WO2003106583A1 - Photosensibilisant utile pour generer de l'oxygene singulet et procede de production d'oxygene singulet - Google Patents

Photosensibilisant utile pour generer de l'oxygene singulet et procede de production d'oxygene singulet Download PDF

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WO2003106583A1
WO2003106583A1 PCT/JP2003/007586 JP0307586W WO03106583A1 WO 2003106583 A1 WO2003106583 A1 WO 2003106583A1 JP 0307586 W JP0307586 W JP 0307586W WO 03106583 A1 WO03106583 A1 WO 03106583A1
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oxygen
singlet oxygen
porous
energy
emission
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PCT/JP2003/007586
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English (en)
Japanese (ja)
Inventor
藤井　稔
ビクター ティモシェンコ
ドミトリー コバレフ
エーゴン グロス
ヨーヒム ディーナー
ニコライ クンツナー
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財団法人新産業創造研究機構
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Priority to JP2004513398A priority Critical patent/JP4608654B2/ja
Priority to AU2003241661A priority patent/AU2003241661A1/en
Publication of WO2003106583A1 publication Critical patent/WO2003106583A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen

Definitions

  • the present invention relates to a singlet oxygen generating photosensitizer and a method for generating singlet oxygen using the same.
  • the present invention relates to a singlet oxygen generating photosensitizer capable of producing a large amount of singlet oxygen, which is an oxygen molecule in an excited state, with high efficiency and a singlet oxygen generating method using the same.
  • Singlet oxygen the excited state of oxygen molecules, is much more active than normal oxygen in the atmosphere and is deeply involved in various chemical reactions and biological activities. In addition, it is a very important substance in the fields of biology and medicine because of its bactericidal action, cytotoxic action, etc. It is also applied to cancer treatment as photodynamic therapy.
  • porous Si a porous Si with a nanometer size
  • the function as a photosensitizer for oxygen molecules is brought out, and the Si state becomes excited. It is intended to provide a singlet oxygen generating photosensitizer formed of Si nanocrystals capable of producing a large amount of an oxygen molecule (singlet oxygen) with high efficiency and a singlet oxygen generating method using the same. Aim. Disclosure of the invention
  • the present inventors have noticed that when a semiconductor crystal is reduced to a size of a nanometer, its electronic state becomes similar to a “molecule”, and it is possible that the nanocrystal acts as a photosensitizer for singlet oxygen. I have been conducting diligent research on nature. As a result, they have recently found that by reducing the size of the Si crystal to a nanometer size (Si nanocrystal), a function as a photosensitizer for singlet oxygen is exhibited, and completed the present invention.
  • the singlet oxygen generating photosensitizer according to the present invention is formed of Si nanocrystals. It is preferable that the Si nanocrystal is terminated with hydrogen. Further, it is preferable that the Si nanocrystal emits light at 1.4 to 2.0 eV and has an emission peak at 1.63 eV. Further, the Si nanocrystal is preferably porous silicon. Further, it is preferable that the porous silicon be subjected to a boost etching process.
  • the singlet oxygen generating method includes: placing the above-described singlet oxygen generating photosensitizer in an atmosphere containing oxygen; Irradiation with light generates singlet oxygen.
  • a method for placing the oxygen atom-generating photosensitizer in an atmosphere containing oxygen a method of adsorbing oxygen on the surface at a low temperature or a method of placing the singlet oxygen-generating photosensitizer in an oxygen gas atmosphere is used.
  • the method is not particularly limited as long as the singlet oxygen-generating photosensitizer is in contact with oxygen, such as a method of placing in a liquid in which oxygen gas is dissolved, or a method of placing in a liquid in which oxygen gas is dissolved.
  • the method of generating singlet oxygen has generally used a method in which an oxygen molecule in a ground state is raised to an excited state by energy transfer from an organic dye molecule photosensitizer to an oxygen molecule. .
  • this method does not disturb singlet oxygen dissolved in the solution (it is difficult to generate a gaseous state), and the light of a specific wavelength matching the absorption spectrum of the dye upon excitation of the photosensitizer.
  • There are problems such as that only energy can be used and energy transfer efficiency is low.
  • Si nanocrystals, and in particular, porous Si firstly, Si nanocrystals are solid, and the energy is transferred to oxygen molecules physically adsorbed or collided on the surface to generate singlet oxygen.
  • the state can generate singlet oxygen.
