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WO2007108360A1 - Procédé permettant de détecter une substance par diffusion raman exaltée de surface au moyen d'un tube aveugle de petit diamètre, dispositif permettant de détecter une substance et dispositif permettant de détecter plusieurs substances, et tube aveugle associé - Google Patents

Procédé permettant de détecter une substance par diffusion raman exaltée de surface au moyen d'un tube aveugle de petit diamètre, dispositif permettant de détecter une substance et dispositif permettant de détecter plusieurs substances, et tube aveugle associé Download PDF

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Publication number
WO2007108360A1
WO2007108360A1 PCT/JP2007/054897 JP2007054897W WO2007108360A1 WO 2007108360 A1 WO2007108360 A1 WO 2007108360A1 JP 2007054897 W JP2007054897 W JP 2007054897W WO 2007108360 A1 WO2007108360 A1 WO 2007108360A1
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WO
WIPO (PCT)
Prior art keywords
blind
metal
tube
detecting
blind tube
Prior art date
Application number
PCT/JP2007/054897
Other languages
English (en)
Japanese (ja)
Inventor
Tomohiro Marui
Mayuko Yasuda
Original Assignee
Intellectual Property Bank Corp.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Intellectual Property Bank Corp. filed Critical Intellectual Property Bank Corp.
Priority to JP2008506250A priority Critical patent/JPWO2007108360A1/ja
Publication of WO2007108360A1 publication Critical patent/WO2007108360A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N2021/651—Cuvettes therefore

