WO2022138854A1 - 温度感受性プローブ - Google Patents

温度感受性プローブ Download PDF

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WO2022138854A1
WO2022138854A1 PCT/JP2021/047991 JP2021047991W WO2022138854A1 WO 2022138854 A1 WO2022138854 A1 WO 2022138854A1 JP 2021047991 W JP2021047991 W JP 2021047991W WO 2022138854 A1 WO2022138854 A1 WO 2022138854A1
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Prior art keywords
temperature
group
sensitive probe
center
doped
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English (en)
French (fr)
Japanese (ja)
Inventor
正浩 西川
明 劉
憲和 水落
出 大木
正規 藤原
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Daicel Corp
Kyoto University NUC
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Daicel Corp
Kyoto University NUC
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Priority to CN202180086824.3A priority Critical patent/CN116670501A/zh
Priority to KR1020237020931A priority patent/KR20230123966A/ko
Priority to EP21910993.1A priority patent/EP4269969A4/en
Priority to AU2021409095A priority patent/AU2021409095A1/en
Priority to US18/265,455 priority patent/US20240044722A1/en
Priority to CA3203222A priority patent/CA3203222A1/en
Priority to JP2022571638A priority patent/JPWO2022138854A1/ja
Publication of WO2022138854A1 publication Critical patent/WO2022138854A1/ja
Anticipated expiration legal-status Critical
Priority to JP2024063638A priority patent/JP2024096141A/ja
Ceased legal-status Critical Current

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00Investigating or analyzing materials by the use of thermal means
    • G01N25/20Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/25Diamond
    • C01B32/26Preparation
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/59Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing silicon
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/65Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing carbon
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/66Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing germanium, tin or lead
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01KMEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/20Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01KMEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K2211/00Thermometers based on nanotechnology

Definitions

  • the present invention relates to a temperature sensitive probe.
  • Non-Patent Document 1 temperature measurement is performed using 200 nm size fluorescent nanodiamond particles having a SiV (silicon-vacancy) center.
  • An object of the present invention is to provide a temperature sensitive probe capable of stably and accurately measuring the temperature of a minute space.
  • the present invention provides the following temperature sensitive probes.
  • a MV center having an average particle size of 1 to 100 nm M represents a Group 14 element selected from the group consisting of Si, Ge, Sn and Pb; V represents a vacancy).
  • M represents a Group 14 element selected from the group consisting of Si, Ge, Sn and Pb; V represents a vacancy).
  • M represents a Group 14 element selected from the group consisting of Si, Ge, Sn and Pb; V represents a vacancy).
  • a temperature sensitive probe containing group 14 element-doped nanodiamonds [2] The temperature sensitive probe according to [1], wherein M is Si.
  • RSD standard relative deviation
  • An MV center having an average particle size of 1 to 100 nm for measuring the temperature of a minute space M is a group 14 element selected from the group consisting of Si, Ge, Sn and Pb, and V is a vacancy. Use of Group 14 element-doped nanodiamonds with (indicating vacancy).
  • M is a group 14 element selected from the group consisting of Si, Ge, Sn and Pb
  • V is a vacancy.
  • a MV center having an average particle size of 1 to 100 nm (M represents a Group 14 element selected from the group consisting of Si, Ge, Sn and Pb; V represents a vacancy).
  • the temperature-sensitive probe is introduced into the cell by mixing the group 14 element-doped nanodiamond with the cell in water, and the cell into which the group 14 element-doped nanodiamond is introduced is irradiated with excitation light to irradiate the ZPL of the MV center.
  • a method of measuring the intracellular temperature including.
  • the present invention it is possible to measure the temperature in a limited microspace such as an organelle in a cell.
  • This utilizes the fact that the peak position of the ZPL (Zero Phonon Line) of the MV center shifts with temperature.
  • the MV center has the advantage of being stable and having a strong emission intensity.