  • porous Si since porous Si is porous and has a huge surface area, it can produce a large amount of singlet oxygen in a very small volume.
  • Si nanocrystals absorb light in the entire visible light range from part of the near-infrared light, so that the excitation light source is not limited. If singlet oxygen can be efficiently generated by natural light (sunlight), it may be possible to use singlet oxygen for air and water pollution countermeasures, and the effect is immense.
  • the electronic state of Si nanocrystals is similar to that of molecules, and has the property that the excited state is split into a triplet state and a singlet state.
  • Si is an indirect transition type semiconductor
  • Si is harmless to the human body and is therefore well suited for biological and medical applications.
  • the Si nanocrystal refers to a Si crystal having a size of several nanometers to several tens of nanometers.
  • the Si nanocrystal has an electronic state different from that of the Balta S ⁇ crystal due to the quantum size effect (quantum confinement effect). While the Balta Si crystal has a band gap in the near-infrared region, the band gap of the Si nanocrystal shifts from the near-infrared region to the visible region as the size decreases.
  • Porous Si refers to porous Si generated by anodizing Si crystals. The skeleton of the porous Si is formed by Si nanowires or nanocrystals.
  • a photosensitizer is a substance that, after being excited by light, transfers its excitation energy to another substance (energy transfer) and raises the substance to an excited state.
  • energy transfer In general, optical transitions are forbidden, light absorption is very small, and they are used to generate excited states of materials.
  • Energy transfer refers to the transfer of excitation energy from one substance to another.
  • a method of exciting the Si nanocrystal either a method of irradiating the Si nanocrystal with light from the outside or a method of injecting and exciting a current to the Si nanocrystal is used. Is also good.
  • the porous Si according to the present invention is obtained by immersing a Si substrate in a mixed solution in which hydrofluoric acid and ethanol alcohol are mixed at a ratio of 1 to 1 and energizing for several minutes to thereby form Si by anodization of Si. It is fabricated by etching i to form a hole with a predetermined depth from the surface.
  • Si substrates that can be used may be single or polycrystalline.
  • FIG. 1 (a) is a diagram showing an example of a transmission electron microscope image of the porous Si.
  • the plane direction of the sample is observed. It can be seen that it has a porous structure.
  • the lattice fringes in the enlarged view correspond to the ⁇ 111 ⁇ plane of Si (0.31 nm), and it can be seen that the pillars remaining without being etched are composed of Si nanocrystals.
  • FIG. 1 (b) shows an electron micrograph of a cross section of the porous Si.
  • FIG. 2 is a schematic diagram of a system for measuring light emission from singlet oxygen.
  • Figure 3 shows the emission spectrum of porous Si at low temperature (4 K).
  • the broken line shows a spectrum measured in a vacuum without adsorbing oxygen to the pores of the porous Si.
  • the solid line is the spectrum with oxygen adsorbed on the pore.
  • the inset (left) shows an enlarged view of the emission spectrum from singlet oxygen, and the inset (right) shows the electron configuration of the oxygen molecule.
  • FIG. 4 is a diagram showing a result obtained by dividing a light emission spectrum measured in a vacuum by a spectrum measured in an oxygen-adsorbed state. The higher the value, the higher the emission emission due to oxygen adsorption. The high energy data was measured under conditions where luminescence was not completely quenched. In order to show the structure more clearly, the derivative of the spectrum is shown twice.
  • FIG. 5 is a diagram showing the result (4) of dividing the emission spectrum measured in a vacuum by the spectrum measured in an oxygen-adsorbed state. Two types of data with different oxygen adsorption amounts are shown (broken line: large adsorption amount, solid line: small adsorption amount).
  • FIG. 6 (a) shows a light emission spectrum of the porous Si at 11 OK, and
  • FIG. 6 (b) shows a degree of light emission caused by introduction of oxygen gas. Oxygen pressure has changed by seven types.
  • FIG. 7 is a diagram showing the relationship between the emission scan Bae spectrum and the size of S i nanocrystals (data S i 0 2 thin S i nanocrystals embedded in). As the size decreases, the emission peak shifts to the higher energy side. Although the size dependence of the emission of porous Si is not completely the same, it is considered that there is no significant difference in this energy region.
  • FIG. 8 (a) shows a light emission spectrum of the porous Si at room temperature
  • FIG. 8 (b) shows a degree of light emission quenching by oxygen gas introduction.
  • Oxygen pressure is changing by 8 kinds.