Definitions

  • Substance detection method substance detection apparatus, multi-substance detection device, blind tube using surface enhanced Raman scattering using small diameter blind tube
  • the present invention relates to a method and an apparatus for detecting a trace substance by surface enhanced Raman scattering (SERS).
  • SERS surface enhanced Raman scattering
  • surface-enhanced Raman scattering light obtained by irradiating a laser beam to a site where analytes, metal particles, and metal colloids are mixed together using a colloid in which metal particles or metal film and metal fine particles are suspended.
  • the present invention uses a thin blind tube also called a Pasteur tube.
  • Patent Document 1 discloses a simple method for preparing a substrate exhibiting high SERS activity by dispersing a SER S substrate in a liquid and fixing it on a solid surface.
  • Patent Document 3 A technique for obtaining strong SERS activity by self-assembling a group of nanoparticles has been studied.
  • Patent Document 2 is also a method of forming a SERS substrate in which particles are periodically aligned and deposited by repeatedly pulling up a flat plate immersed in a solution containing metal fine particles at a predetermined speed.
  • SERS substrate manufacturing methods For example, there is a method for producing a SERS substrate using a surface having affinity with water (hydrophilicity and water repellency) (see Patent Document 5).
  • a colloidal SERS substrate is easier to produce than a solid-phase SERS substrate, but has the disadvantage that the SERS activity disappears in the state of separation and precipitation and in the state of separation and precipitation. For this reason, methods for stabilizing a SERS substrate for a long period of time with a clay-like substance such as smectite (see Patent Document 4) have been studied.
  • Patent Document 8 discloses a trace substance detection method and apparatus using the "Blasmon mirror effect".
  • the plasmon mirror effect means that a group of nanoparticles is self-assembled (self-aligned) in the vicinity of a relatively clean metal surface that induces surface plasmon polaritons with the same applied light energy, and obtains stronger and SERS activity. That is.
  • the conditions and mechanism for obtaining the plasmon mirror effect are not clear, but it is considered important to self-assemble the nanoparticle group in the vicinity of a relatively clean metal surface (Patent Document 8). reference).
  • the nanoparticles are self-assembled (self-aligning IJ) on the metal surface, and further metal deposition is performed on the upper surface, or the nanoparticles are stacked in two steps on the metal surface, thereby sandwiching the sandwich.
  • “Sandwich Substrates” or “Sandwich architecture” is also known. Power, In some sandwich configurations, SERS activity stronger than a single layer may be obtained (see Patent Document 9, Non-Patent Document 4, and Non-Patent Document 5).
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2005-077362 “Method for producing surface-enhanced Raman scattering active substrate” (Keio University)
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-170334 “Raman scattering measurement sensor and manufacturing method thereof” (Japan Science and Technology Agency, etc.)
  • Patent Document 3 Japanese Laid-Open Patent Publication No. 2005-233637 “Raman Spectroscopic Analysis with Gold Nanorod Thin Film” (Japan Science and Technology Agency)
  • Patent Document 4 Japanese Patent Application Laid-Open Publication No. 2004-205435 “Analytical method of binding analysis target substance that does not require labeling dye and analysis kit used therefor” (Fukuo Takao)
  • Patent Document 5 Japanese Laid-Open Patent Publication No. 2005-219184 “Metal Nano-Triangular Column Structure for Single-Molecular Raman Spectroscopy, Array Substrate Formation Method and Single-Molecule Analysis Method Using the Same” (AIST)
  • Patent Document 6 Patent No. 3462339 No. "Capillary electrophoresis detector” (Nippon Telegraph and Telephone Corporation)
  • Patent Document 7 Special Table 2005-507500 Publication “Detection of microfluids by surface-enhanced resonance Raman scattering” (University of Strathclyde et al.)
  • Patent Document 8 International Publication WO2005 114298 Publication ⁇ OPTICAL SENSOR WITH LAYERED P LASMON STRUCTURE FOR ENHANCED DETECTION OF CHEMICAL GROUPS BY SERSJ VP HODLINGS'LLC
  • Patent Document 9 US Patent US6149868 ⁇ Surface enhanced raman scattering from meta
  • Non-Patent Document 2 Takayuki Okamoto (RIKEN) “Investigative Research on Metal Nanoparticle Interactions and Biosensors” 2002 Grant-in-Aid for Scientific Research (C) “Localization of surface plasmons and their applications Investigative research ”report on research results Individual report
  • Non-Patent Document 3 Keir R, Igata E, Arundell M, Smith WE, Graham D, McHugh C, Coop er JM. "SERRS. In situ substrate formation and improved detection using microfluidic sJ Anal Chem. 2002 Apr 1; 74 (7): 1503— 8 ⁇
  • Non-Patent Document 4 Jacquitta K. Daniels and George Chumanov (Clemson University) “Na noparticle-Mirror Sandwich Substrates for Surface-Enhanced Raman Scattering” _J. Phys. Chem. B, 109 (38), 17936 -17942, 2005.
  • Non-Patent Document 5 Orendorff, CJ Gole, A. Sau, TK Murphy, CJ (University of South Carolina) ⁇ Surface-enhanced Raman spectroscopy of Self-assembled monolayers: S andwich architecture and nanoparticle shape dependencej Anal Chem. 2005 May 15 ; 77 (10): 3261--6.
  • An object of the present invention is to propose a method and apparatus that are more practical than conventional methods and apparatuses for detecting trace substances using a SERS substrate or SERS substrate.
  • a method and apparatus that uses a colloidal SERS substrate but does not cause separation and precipitation of the substrate, without using a substrate in which metal fine particles are arranged through complicated processes.
  • An object of the present invention is to propose an effective method and apparatus using both metal particles (or metal films) and metal colloids. Means for solving the problem
  • the method of the present invention is a surface-enhanced Raman scattering light obtained by irradiating laser light to a site where analyte, metal particles, and metal colloid are close to each other.
  • a method for discriminating and detecting an analyte in which the analyte and the metal fine particle colloid prepared in advance are provided in a blind tube in which a metal lump is disposed in the blind part or in a blind tube in which a metal film is disposed on the inner surface of the blind part And a step of injecting a mixture of the analyte and the metal fine particle colloid into the blind tube, and in the vicinity of the solid-liquid interface where the mixture of the injected blind tube is in contact with the blind metal mass.
  • This is a method for detecting trace substances by surface-enhanced Raman scattering, which has a step of observing Raman scattered light by irradiating laser light.
  • the analyte has a small amount of several ⁇ litter, so that the inner diameter is preferably about 1 millimeter. If the mixture is sucked by capillary action (cylinder) and the opening is closed after suction, the inner diameter may be on the order of 100 micrometers.