  • the temperature-sensitive probe of the present invention can finely set the temperature response region in the cell by uniformly dispersing it in the cell or arranging or binding it in a specific place, and can be used as an intracellular fluorescent temperature sensor. can.
  • the temperature sensitive probe of the present invention represents a Group 14 element selected from the group consisting of MV centers (M is Si, Ge, Sn and Pb) having an average particle size of 1 to 100 nm. V indicates a vacancy.
  • Group 14 element-doped nanodiamonds with. Group 14 element-doped nanodiamonds are nanoparticles, the upper limit of their average particle size being preferably 100 nm, more preferably 70 nm, even more preferably 50 nm, particularly preferably 30 nm, particularly more preferably 20 nm.
  • the average particle size of the Group 14 element-doped nanodiamond is small because it does not interfere with the movement or structural change of biomolecules such as intracellular proteins.
  • the standard relative deviation (RSD) of the particle size of Group 14 element-doped nanodiamonds is preferably 25-40%, and the average particle size and standard relative deviation (RSD) are measured by the Small Angle X-ray Scattering Method (SAXS). can do.
  • SAXS Small Angle X-ray Scattering Method
  • the relative standard deviation (%) can be calculated by the following formula.
  • the temperature-sensitive probe of the present invention is suitable for measuring temperature in a microspace, for example, not only can measure the temperature of the whole cell, but also intracellular small organs (for example, endoplasmic reticulum, mitochondria, Gorgi, peroxysome, lysosome, micro).
  • intracellular small organs for example, endoplasmic reticulum, mitochondria, Gorgi, peroxysome, lysosome, micro.
  • the temperature of tubes and microscopic bodies can be measured separately.
  • cells for which temperature is to be measured include microorganisms such as yeast, animal cells, plant cells, and the like, which can be easily introduced into cells.
  • the temperature-sensitive probe of the present invention utilizes the fact that the fluorescence peak position at the time of irradiation with excitation light shifts with temperature.
  • the temperature-sensitive probe detects the temperature by fluorescence (ZPL) near 738 nm from the SiV center, but this fluorescence near 738 nm measures the intracellular temperature because it is hardly absorbed by the cell or its organelles. Suitable for. Since the fluorescence of the GeV center with ZPL of 602 nm, the SnV center with ZPL of 620 nm, and the PbV center with ZPL of 520 nm and 552 nm is strong, it is possible to measure the intracellular temperature.
  • the "cell” in the present invention consists of prokaryotic cells and eukaryotic cells, which are a general classification, and does not particularly depend on the species of the organism.
  • prokaryotic cells are divided into eubacteria and paleobacteria, and eubacteria are broadly divided into gram-positive bacteria such as Radical Bacteria and Gram-negative bacteria such as Proteobacterium, depending on the thickness of the peptidoglycan layer.
  • the applicable range of temperature-sensitive probes is not limited.
  • eukaryotic cells mainly include cells belonging to eukaryotes (protists, fungi, plants, animals).
  • yeast which is generally used in research such as molecular biology and is also used industrially, belongs to fungi.
  • the fluorescence (ZPL) near 738 nm at various temperatures (for example, 35 ° C to 40 ° C when the measurement target is a cell)
  • the peak position can be measured and the temperature of the object to be measured can be measured based on the result.
  • the temperature of the object to be measured (for example, cell) is measured.
  • the temperature of the object to be measured can do.
  • a calibration curve can be created by measuring the peak position of fluorescence (ZPL) near the ZPL of the MV center at each temperature, and the temperature can be measured based on this calibration curve.
  • the calibration curve can be created by heating and cooling the Group 14 element-doped nanodiamond particles carried or coated on the substrate.
  • the calibration curve can be created by changing the measurement conditions depending on the measurement target.
  • the conditions under which the calibration curve is used are not limited, but for example, a curve plotting the temperature-dependent change in the fluorescence intensity of the temperature-sensitive probe in a potassium chloride solution that mimics the intracellular can be used. can. More specifically, when a temperature-sensitive probe-introduced cell population is used to perform a heat-sensitive response test and plot changes in the peak position of fluorescence (ZPL), the cells actively engage in metabolic activity.