  • FIG. 9 is a diagram showing the relationship between the degree of quenching of light emission and oxygen pressure. ( ⁇ : 120 K, ⁇ : 200 K, ⁇ : 300 ⁇ ). The solid line shows the result of the fitting by equation (4).
  • FIG. 10 is a diagram showing the relationship between the post-etching time and the luminous intensity and the quenching intensity.
  • FIG. 11 is a table summarizing 4 ( ⁇ ) ⁇ ( ⁇ ) obtained from the fitting result shown in FIG. 9. BEST MODE FOR CARRYING OUT THE INVENTION
  • Si wafer (p-type (100), lm Q cm to 100 ⁇ cm) is immersed in a one-to-one solution of hydrofluoric acid (50%) and ethanol alcohol, and 10 to 50 O The current was passed at mA / cm 2 for several minutes.
  • the anodization of Si allows porous silicon to reach a depth of about 40 // m from the surface of the Si wafer.
  • Got Si The average diameter of the Si nanowires (nanocrystals) left unetched is a few nm, and the porosity (porosity) is about 10% to 90%. At this time, the Si nanocrystal is terminated with hydrogen.
  • Fig. 1 (a) shows a plane transmission electron micrograph of the porous Si. The observation was made in the plane direction of the sample. It can be seen that the sample has a sponge-like porous structure. The lattice fringes in the enlarged view correspond to the (11 1) plane of Si, and it can be seen that the pillars left unetched are composed of Si nanocrystals.
  • FIG. 1 (b) shows a scanning electron micrograph of a cross section of the porous Si.
  • Fig. 2 shows an outline of a system that can detect near-infrared light (about 1.26 ⁇ ) emitted when singlet oxygen relaxes to triplet oxygen.
  • the detection system consists of a near-infrared emission spectrometer 2 (InGaAs diode array, sensitivity range (800-1700 nm)), a time-resolved emission spectrometer 3 (SiI CCD), and It consists of a cold finger type 1 cryostat 1 (4K-300K) for cooling Si nanocrystals. Specifically, a porous Si sample is fixed in a cold finger type cryostat 1, and the Si sample is irradiated with excitation light from outside.
  • a near-infrared emission spectrometer 2 InGaAs diode array, sensitivity range (800-1700 nm)
  • SiI CCD time-resolved emission spectrometer 3
  • It consists of a cold finger type 1 cryostat 1 (4K-300K)
  • the cryostat 1 is provided with a precision gas valve 4 for strictly controlling the oxygen concentration, and is connected to the turbo molecular pump 5 and the oxygen cylinder 6 via the valve 4.
  • this system includes an optical fiber as needed in the middle of the optical system so that the visible light emission from the porous Si can be constantly monitored under the same sample conditions as in the near-infrared light emission measurement. It can be installed, and the emission in the visible region can be measured by SICCD 3 through an optical fiber. With this configuration, exactly the same environment (sample temperature, oxygen concentration, adsorbed oxygen amount, etc.) over a wide range from the near infrared region to the visible region The emission can be measured below.
  • Fig. 3 shows the emission spectrum of porous Si at cryogenic temperature (4K).
  • the vertical axis is represented by a logarithm.
  • the dashed line shows the spectrum measured in vacuum without adsorbing anything on the pores of the porous Si, and the solid line shows the spectrum with oxygen adsorbed on the pores.
  • Oxygen adsorption was performed by introducing oxygen at an appropriate pressure into the cryostat at high temperature (over 1 OOK), and then cooling the sample.
  • porous Si has two broad emission bands.
  • the band on the high energy side is light emission from excitons confined in the porous Si, and the spectrum becomes very broad reflecting the size and shape distribution of the nanocrystals constituting the porous Si. ing.
  • Light emission on the low energy side is light emission due to defects (dangling bonds) on the porous Si surface.
  • the spectrum shape changes greatly as follows. (1) emits light at a second 1 corresponds to the energy difference between the excited state sigma) and the ground state (3 ⁇ ). 6 3 e V than the high energy side of the oxygen molecules is very weak, also observed in CCD ultra-sensitive Becomes difficult. The vertical axis is logarithmic. (2) Even at 1.63 eV or less, the emission intensity is reduced by one digit or more, and a periodic vibration structure is observed.
  • the degree of singlet oxygen generation can be indirectly measured by measuring the degree of luminescence quenching of the Si nanocrystals without directly observing the luminescence from singlet oxygen. Can be investigated.
  • Fig. 3 shows the spectrum observed in the state where oxygen is adsorbed in Fig. 3 to the non-uniform spread of the spectrum due to the coupling strength and the size and shape distribution of the Si nanocrystals constituting the porous Si. It has been combined.
  • Fig. 4 shows the results of dividing the vacuum spectrum by the oxygen-adsorbed spectrum to remove the effects and to purely extract the relationship between coupling strength and energy. .