  • mechanical vibration including sound wave vibration may be applied from the outside in the vicinity of the blind portion.
  • Fig. 2 is a means to vibrate the blind tube (a means to induce a mixture of A and C to the blind part in the blind tube by vibration).
  • Figure 3 shows the Raman scattered light observation process when the blind tube is laid sideways
  • Figure 4 shows the Raman scattered light observation process when the blind tube is upright
  • Figs. 5 and 6 show the observation example and figure. 7 is a photograph of the cecum and blind part used in the examples.
  • the position in the blind part of the metal mass or the inner surface of the blind part of the metal film it is preferable to have a step of measuring the position and arranging a marker at the position of the blind tube based on the measured position so that the measurement position information can be read by observation of the blind tube.
  • the present invention is more practical than conventional SERS substrates and methods and apparatuses for detecting trace substances using SERS substrates. This is because the detection can be carried out only with a blind tube such as glass and a pre-fabricated metal microparticle colloid, which is low in cost. A substrate in which metal fine particles are aligned through a complicated process is not used, but a colloidal SERS substrate is used, but the separation and precipitation of the substrate is not a problem. Even if a metal thin film is disposed on the inner surface of the blind tube, the cost is low. It can be said that this technique is suitable for automatic analysis of a large amount of various analytes.
  • FIG. 1 is an explanatory view of a blind tube of the present invention.
  • A is an example in which metal particles P, which are metal lumps, are arranged in the blind portion
  • (b) is an example in which the diameter of the metal particles is relatively small as in (a).
  • C) is an example in which the metal film S is arranged on the inner surface of the blind part, and (d) is the same as (c), and the arrangement part of the metal film S is arranged so as not to interfere with the Raman measurement from the side of the blind tube.
  • An example of discontinuous dispersion is an example in which metal particles P, which are metal lumps, are arranged in the blind portion
  • (b) is an example in which the diameter of the metal particles is relatively small as in (a).
  • C) is an example in which the metal film S is arranged on the inner surface of the blind part, and (d) is the same as (c), and the arrangement part of the metal film S is arranged so as not to interfere with the Raman measurement from the side of the blind
  • FIG. 2 is a flow explanatory diagram of the detection method of the present invention. 2 by vibration to the blind in the blind tube
  • An oscillating means having an ultrasonic vibrator or an eccentric rotor that applies mechanical vibration including sound waves to the blind tube by means of guiding the mixture.
  • FIG. 5 Data of an embodiment of the present invention, where Peakl is Raman data of a site where the analyte and metal colloid are close together, and Peak2 is a site where the analyte and metal colloid are close together.
  • Datal Raman data, Raman data of the site (data2) where Peak2 analyte, metal particle, and metal colloid are close together.
  • the analyte is adenosine.
  • leveU ⁇ -leveLn is the horizontal plane level including the position of the metal mass or metal film of the 1st ⁇ nth blind tube blind portion of the multiple blind tubes
  • dl ⁇ 'dn is leveU from the optical system reference part of the Raman measurement means, for example ⁇
  • the distance to 'leveLn' is set so that the optical focus of the optical system is all at the horizontal plane level including the position of the metal mass or metal film of the 1st ⁇ nth blind tube blind.
  • FIG. 9 An example of a blind tube in which the position of the metal lump (metal film) in the blind part is measured in advance and a storage medium is provided as a storage means for storing position information in the blind part of the metal lump (metal film).
  • Position information Bl, B2, B3 for the optical marker M placed in the blind part of the blind canal as a reference for the measurement position is encoded by the encoding means 4 and printed by the printing means 5, for example, a bar code 9 (printed on the blind pipe) Printed as Bl, B2 and B3).
  • FIG. 10 An example of a blind tube in which the position of the metal lump (metal film) in the blind portion is measured in advance, and a marker is disposed at the position of the blind tube based on the measured position, as shown in FIG.
  • Position information Bl, B2, B3 is grasped from the marker placement position itself.
  • Ml is the first optical marker placed in the blind canal after the actual measurement of the position of the metal lump or metal film
  • M2 is the blind in the blind canal after the actual measurement of the position of the metal lump or metal film.
  • the arranged second optical marker, ML is a predetermined distance apart from the position of the metal block or metal film (the marker position is separated so as not to obstruct the Raman measurement).
  • FIG.11 There is a margin for grinding 7 at the end of the blind tube, and the grinding margin 7 is ground according to the position of the metal mass of the blind part or the metal film on the inner surface of the blind part, and multiple blind pipes are ground to the reference surface
  • 7 is the margin of the bottom of the blind tube for leveling the metal lump or metal film
  • 8 is the bottom of the blind tube after being ground for leveling
  • G is the reference plane corresponding to the focal point of the laser beam irradiation
  • H is one of the focal planes of the actual laser beam irradiation, and is the highest level in the horizontal plane including the position of the metal block or metal film
  • J is a certain level difference from the actual focal plane H of the reference plane G.
  • a cone-shaped reference shape 7A is provided at the end of the blind tube, and has a reference surface corresponding to the focal point of the laser beam irradiation, and a conical knife that fits the above-described cone-shaped shape on the reference surface.
  • the mold is opened, and the depth of the cone-female mold is determined according to the position of the blind metal block or the metal film on the inner surface of the blind part.
  • a plurality of blind tubes are arranged in parallel by fitting the cone-shaped reference shape 7A at the end of the blind tube into the conical female-type opening.
  • 7A is a cone-shaped reference shape for leveling the metal mass or metal film position.
  • FIG. 13 This is an example of a blind tube according to the present invention, in which (a) is a method of charging a metal material into a glass empty blind tube, (b) is a metal melting by heating the blind portion of a glass empty blind tube, c) shows the steps of forming the constricted part to prevent the metal from falling off by pressurizing and constricting the blind part.
  • Printing method 6 Trace substance detection chip with multiple blind tubes 1 arranged in parallel
