producing water according to claim 1, in which a gas containing oxygen or a gas consisting of oxygen is supplied to water having an electrical conductivity of less than 300 μS/cm to which divalent iron ions have been added so as to have a concentration of 1 to 100 ppb, thereby generating microbubbles having a particle size of 50 μm or less.
In addition, the manufacturing method described in claim 3 is the manufacturing method described in claim 2, wherein the divalent iron ions are added in the form of at least one selected from iron (II) chloride, iron (II) sulfate, and iron (II) nitrate.
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 that contains 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。 The water containing oxygen-containing nanoparticles provided by the present invention, which is different from oxygen nanobubble water, is water that has an uneven structure with a height of 2 nm or less on at least a part of its surface as observed by atomic force microscope, contains nanoparticles with a particle size of 50 nm or less that contain oxygen, and generates hydroxyl radicals when 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 are observed to have an uneven structure with a height of 2 nm or less on at least a part of their surface when observed with an atomic force microscope. Nanobubbles, whose surfaces are gas-liquid interfaces, cannot have such a surface structure, so the present inventors have named these nanoparticles "nanocavities" (hereinafter, these nanoparticles may also 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 can be produced by supplying a gas containing or consisting of oxygen to water having an electrical conductivity of less than 300 μS/cm to which divalent iron ions have been added to give a concentration of 1 to 100 ppb, generating microbubbles with a particle size of 50 μm or less, and allowing the generated microbubbles to 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 water with an electrical conductivity of less than 300 μS/cm, for example, pure water with an electrical conductivity of 3 μS/cm or less can be suitably used, but tap water or groundwater can also be used. The pH of the 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, with 7 to 8 being 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。 Divalent iron ions can be added in the form of iron(II) chloride, iron(II) sulfate, iron(II) nitrate, etc.
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 a gas containing oxygen, for example, air with an oxygen concentration of about 20% can be used, and as a gas consisting 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 of generating oxygen-containing microbubbles having a particle size of 50 μm or less in water may be a known method, and for example, microbubbles can be generated using a microbubble generator using a known two-phase flow swirling method or a pressurized dissolution method. When the two-phase flow swirling method is adopted, a vortex with a radius of 10 cm or less is forcibly generated using a rotor or the like, and the oxygen-containing gas-liquid mixture is struck against an obstacle such as a wall surface or a fluid with a different relative speed, thereby dispersing the oxygen-containing gas components acquired in the vortex as the vortex disappears, thereby generating a large amount of microbubbles containing the desired oxygen. In addition, when the pressurized dissolution method is adopted, oxygen-containing gas is dissolved in water under a high pressure of 2 atmospheres or more, and then released to atmospheric pressure, whereby oxygen-containing bubbles can be generated from the supersaturated condition of the dissolved oxygen-containing gas. In this case, a large number of vortices with a radius of 1 mm or less are generated at the pressure release site using the water flow and obstacles, and a large number of gas phase nuclei (bubble nuclei) are formed due to the molecular vibration of water in the central region of the vortex flow, and oxygen-containing gas components in the water are diffused toward these bubble nuclei under supersaturated conditions, causing the bubble nuclei to grow, thereby generating a large amount of microbubbles containing the desired oxygen. The microbubbles generated in this way have a particle size of 50 μm or less, a particle size peak at 5 to 15 μm when measured using a liquid particle counter using a laser light blocking method, and the number of microbubbles in the peak region is 1000/mL or more (see JP 2000-51107 A, JP 2003-265938 A, 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 key point in producing water containing oxygen-containing nanoparticles of the present invention is that divalent iron ions must be added to water having an electrical conductivity of less than 300 μS/cm at an extremely low concentration of 1 to 100 ppb. If the amount of divalent iron ions added is less or more than this amount, the desired nanocavities are not formed and are not stably maintained in the water. The inventor considers the reason for this as follows. As described above, the nanocavities have an uneven structure with a height of 2 nm or less on at least a part of the surface, which nanobubbles cannot have, and this unique surface is composed of a solid phase mainly composed of hydroxides of trivalent iron ions (Fe(OH) 3 ) generated by oxidation of divalent iron ions by ozone generated from oxygen when oxygen-containing microbubbles shrink, and it is presumed that the nanocavities are formed by this solid phase acting as a shell surrounding the oxygen present as an encapsulated gas inside. This is supported by the fact that when acid is added, this solid phase dissolves and disappears, causing the bubbles to shrink, and when they eventually disappear in water, they generate hydroxyl radicals, just as microbubbles do when they disappear, and when ozone is added to the oxygen being supplied, the oxidation of divalent iron ions to trivalent iron ions is promoted, and the number of nanocavities formed increases, which also increases the amount of hydroxyl radicals generated. This solid phase is gradually formed as the microbubbles shrink, becoming 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 that results in a concentration of 1 ppb, sufficient trivalent iron ions will not be supplied to fully form this solid phase, and if the amount is more than the amount that results in a concentration of 100 ppb, excessive hydroxides of trivalent iron ions will be produced, and even if nanocavities are formed, the nanocavities will agglomerate into precipitates and will no longer exist in water (accordingly, in order to form nanocavities and maintain them stably in water, it is not desirable for other electrolyte ions to be present in large quantities, so the electrical conductivity of the water to which divalent iron ions are added is set to less than 300 μS/cm).