  • the rate of energy transfer with the emission of phonons is higher than that of resonant energy transfer because the rate of energy transfer is strongly dependent on the overlapping of the spectrums of the donor (donor) and receiver (acceptor). Extremely small. We believe that the cause of the observed structure due to energy transfer accompanied by the release of up to eight TO phonons was the extremely long exciton lifetime of Si nanocrystals at low temperatures. At 4 K with oxygen adsorbed, light emission is usually hardly observed above 1.63 eV. However, when the measurement is carried out at a slightly high temperature (about 40 K: about 50 K), the tangency becomes small and weak light emission is observed even at 1.63 eV or more. In FIG.
  • Figure 5 compares two types of data obtained at different temperatures (4 K) with different amounts of oxygen adsorption.
  • the vertical axis indicates the degree of tangency as in FIG. It can be seen that when the amount of adsorption is large (broken line), the degree of light emission is greater than that when the amount is small (solid line), and the light emission from singlet oxygen is also strong (Fig. 5 shows the oxygen adsorption state). Since the vector is divided by the vacuum vacuum, the emission from singlet oxygen appears as a downward peak.) When the amount of oxygen adsorbed is large, the degree of tangency changes gradually below 1.63 eV, until the band gap of the balta Si goes below the band gap. It is continuous.
  • Taenchi of light emission is also observed in the low energy side than the energy of 1 delta state.
  • the amount of adsorbed oxygen is small, hardly any entanglement is observed from 1.63 eV to the band gap of Balta Si, and entanglement is observed again at an energy less than the band gap. This result has very important implications.
  • the emission below the band gap of the Balta Si is caused by dangling bonds on the surface of the Si nanocrystal.
  • a nanocrystal having at least one dangling pound does not emit light at room temperature, and the existence of such nanocrystals Determine the emission quantum efficiency of the entire porous Si sample.
  • the ability to transfer energy from “blue” nanocrystals, which do not contribute to light emission, indicates that highly efficient singlet oxygen generation is possible.
  • Fig. 6 shows the emission spectrum of porous Si at 110K (a) and the degree of light emission (b).
  • Oxygen concentration is changed in 7 ways. It can be seen that the emission intensity decreases (the emission quenching increases) as the oxygen concentration increases.
  • the light emission tangency is remarkable even at 1.63 eV, and the structure is also seen at 1.85 eV. Quench is hardly observed in other areas.
  • 1.6 3 Peak of e V are consistent with the energy of 1 sigma state of the oxygen molecule, that see that this Taenchi is due energy first moving to oxygen molecules from the S i nanocrystal. That is, Si functions as a photosensitizer also for oxygen molecules in a gas state.
  • 1.8 5 structure e V is to 1 delta state of the pair of the two oxygen molecules It corresponds to excitation, and this structure is also due to singlet oxygen formation.
  • the degree of Taenchi even higher energy side of the state decreases with distance from the energy-saving one 1 sigma state. That is, the energy or the 1 sigma state of the oxygen partial element is in the gaseous state, only S i nanocrystals resonantly energy transfer to oxygen molecules having a band gap energy that matches the energy one 2 E state oxygen molecule pair be able to.
  • the possible causes are as follows. In the gas state, energy transfer occurs during the collision event of molecular oxygen on the porous Si surface. The force coupling between excitons and states in the nanocrystal is so strong that energy transfer can be terminated during collisions, but coupling with the ⁇ state is relatively weak (energy transfer time is long) However, it is considered difficult to transfer energy during a collision event.
  • the exciton energy and 1 delta state it is necessary to release the phonon nano crystal to satisfy the certain energy mismatch between the state energy conservation law, according to the number of follower non to release The energy transfer rate decreases.
  • the oxygen content The excitons are adsorbed on the nanocrystal surface, and the exciton has a very long lifetime, so that non-resonant energy transfer accompanied by phonon emission is possible, but such a process would be more difficult in the gas state.
  • the band gap (emission energy) of a Si nanocrystal changes depending on its size.
  • Figure 7 shows the relationship between the emission peak energy (corresponding to the band gap) and the size of the Si nanocrystal.
  • Figure 7 does not coincide completely from those of S i 0 is data S i nanocrystals embedded 2 thin film porous S i, big difference is not considered to be the energy region (same When compared by size, the emission peak energy of porous Si tends to be on the higher energy side.)