  • ACP AC is close to P (or metal film)
  • level_2 The horizontal plane including the position of the metal mass or metal film of the second blind canal of multiple blind tubes
  • level_3 Horizontal plane level including the location of the metal mass or metal film of the 3rd culm
  • n Horizontal plane level including the position of the metal mass or metal film of the nth cephalic blind region of several culm
  • Peak2 A characteristic peak of adenosine (analyte) in data2
  • QL1 A level corresponding to the PL1 level. It corresponds to a female cone to be fitted.
  • QL2 Level corresponding to PL2 level Corresponds to the female cone to be fitted.
  • QL3 A level corresponding to the PL3 level. It corresponds to a female cone to be fitted.
  • the device according to the present invention includes a blind tube in which a metal lump is disposed in the blind part, or a blind tube in which a metal film is disposed on the inner surface of the blind part, and laser light is applied to the blind tube.
  • the device according to the present invention may be provided with means for applying vibration to the blind tube to guide the mixture of the analyte and the metal fine particle colloid to the blind part.
  • the device according to the present invention (Claim 7) is provided in the position of the blind portion of the metal mass or the inner surface of the blind portion of the metal film before the step of mixing the analyte and the colloidal metal colloid prepared in advance.
  • the position is measured in advance, and a blind tube in which a single force is arranged at the position of the blind tube based on the measurement position, and the detection device has a means for reading the marker position and also has a fixed position.
  • the means for focusing the laser beam near the liquid interface discriminates and focuses the solid-liquid interface based on the marker position read by the reading means.
  • the marker is located most in the plane group perpendicular to the tube axis of the blind tube and including the blind metal mass or the metal film of the blind inner surface.
  • the position included in the plane close to the open end of the cephalic tube (see PLU in Figure 4) and / or the position closest to the blind end of the cephalic canal and the position of the plane (see PLL in Figure 4) is preferred.
  • the storage means for storing the measurement position information and the information reading means for the storage means are combined, and the laser beam is focused near the solid-liquid interface.
  • the means for determining and focusing the solid-liquid interface based on the position information on the blind portion of the metal lump read by the reading means or the position information on the inner surface of the blind portion of the metal film may be used.
  • a storage medium as storage means for storing measurement position information in the blind tube is provided, and information reading means in the storage means is information reading means in the storage medium provided in the blind tube. Is preferred (see brief description of FIGS. 9 and 9).
  • the present invention provides a multiple detection for detecting a minute amount of analyte latent in a plurality of sampling solutions. It may constitute a several substance detection device. Here, it is hoped that the position of the metal inside the plurality of blind tubes approximately coincides with the axial direction of the blind tubes so that the focusing of the laser light can be omitted in the vicinity of each solid-liquid interface. Masle.
  • the parallel condition is as follows: the parallel condition is: in a plane perpendicular to one blind tube axis and in a group of planes including a blind metal mass or a metal film on the inner surface of the blind. The surface closest to the open end of the blind canal or the surface closest to the blind canal is perpendicular to the axis of the other canal and is included in the group of surfaces including the blind metal mass or the metal film on the inside of the blind (See Figure 8).
  • this is a multi-substance detection device having the following structure (refer to claims 12, FIG. 11 and a brief description of FIG. 11).
  • the multiple substance detection device has a reference surface corresponding to the focal point of the laser beam irradiation.
  • the grinding margin at the end of the blind pipe is ground according to the position of the metal block of the blind block or the metal film on the inner surface of the blind block.
  • a plurality of blind tubes are arranged in parallel with the ground surface ground to the reference surface.
  • FIG. 12 and FIG. 12 Another specific embodiment (see the brief description of claim 13, FIG. 12 and FIG. 12) is as follows: 1) There is a conical oscillating reference shape at the end of the blind tube before the parallel arrangement. . 2) The multi-substance detection device has a reference plane corresponding to the focal point of the laser beam irradiation, and a conical knife type that fits the circular cone type is opened on the reference plane. 3) The depth of the conical knife type is determined in accordance with the position of the blind metal block or the metal film on the inner surface of the blind part. 4) A plurality of blind tubes are arranged in parallel by fitting the cone-shaped reference shape at the end of the blind tube into the conical female opening.
  • FIG. 13 A preferred embodiment of the blind tube of the present invention is shown in FIG. 13 together with its production method. That is, (Claim 14) is a blind tube in which metal is disposed in the blind part, and after the step of introducing the metal material into the blind tube (FIG. 13 (a)), the metal in the blind part is melted. A blind tube in which the input metal material is melted and fixed to the inner surface of the blind tube blind part by the step of heating above the temperature (FIG. 13 (b)) is suitable.
  • (Claim 15) A blind tube in which a thin film in which the above-mentioned metal material is melt-extended is disposed on the inner surface of the blind tube blind portion by the same metal material charging step and heating step is also suitable.
  • (Claim 16) is a blind tube in which metal is disposed in the blind portion, and after the step of disposing the metal material in the blind tube, the open end side of the blind tube metal disposed portion. Even if a part having an inner diameter smaller than the inner diameter of the blind tube metal placement part is formed on the open end side of the metal placement part by the process of constricting the pressure from the outside of the blind pipe (Fig. 13 (c)) Good. This small inner diameter portion is suitable because it is difficult for the metal material to separate from the blind portion without being melt-fixed or melt-extended by heating.
  • the blind tube member is made of heat resistant material (heat resistant glass), it is easy to heat, and only the metal in the blind tube blind part is locally heated by local heating means such as laser heating to avoid melting of the blind tube material. You can do it.
  • all or part of the metal may be a low melting point alloy having a low melting point, and only the alloy may be melted.