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。 In addition, organic compounds such as amino acids, carboxylic acids, and amines may be added to the water with an electrical conductivity of less than 300 μS/cm to which the divalent iron ions are added. By adding such organic compounds to 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。 Water containing the oxygen-containing nanoparticles of the present invention has the same effect as oxygen nanobubble water in enhancing the physiological activity of oxygen on living organisms. In addition, because the nanoparticles have an uneven structure with a height of 2 nm or less on at least a part of their surface, they are expected to have a nucleophilic effect on organic matter (which may be living organisms or microorganisms, including tissues and cells, or substances at the molecular level, etc.), an effect that oxygen nanobubble water does not have. In such sub-nano-sized structures, the shielding effect (electron shielding effect) of electrons close to the atomic nucleus tends to be strengthened, so that electrons present near the surface of the solid phase are freed from the constraints of the atomic nucleus and can behave relatively freely, and are therefore thought to act nucleophilically on organic matter that has 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。 The present invention will be described in detail below with reference to examples, but the present invention should not be interpreted 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 with a volume of 15 L, 10 L of ultrapure water with an electrical conductivity of 0.06 μS/cm was placed, and iron (II) chloride was added to the container so that the concentration was 0.5 μM (approximately 25 ppb as divalent iron ions). In this liquid, microbubbles with a particle size of 15 to 50 μm were generated for 10 minutes using a pressure dissolution type microbubble generator. The device was driven while circulating the water inside. Pure oxygen was supplied to the device at approximately 1.0 L/min. The device was stopped and left to stand naturally in an indoor environment for a day and night to reduce the microbubbles, and then filtered with a 1.2 μm membrane filter to obtain water containing the oxygen-containing nanoparticles of the present invention (pH: approximately 7).
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 the filtered water was dropped onto a mica substrate whose surface was coated with positively charged 3-aminopropyltriethoxysilane, and observed with an atomic force microscope (AFM). The results are shown in FIG. 1. As is clear from FIG. 1, it was confirmed that particles (nano cavities) with a particle size of up to about 30 nm were present in the water, accumulating so as to be adsorbed to the substrate. Therefore, it was found that the nano cavities were negatively charged in water with a pH of about 7, similar to nano bubbles. In addition, in the observation with an atomic force microscope, it was confirmed that the nano cavities had an uneven structure with a height of 2 nm or less on at least a part of the surface (there were also many uneven structures with a height of 1 nm or less). The uneven structure with a height of 2 nm or less on the surface of the nano cavities could also be confirmed from the cross-sectional analysis (Z-axis direction) of the nano cavities (FIG. 2). The observation conditions with the atomic force microscope were as follows.
(Observation conditions)
Equipment: High-speed atomic force microscope NanoExplorer (Biomolecular Measurement Laboratory)
Observation environment: Room temperature (21°C)
Cantilever: BL-AC10DS-A2 (Olympus)
Resolution: 200 x 200 pixels Observation image: AC mode shape image in liquid
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 of the filtered water was sampled, and ethylenediaminetetraacetic acid (EDTA) was added to the sample to a concentration of 20 mM. Then, 5,5-dimethyl-1-pyrroline N-oxide (DMPO) was added to a concentration of 200 mM, and hydrochloric acid was added to a concentration of 500 mM. The resulting mixture was sucked into a quartz cell and measured with an electron spin resonance (ESR) device, and a prominent DMPO-OH signal with a 1:2:2:1 peak pattern was confirmed. Before adding hydrochloric acid, 0.2 mL of methanol was added and the same measurement was performed, and a signal with a 1:2:2:1 peak pattern was confirmed, but the peak length was 1/3 or less. Methanol acts as a scavenger that captures and deactivates hydroxyl radicals, so the above results show that water containing the oxygen-containing nanoparticles of the present invention generates hydroxyl radicals when acid is added. In addition, the filtered water was placed in a plastic bottle and stored in a cool, dark place. A similar measurement was then performed three months later. A signal with a 1:2:2:1 peak pattern was confirmed, and the peak length was 90% or more of the peak length immediately after production, confirming the excellent storage stability of the water containing the 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:
Water containing the oxygen-containing nanoparticles of the present invention was obtained by carrying out the same operation as in Example 1, except that iron (II) chloride was added to a concentration of 0.02 μM (approximately 1 ppb as divalent iron ion). When the filtered water was measured using an electron spin resonance device, a peak of DMPO-OH was confirmed, and the peak length was approximately 1/5 times that of the filtered water of Example 1.