  • ZPL peak position of fluorescence
  • the cells are kept at a specific temperature for a certain period of time, and the external temperature and the internal temperature of the cells are in an equilibrium state. There is a method of measuring the fluorescence intensity in the situation where it is considered that the temperature has been reached.
  • the temperature sensitive probe of the present invention can be applied to various fields of research and development. For example, in the field of biotechnology, in the fermentation production of useful substances using microorganisms, it is expected that the efficiency of examination of culture conditions will be improved by adding the intracellular temperature, which has been difficult to measure accurately, to the analysis parameters. To.
  • the temperature sensitive probe of the present invention can be applied to various medical applications. For example, by using the temperature-sensitive probe according to the present invention on a part of a patient's tissue, it is possible to distinguish between cancer cells that are said to produce a large amount of heat and normal cells that do not. be. Furthermore, by applying it, it can be used for the development of more effective hyperthermia treatment methods.
  • a temperature-sensitive probe according to the present invention by introducing a temperature-sensitive probe according to the present invention into brown adipocytes having a large amount of heat production and measuring the temperature change due to the addition of various materials to the cells, it is effective for burning fat by consuming energy.
  • Materials that activate brown adipocytes can be screened. Such materials are effective for weight loss or slimming by promoting fat burning.
  • the temperature-sensitive probe of the present invention can also be applied to elucidate various physiological phenomena. For example, by investigating how temperature-sensitive (Transient Receptor Potential, TRP) channels, which are receptors that sense in vitro temperature and trigger biological reactions, are related to intracellular temperature. Activation of TRP channels with different approaches is conceivable. In addition, by investigating the relationship between the intracellular temperature distribution and the biological reaction that occurs inside and outside the cell, it is possible to investigate the effect of the local temperature distribution on the biological reaction. It is also possible to control. Furthermore, since the temperature-sensitive probe of the present invention is not toxic, it can be safely used for microorganisms, animal cells or plant cells, or mammalian cells such as humans, mice and rats.
  • TRP Transient Receptor Potential
  • the present invention is further a method for measuring the intracellular temperature.
  • a step of introducing the temperature-sensitive probe into the cell by mixing the temperature-sensitive probe according to any one of [1] to [4] with the cell in water.
  • B) The cells into which the temperature-sensitive probe has been introduced are irradiated with excitation light, and the MV center (M indicates a Group 14 element selected from the group consisting of Si, Ge, Sn and Pb. V indicates a vacancy.
  • Group 14 element-doped nanodiamonds can preferably be produced by the detonation method.
  • the shape of the Group 14 element-doped nanodiamond is preferably spherical, ellipsoidal, or a polyhedron close to them.
  • the amount of Group 14 element (M) atom introduced (number of doped atoms (M) / number of C atoms) ⁇ 100 [%]) in the Group 14 element-doped nanodiamond of the present invention is preferably 0.5 to 40%. More preferably, it is 1 to 36%.
  • Pore can be introduced into the group 14 element-doped nanodiamond by ion beam irradiation or electron beam irradiation.
  • the upper limit of the pore concentration to be introduced is preferably 1 ⁇ 10 21 / cm 3 or less capable of retaining the structure of the diamond, and the lower limit of the pore concentration is, for example, 1 ⁇ 10 16 / cm 3 or more, 5 ⁇ 10 16 / Cm 3 or more, 1 ⁇ 10 17 / cm 3 or more, 5 ⁇ 10 17 / cm 3 or more, 1 ⁇ 10 18 / cm 3 or more.
  • the ion beam is preferably a hydrogen (H) or helium (He) ion beam.
  • the energy of the hydrogen ion beam is preferably 10 to 1500 keV, and the energy of the helium ion beam is preferably 20 to 2000 keV.
  • the energy of the electron beam is preferably 500 to 5000 keV.