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  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

Cette invention concerne un procédé et un dispositif permettant de détecter une très petite quantité d'une substance par diffusion Raman exaltée de surface (DRES), lequel procédé permettant d'obtenir une excellente mise en oeuvre pratique et une observation rapide. Le procédé permettant de détecter une très petite quantité d'une substance par diffusion Raman exaltée de surface comprend l'étape qui consiste à mélanger un produit à analyser et un colloïde de particules métalliques fines préalablement élaboré, afin de préparer un mélange qui sera placé dans un tube aveugle dans lequel une masse métallique est installée dans la partie aveugle du tube; l'étape qui consiste à verser le mélange constitué du produit à analysé et du colloïde de particules métalliques fines dans le tube aveugle; et l'étape qui consiste à appliquer un faisceau laser à une partie autour d'une interface entre le solide et le liquide dans laquelle ledit mélange, à l'intérieur du tube aveugle, est en contact avec la masse métallique de la partie aveugle pour observer la lumière diffusée par diffusion Raman. Cette invention concerne également un dispositif permettant la mise en oeuvre du procédé susmentionné.
PCT/JP2007/054897 2006-03-17 2007-03-13 Procédé permettant de détecter une substance par diffusion raman exaltée de surface au moyen d'un tube aveugle de petit diamètre, dispositif permettant de détecter une substance et dispositif permettant de détecter plusieurs substances, et tube aveugle associé WO2007108360A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008506250A JPWO2007108360A1 (ja) 2006-03-17 2007-03-13 細径盲管を用いた表面増強ラマン散乱による物質検知方法および物質検知装置、複数物質検知デバイス、盲管