  • the size of the Si nanocrystals must be about 2.5 nm or less in order to transfer energy from the Si nanocrystal force to gaseous oxygen molecules to generate singlet oxygen. It turns out that there is.
  • Nanocrystals are not spherical but oval or wire-shaped, and the size is not particularly limited.
  • Fig. 8 shows the emission spectrum of porous Si at room temperature and the degree of light emission due to oxygen introduction. ⁇ The degree of tangency is smaller than in the case of 10 K, but it can be seen that the luminescence is tangent depending on the oxygen concentration. This indicates that singlet oxygen is generated even at room temperature by energy transfer from the Si nanocrystal. Also, as in the case of 110 K, the emission entanglement is largest at 1.63 eV, and even at room temperature, the energy transfer of the Si nanocrystal having a diameter of about 2.5 nm is small. It can be seen that this is performed most efficiently.
  • FIG. 9 shows the results (9: 120 K, ⁇ : 20 OK, ⁇ : 300 ⁇ ).
  • the horizontal axis indicates the oxygen pressure
  • the vertical axis indicates the degree of emission intensity due to oxygen introduction. It can be seen that the light emission is larger at lower temperatures.
  • the degree of the taint saturates at a certain oxygen concentration, and even if the oxygen concentration is further increased, the degree of the taint does not become so large.
  • the amount of oxygen molecules adsorbed on the porous Si surface under each condition is considered by the Langmuir adsorption isotherm.
  • the ratio of the sites adsorbed by oxygen molecules to the total adsorption sites of oxygen molecules on the porous Si surface ⁇ is
  • Equation (2) shows that the experimental results were reproduced very well. In other words, the rate of energy transfer from Si nanocrystals to gaseous oxygen molecules is proportional to the oxygen coverage on the nanocrystal surface.
  • the porous Si is immersed in a 1: 1 mixed solution of hydrofluoric acid (50%) and ethanol alcohol and subjected to post etching.
  • the singlet oxygen-generating photosensitizer according to the present invention can easily generate singlet oxygen by giving excitation light.
  • sandwiched glass S i 0 2 or the like has a hole that can pass Accordingly, formed in the cassette-like, by providing the excitation light to the cassette surface from either before or after the air passes out of the air passing through, Oxygen becomes singlet oxygen, and it can be used as a filter capable of sterilizing or sterilizing bacteria in the passing air.
  • the ability to release the required singlet oxygen by continuing to release singlet oxygen for a long period of time can make it difficult to release the required singlet oxygen.
  • the singlet oxygen-generating photosensitizer according to the present invention is configured as described above, and is simplified by adsorbing oxygen to Si nanocrystals and providing excitation light. Since only capable of generating singlet oxygen, for example, pinching Te cowpea the glass S io 2 or the like has a hole that the singlet oxygen generation photosensitizer oxygen can pass, formed in a cassette shape, By supplying excitation light to the cassette surface either before or after the air passes, oxygen in the passing air becomes singlet oxygen, and as a filter capable of sterilizing or sterilizing bacteria and the like in the passing air. It can be used.
  • the generated singlet oxygen comes into direct contact with humans, the generated singlet oxygen is once passed through a water tank, etc., and bapped so as not to be released directly to the outside. It is preferred to use. This is because singlet oxygen is immediately changed into normal triplet state oxygen in a solution in a unit of Z seconds.
  • the Si nanocrystal shown as an example of the above-described embodiment for example, it can be used as a powder.
  • the singlet oxygen evolution sensitizer in powder form is introduced into a necessary part of the body, and the lesion formed in various parts of the body by irradiating light from outside the body causes the generated singlet. It can be made smaller with oxygen, making it applicable to medical uses other than industrial use. Industrial applicability
  • the present invention uses a nanometer-sized Si crystal as a singlet oxygen generation photosensitizer. Therefore, unlike organic dye molecule photosensitizers that have been used as conventional singlet oxygen generating photosensitizers, (1) abundant and inexpensive materials (low cost), (2) harmless to humans, 3) Simple manufacturing process, (4) Easy mass production, (5) Effective use of ultraviolet to visible light regardless of excitation light wavelength, (6) High energy transfer efficiency, (7) Gas state (Gas state) or an effect that singlet oxygen dissolved in a solution can be generated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