  • the ZPL of the SiV center is 738 nm, which is located in the so-called window of the living body (wavelength band where excitation light and fluorescence pass through the living body), and is an ideal light emitting center that enables external excitation and external measurement as a probe for biological imaging. Is.
  • the ZPL of the GeV center is 602 nm
  • the ZPL of the SnV center is 620 nm
  • the ZPL of the PbV center is 520 nm and 552 nm.
  • the concentration of the MV center in the preferred Group 14 element-doped nanodiamond of the present invention is preferably 1 ⁇ 10 14 / cm 3 or more, and more preferably 2 ⁇ 10 14 to 1 ⁇ 10 19 / cm 3 .
  • the center of the preferred Group 14 element-doped nanodiamond particles of the present invention has a diamond structure containing sp3 carbon and doped Group 14 element atoms, the surface of which is covered with an amorphous layer composed of sp2 carbon. ing.
  • the outside of the amorphous layer may be covered with a graphite oxide layer. Further, a hydration layer may be formed between the amorphous layer and the graphite oxide layer.
  • the surface of the Group 14 element-doped nanodiamond particles has one or more oxygen-containing functional groups.
  • the Group 14 element-doped nanodiamonds have a positive or negative zeta potential.
  • the zeta potential of the Group 14 element-doped nanodiamond is preferably ⁇ 70 to 70 mV, more preferably ⁇ 60 to 30 mV.
  • the Group 14 element-doped nanodiamond of the present invention is a step of mixing an explosive material with a Group 14 element compound such as a silicon compound, a germanium compound, a tin compound, and a lead compound in a closed container, and the obtained mixture is used as a cooling medium. It can be manufactured by a manufacturing method comprising the step of exploding under the condition of negative oxygen balance in the presence of.
  • the explosive material is not particularly limited, and known explosive materials can be widely used.
  • TNT trinitrotoluene
  • RDX cyclotrimethylene trinitramine
  • octogen cyclotetramethylenetetranitramine
  • PTN pentaerythritol tetranitrate
  • TNM Tetranitromethane
  • TNM triamino-trinitrobenzene, hexanitrostylben, diaminodinitrobenzofuroxane and the like, and these can be used alone or in combination of two or more.
  • the Group 14 element compound any organic or inorganic compound is widely used as long as it has a Group 14 element atom such as silicon (Si), germanium (Ge), tin (Sn), and lead (Pb). can do.
  • the organic silicon compound is -Acetoxytrimethylsilane, diacetoxydimethylsilane, triacetoxymethylsilane, acetoxytriethylsilane, diacetoxydiethylsilane, triacetoxyethylsilane, acetoxytripropylsilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, ethoxytrimethylsilane , Silanes with lower alkyl groups such as diethoxydimethylsilane, triethoxymethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, trimethylphenoxysilane, -Trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, trichloroethylsilane, dichlorodiethy
  • Aromatic silane in which a silicon atom is incorporated in an aromatic ring such as silabenzene or disilabenzene ⁇ trimethylsilanol, dimethylphenylsilanol, triethylsilanol, diethylsilanediol, tripropylsilanol, dipropylsilanediol, triphenylsilanol, diphenylsilanediol, etc.
  • -Silanes having an alkyl group such as methylsilane, dimethylsilane, trimethylsilane, diethylsilane, triethylsilane, tripropylsilane, diphenylsilane, triphenylsilane, or an aryl group and a hydrogen atom
  • -Tetrakis (chloromethyl) silane tetrakis (hydroxymethyl) silane, tetrakis (trimethylsilyl) silane, tetrakis (trimethylsilyl) methane
  • tetrakis (dimethylsilanolyl) silane tetrakis (tri (hydroxymethyl) silyl) silane, tetrakis (nitrate) Methyl) silane, And so on.
  • Examples of the inorganic silicon compound include silicon oxide, silicon oxynitride, silicon nitride, silicon oxide, silicon nitride, silane, and a silicon-doped carbon material.