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:
Water containing the oxygen-containing nanoparticles of the present invention was obtained by carrying out the same operation as in Example 1, except that iron (II) chloride was added to a concentration of 2 μM (approximately 100 ppb as divalent iron ion). When the filtered water was measured using an electron spin resonance device, a peak of DMPO-OH was confirmed, and the peak length was approximately 1/5 times that of the filtered water of Example 1.
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:
An attempt was made to obtain water containing the oxygen-containing nanoparticles of the present invention by carrying out the same procedure as in Example 1, except that iron (II) chloride was added to a concentration of 0.01 μM (approximately 0.5 ppb as divalent iron ion), but this was not possible (no DMPO-OH peak was observed in the measurement of the filtered water using 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:
An attempt was made to obtain water containing the oxygen-containing nanoparticles of the present invention by carrying out the same procedure as in Example 1, except that iron (II) chloride was added to a concentration of 6 μM (approximately 300 ppb as divalent iron ion), but this was not possible (a brown precipitate mainly composed of iron hydroxide (Fe(OH) 3 ) was clearly observed at the bottom of the glass container, and no DMPO-OH peak was confirmed when the water after filtering out this precipitate was measured using an electron spin resonance device).
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:
Water containing oxygen-containing nanoparticles of the present invention was obtained by carrying out the same operations as in Example 1, except that the pure oxygen supplied to the microbubble generator was passed through an ozone generator using silent discharge before being supplied. When the filtered water was measured using an electron spin resonance apparatus, a peak of DMPO-OH was confirmed, and the peak length was about 1.5 times that of the filtered water of Example 1.
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 oxygen-containing nanoparticles of the present invention was obtained by carrying out the same operations as in Example 1, except that the pure oxygen supplied to the microbubble generator was changed to air. When the filtered water was measured using an electron spin resonance apparatus, a peak of DMPO-OH was confirmed, and the peak length was about 1/5 times that of the filtered water of Example 1.
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:
Water containing oxygen-containing nanoparticles of the present invention was obtained by carrying out the same operation as in Example 1, except that iron sulfate (II) was added instead of iron chloride (II). When the filtered water was measured using an electron spin resonance apparatus, a peak of DMPO-OH was confirmed, and the peak length was approximately the same as that 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:
Water containing oxygen-containing nanoparticles of the present invention was obtained by carrying out the same operation as in Example 1, except that iron nitrate (II) was added instead of iron chloride (II). When the filtered water was measured using an electron spin resonance apparatus, a peak of DMPO-OH was confirmed, and the peak length was almost the same as that of the filtered water in 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 carrying out the same operation as in Example 5, except that glycine was added to the ultrapure water in advance to a concentration of 10 μM. When the filtered water was measured using an electron spin resonance device, a peak of DMPO-OH was confirmed, and the peak length was about three times that of the filtered water of Example 5.
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:
Water containing the oxygen-containing nanoparticles of the present invention was obtained by carrying out the same operations as in Example 1, except that tap water with an electrical conductivity of about 100 μS/cm was used instead of ultrapure water. When the filtered water was measured using an electron spin resonance apparatus, a peak of DMPO-OH was confirmed, and the peak length was about 2/3 times that of the filtered water of Example 1.
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:
Water containing the oxygen-containing nanoparticles of the present invention was obtained by carrying out the same operations as in Example 1, except that groundwater (total organic carbon (TOC) of about 0.5 mg/L and divalent iron ion concentration of about 50 ppb) with an electrical conductivity of about 250 μS/cm was used instead of ultrapure water and iron (II) chloride was not added. When the filtered water was measured using an electron spin resonance apparatus, a peak for DMPO-OH was confirmed, and the peak length was about 1/5 times that of the filtered water of Example 1.