La présente invention concerne un photosensibilisant qui permet de générer de l'oxygène singulet et qui comprend un nanocristal de silicium, notamment un silicium poreux. Le photosensibilisant utile pour générer de l'oxygène singulet permet de produire à grande échelle et avec une grande efficacité de l'oxygène singulet.
PCT/JP2003/007586 2002-06-18 2003-06-13 Photosensibilisant utile pour generer de l'oxygene singulet et procede de production d'oxygene singulet WO2003106583A1 (fr)

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JP2004513398A JP4608654B2 (ja) 2002-06-18 2003-06-13 一重項酸素発生光増感剤及びそれを用いた一重項酸素発生方法
AU2003241661A AU2003241661A1 (en) 2002-06-18 2003-06-13 Photosensitizer for generating singlet oxygen and method for generating singlet oxygen

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JP2002-176515 2002-06-18
JP2002176515 2002-06-18

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007537965A (ja) * 2004-05-21 2007-12-27 サイメデイカ リミテツド ケイ素構造体
JP2008229335A (ja) * 2007-03-16 2008-10-02 Inha-Industry Partnership Inst 多孔性シリコンからなる光線力学的療法用製剤及びそれから発生する活性酸素の定量的測定方法
JP2009242191A (ja) * 2008-03-31 2009-10-22 Furukawa Electric Co Ltd:The 一重項酸素生成装置
JP2011161416A (ja) * 2010-02-15 2011-08-25 Tokyo Institute Of Technology マイクロ反応装置および反応方法
RU2459827C2 (ru) * 2010-10-26 2012-08-27 Государственное Научное Учреждение "Институт Физики Имени Б.И. Степанова Национальной Академии Наук Беларуси" Способ получения гибридного фотосенсибилизатора
WO2022103987A1 (fr) * 2020-11-12 2022-05-19 California Institute Of Technology Génération photocatalytique d'oxygène singulet pour purification d'air

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WO1997005203A1 (fr) * 1995-07-25 1997-02-13 The Procter & Gamble Company Photodesinfectants faiblement teintes
WO1997049119A1 (fr) * 1996-06-19 1997-12-24 Matsushita Electric Industrial Co., Ltd. Materiau photoelectronique, dispositif faisant appel a ce materiau et procede de fabrication

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JP3196644B2 (ja) * 1995-06-26 2001-08-06 松下電器産業株式会社 光電子材料の製造方法、並びにその光電子材料を用いた応用素子及び応用装置
JP3447859B2 (ja) * 1995-09-13 2003-09-16 株式会社東芝 シリコン系発光材料の製造方法
JP3405099B2 (ja) * 1996-11-27 2003-05-12 松下電器産業株式会社 カラーセンサ

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Publication number Priority date Publication date Assignee Title
WO1997005203A1 (fr) * 1995-07-25 1997-02-13 The Procter & Gamble Company Photodesinfectants faiblement teintes
WO1997049119A1 (fr) * 1996-06-19 1997-12-24 Matsushita Electric Industrial Co., Ltd. Materiau photoelectronique, dispositif faisant appel a ce materiau et procede de fabrication

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007537965A (ja) * 2004-05-21 2007-12-27 サイメデイカ リミテツド ケイ素構造体
JP2008229335A (ja) * 2007-03-16 2008-10-02 Inha-Industry Partnership Inst 多孔性シリコンからなる光線力学的療法用製剤及びそれから発生する活性酸素の定量的測定方法
EP1980270A3 (fr) * 2007-03-16 2009-06-24 Inha-Industry Partnership Institute Agent pour thérapie photodynamique contenant silicium poreux et procédé de mesure quantitative d'espèces d'oxygène réactives produites à partir de l'agent
JP2009242191A (ja) * 2008-03-31 2009-10-22 Furukawa Electric Co Ltd:The 一重項酸素生成装置
JP2011161416A (ja) * 2010-02-15 2011-08-25 Tokyo Institute Of Technology マイクロ反応装置および反応方法
RU2459827C2 (ru) * 2010-10-26 2012-08-27 Государственное Научное Учреждение "Институт Физики Имени Б.И. Степанова Национальной Академии Наук Беларуси" Способ получения гибридного фотосенсибилизатора
WO2022103987A1 (fr) * 2020-11-12 2022-05-19 California Institute Of Technology Génération photocatalytique d'oxygène singulet pour purification d'air

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