  • Examples of the carbon-doped carbon material include graphite, graphite, activated carbon, carbon black, Ketjen black, coke, soft carbon, hard carbon, acetylene black, carbon fiber, and mesoporous carbon.
  • Germanium compounds include methyl germanium, ethyl germanium, trimethyl germanium methoxyd, dimethyl germanium diacetate, tributyl germanium acetate, tetramethoxy germanium, tetraethoxy germanium, tetraphenyl germanium, isobutyl germanium, alkyl germanium trichloride, dimethyl amino germanium trichloride.
  • Organic germanium compounds such as, nitrotriphenol complex (Ge 2 (ntp) 2 O), catechol complex (Ge (cat) 2 ) or aminopyrene complex (Ge 2 (ap) 2 Cl 2 ) and the like, germanium ethoxydo , Germanium alkoxides such as germanium tetrabutoxide.
  • tin compound examples include tin oxide (II), tin oxide (IV), tin sulfide (II), tin sulfide (IV), tin chloride (II), tin chloride (IV), tin bromide (II), and the like.
  • Inorganic tin compounds such as tin fluoride (II), tin acetate, tin sulfate, alkyl tin compounds such as tetramethyltin, monoalkyl tin oxide compounds such as monobutyl tin oxide, dialkyl tin oxide compounds such as dibutyl tin oxide, tetra.
  • Examples thereof include aryl tin compounds such as phenyl tin, organotin compounds such as dimethyl tin maleate, hydroxybutyl tin oxide, and monobutyl tin tris (2-ethylhexanoate).
  • Examples of lead compounds include lead monoxide (PbO), lead dioxide (PbO 2 ), lead tan (Pb 3 O 4 ), lead white (2PbCO 3 ⁇ Pb (OH) 2 ), and lead nitrate (Pb (NO 3 )).
  • Inorganic lead compounds such as lead fluoride (PbF 2 ), lead tetrafluoride (PbF 4 ), lead bromide (PbBr 2 ), lead iodide (PbI 2 ), lead acetate (Pb (CH 3 COO) 2 ), 4 Lead carboxylate (Pb (OCOCH 3 ) 4 ), Tetraethyl lead (Pb (CH 3 CH 2 ) 4 ), Tetramethyl lead (Pb (CH 3 ) 4 ), Tetrabutyl lead (Pb (C 4 H 9 ) 4 ) Examples thereof include organic lead compounds such as.
  • the organic or inorganic Group 14 element compound may be used alone or in combination of two
  • the proportion of the explosive material in the mixture containing the explosive material and the Group 14 elemental compound is preferably 85 to 99.9% by mass, more preferably 86 to 99% by mass, and the proportion of the Group 14 elemental compound is It is preferably 0.1 to 15% by mass, more preferably 1 to 14% by mass.
  • the content of the Group 14 element in the mixture containing the explosive material and the Group 14 element compound is preferably 0.007 to 4.5% by mass, more preferably 0.06 to 4.3% by mass.
  • the above carbon material containing no Group 14 element can be further added.
  • the mixture of the explosive material and the Group 14 element compound may be powder-mixed when both are solid, or may be dissolved or dispersed in an appropriate solvent and mixed.
  • the mixture of explosive material and Group 14 elemental compound further comprises a cooling medium.
  • the cooling medium may be a solid, a liquid, or a gas.
  • Examples of the method using a cooling medium include a method of detonating a mixture of an explosive material and a Group 14 element compound in the cooling medium.
  • Examples of the cooling medium include inert gas (nitrogen, argon, CO), water, ice, liquid nitrogen, an aqueous solution of a Group 14 element-containing salt, and crystalline hydrate.
  • the silicon-containing salt contained in the Group 14 element-containing salt examples include ammonium hexafluorosilicate, ammonium silicate, and tetramethylammonium silicate.
  • the cooling medium is preferably used about 5 times the weight of the explosive.