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)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020009559A JP7475025B2 (en) | 2020-01-23 | 2020-01-23 | Water containing oxygen-containing nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020009559A JP7475025B2 (en) | 2020-01-23 | 2020-01-23 | Water containing oxygen-containing nanoparticles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021115507A JP2021115507A (en) | 2021-08-10 |
| JP7475025B2 true JP7475025B2 (en) | 2024-04-26 |
Family
ID=77173560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020009559A Active JP7475025B2 (en) | 2020-01-23 | 2020-01-23 | Water containing oxygen-containing nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7475025B2 (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003245662A (en) | 2002-02-21 | 2003-09-02 | Fm Ecology Kenkyusho:Kk | Waste water treatment system |
| JP2003334548A (en) | 2002-05-20 | 2003-11-25 | National Institute Of Advanced Industrial & Technology | Method for producing nanometer air bubble |
| JP2005245817A (en) | 2004-03-05 | 2005-09-15 | National Institute Of Advanced Industrial & Technology | Production method of nano-bubble |
| JP2005246294A5 (en) | 2004-03-05 | 2006-03-16 | ||
| JP2008272739A (en) | 2006-05-23 | 2008-11-13 | Hideyasu Tsuji | Fine bubble generating apparatus |
| JP2009226386A (en) | 2008-03-21 | 2009-10-08 | Makoto Yafuji | Ultrafine-bubble water |
| JP2010167365A (en) | 2009-01-22 | 2010-08-05 | Reo Laboratory Co Ltd | Functional water production method |
| JP2016221479A (en) | 2015-06-02 | 2016-12-28 | 日本建設機械商事株式会社 | Soil cleaning method, soil cleaning system, and sparging rod assembly |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4080440B2 (en) | 2004-03-05 | 2008-04-23 | 独立行政法人産業技術総合研究所 | Oxygen nanobubble water and method for producing the same |
-
2020
- 2020-01-23 JP JP2020009559A patent/JP7475025B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003245662A (en) | 2002-02-21 | 2003-09-02 | Fm Ecology Kenkyusho:Kk | Waste water treatment system |
| JP2003334548A (en) | 2002-05-20 | 2003-11-25 | National Institute Of Advanced Industrial & Technology | Method for producing nanometer air bubble |
| JP2005245817A (en) | 2004-03-05 | 2005-09-15 | National Institute Of Advanced Industrial & Technology | Production method of nano-bubble |
| JP2005246294A5 (en) | 2004-03-05 | 2006-03-16 | ||
| JP2008272739A (en) | 2006-05-23 | 2008-11-13 | Hideyasu Tsuji | Fine bubble generating apparatus |
| JP2009226386A (en) | 2008-03-21 | 2009-10-08 | Makoto Yafuji | Ultrafine-bubble water |
| JP2010167365A (en) | 2009-01-22 | 2010-08-05 | Reo Laboratory Co Ltd | Functional water production method |
| JP2016221479A (en) | 2015-06-02 | 2016-12-28 | 日本建設機械商事株式会社 | Soil cleaning method, soil cleaning system, and sparging rod assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021115507A (en) | 2021-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5294370B2 (en) | Method for producing water containing reactive species and water containing reactive species | |
| Noqta et al. | Recent advances in iron oxide nanoparticles (IONPs): synthesis and surface modification for biomedical applications | |
| JP4921333B2 (en) | Method for producing carbon dioxide nanobubble water | |
| Kikuchi et al. | Concentration determination of oxygen nanobubbles in electrolyzed water | |
| JP2008093611A (en) | Manufacturing method of water containing extremely fine air bubble and water containing extremely fine air bubble | |
| JP2005246294A (en) | Oxygen-nanobubble water and production method therefor | |
| CA2859694C (en) | Radioactive and/or magnetic metal nanoparticles and process and apparatus for synthesizing same | |
| JP2005246294A5 (en) | ||
| JP2016221513A (en) | Measurable ultra-fine bubble water having oxidizing radical or reducing radical, and ultra-fine bubble solution | |
| CN105860957A (en) | Preparation method of oxidized graphene composite for drug carrier | |
| JP2008237950A (en) | Production method for hydroxyl radical-containing water and hydroxyl radical-containing water | |
| Zhang et al. | Basic characteristics and application of micro-nano bubbles in water treatment | |
| JP4921332B2 (en) | Method for producing nitrogen nanobubble water | |
| Liao et al. | Rational assembly of GO-based heterocyclic sulfur-and nitrogen-containing aerogels and their adsorption properties toward rare earth elementals | |
| JP7475025B2 (en) | Water containing oxygen-containing nanoparticles | |
| CN101654284B (en) | Preparation method of magnetic ferroferric oxide nanocrystal | |
| WO2016017820A1 (en) | Water including permanganate ions, and method for producing same | |
| JP2011050931A (en) | Method for generating hydroxyl radical in water | |
| KR101765889B1 (en) | A composition for removing toxic and refractory organics, a method for preparing the same, and an apparatus for treating water comprising the same | |
| JP6341581B2 (en) | Production method of ozone water | |
| Zhang et al. | Facile formation of controlled facet-dependent Cu2O beads with highly efficient U (VI) removal | |
| CN106040232B (en) | For wastewater treatment catalyst, prepare the method for catalyst and including the sewage treatment equipment of catalyst | |
| JP2006289289A (en) | Active hydrogen water production method and its production device | |
| KR20130077452A (en) | Method for synthesis of gold nanoparticles | |
| JP2010242193A (en) | Functional stainless steel nano ball and stainless steel nano ball catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20221109 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230920 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20231107 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240106 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20240402 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240409 |