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-073816 2006-03-17
JP2006073816 2006-03-17

Publications (1)

Publication Number Publication Date
WO2007108360A1 true WO2007108360A1 (fr) 2007-09-27

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011500818A (ja) * 2007-10-23 2011-01-06 アラーガン インコーポレイテッド 治療用置換ラクタム類
JP2012181022A (ja) * 2011-02-28 2012-09-20 Canon Inc ラマン振動の強度分布情報と質量分布情報とを位置合わせする方法

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Publication number Priority date Publication date Assignee Title
JP2003511666A (ja) * 1999-10-06 2003-03-25 サーロメッド・インコーポレーテッド 新規な表面強化されたラマン散乱（ｓｅｒｓ）−活性基体及びラマン分光とキャピラリー電気泳動（ｃｅ）を接続する方法
JP2004530867A (ja) * 2001-03-01 2004-10-07 ニューメキシコ ステート ユニバーシティ テクノロジー トランスファー コーポレーション ナノ粒子、マイクロキャビティ、および半連続金属膜を使用した光デバイスおよび光学的方法
WO2007049487A1 (fr) * 2005-10-25 2007-05-03 Kyushu University, National University Corporation Substrat pour analyse destine a un usage dans une analyse spectroscopique raman et ensemble de substrat pour analyse

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003511666A (ja) * 1999-10-06 2003-03-25 サーロメッド・インコーポレーテッド 新規な表面強化されたラマン散乱（ｓｅｒｓ）−活性基体及びラマン分光とキャピラリー電気泳動（ｃｅ）を接続する方法
JP2004530867A (ja) * 2001-03-01 2004-10-07 ニューメキシコ ステート ユニバーシティ テクノロジー トランスファー コーポレーション ナノ粒子、マイクロキャビティ、および半連続金属膜を使用した光デバイスおよび光学的方法
WO2007049487A1 (fr) * 2005-10-25 2007-05-03 Kyushu University, National University Corporation Substrat pour analyse destine a un usage dans une analyse spectroscopique raman et ensemble de substrat pour analyse

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011500818A (ja) * 2007-10-23 2011-01-06 アラーガン インコーポレイテッド 治療用置換ラクタム類
JP2012181022A (ja) * 2011-02-28 2012-09-20 Canon Inc ラマン振動の強度分布情報と質量分布情報とを位置合わせする方法

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