  • a mixture containing an explosive material and a Group 14 elemental compound is converted to diamond by shock wave compression under high pressure and high temperature conditions produced by the explosion of the explosive material (explosion). Detonation method). During the explosion of explosive materials, Group 14 element atoms are incorporated into the diamond lattice.
  • the carbon source of the nanodiamond can be an explosive material and an organic Group 14 element compound, but if the mixture containing the explosive material and the Group 14 element compound further contains a carbon material that does not contain the Group 14 element, this Carbon materials can also be a carbon source for nanodiamonds.
  • the Group 14 element-doped nanodiamond obtained by the detonation method can be purified and annealed according to a conventional method.
  • Example 1 (1) Synthesis of silicon-doped nanodiamond TNT and cyclotrimethylene trinitramine (hexogen, RDX) were used as explosives, and 0.21 mol of triphenylsilanol (SiPh 3 OH) was used as a silicon compound per 1 mol of TNT, and the temperature was (1).
  • SiPh 3 OH triphenylsilanol
  • the fluorescence spectrum of the obtained silicon-doped nanodiamond having a SiV center is shown in FIG.
  • the obtained evaluation sample was prepared in a 1 wt% aqueous dispersion, a few drops were dropped on a glass plate, and the mixture was dried.
  • the dried sample is irradiated with SiV fluorescent nanodiamonds with excitation light of 532 nm using a micro Raman spectroscope (trade name: Micro Laser Raman spectrophotometer LabRAM HR Evolution, manufactured by HORIBA, Ltd.), and the fluorescence spectrum is obtained with. did.
  • the measurement conditions were excitation light power: 100 ⁇ W, exposure time 1 second, and integration frequency 1 time.
  • Example 2 The silicon-doped nanodiamond having a SiV center obtained in Example 1 was dispersed in water at a concentration of 1% by mass, and the obtained dispersion was dropped onto a glass substrate and dried to prepare an evaluation sample.
  • the obtained evaluation sample was subjected to high-speed mapping (excitation light wavelength: 532 nm, excitation light power: 100 ⁇ W) with a confocal microscope (Fig. 5) (Fig. 2). Furthermore, the point indicated by the arrow in FIG. 2, which is the bright point, was peaked up, the fluorescence spectrum was measured in detail, and it was confirmed that the point indicated by the arrow in FIG. 2 was the fluorescence ZPL of SiV (FIG. 3).
  • RDX cyclotrimethylene trinitramine
  • Example 4 The germanium-doped nanodiamond having a GeV center obtained in Example 3 was dispersed in water at a concentration of 1% by mass, and the obtained dispersion was dropped onto a glass substrate and dried to prepare an evaluation sample.
  • the obtained evaluation sample was subjected to high-speed mapping (excitation light wavelength: 532 nm, excitation light power: 100 ⁇ W) with a confocal microscope (Fig. 5). Furthermore, the point that was the bright spot was peaked up, and the fluorescence spectrum was measured in detail, and it was confirmed that the point was the fluorescence ZPL of GeV (FIG. 6).

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PCT/JP2021/047991 2020-12-25 2021-12-23 温度感受性プローブ Ceased WO2022138854A1 (ja)

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Application Number Priority Date Filing Date Title
CN202180086824.3A CN116670501A (zh) 2020-12-25 2021-12-23 温度敏感性探针
KR1020237020931A KR20230123966A (ko) 2020-12-25 2021-12-23 온도 감수성 프로브
EP21910993.1A EP4269969A4 (en) 2020-12-25 2021-12-23 Temperature sensitive probe
AU2021409095A AU2021409095A1 (en) 2020-12-25 2021-12-23 Temperature sensitive probe
US18/265,455 US20240044722A1 (en) 2020-12-25 2021-12-23 Temperature sensitive probe
CA3203222A CA3203222A1 (en) 2020-12-25 2021-12-23 Temperature sensitive probe
JP2022571638A JPWO2022138854A1 (https=) 2020-12-25 2021-12-23
JP2024063638A JP2024096141A (ja) 2020-12-25 2024-04-10 温度感受性プローブ

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