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WO2016031616A1 - Matériau d'échantillonnage pour chromatographie liquide à haute performance - Google Patents

Matériau d'échantillonnage pour chromatographie liquide à haute performance Download PDF

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Publication number
WO2016031616A1
WO2016031616A1 PCT/JP2015/073084 JP2015073084W WO2016031616A1 WO 2016031616 A1 WO2016031616 A1 WO 2016031616A1 JP 2015073084 W JP2015073084 W JP 2015073084W WO 2016031616 A1 WO2016031616 A1 WO 2016031616A1
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Prior art keywords
liquid chromatography
performance liquid
sample
carbon nanotubes
carbon nanotube
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English (en)
Japanese (ja)
Inventor
前野　洋平
卓哉 湯峯
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Nitto Denko Corp
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Nitto Denko Corp
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86

Definitions

  • the present invention relates to a sample sampling material for high performance liquid chromatography.
  • HPLC high-performance liquid chromatography
  • a liquid moving bed is pressurized by a pump or the like and passed through a column, and analytes interact with the stationary phase and the mobile phase (adsorption, distribution, ion exchange, size exclusion, etc.). It is an analysis method that uses the difference to perform high-performance separation and detection.
  • An object of the present invention is to provide a sample sampling material for high-performance liquid chromatography that can be sampled without damaging the sample and without being contaminated.
  • Sample sampling material for high performance liquid chromatography of the present invention A sampling material for sampling a sample of high performance liquid chromatography, Including a base material and a fibrous columnar structure,
  • the fibrous columnar structure is a fibrous columnar structure including a plurality of fibrous columnar objects,
  • the fibrous columnar material is oriented in a substantially vertical direction with respect to the substrate.
  • the fibrous columnar structure is a carbon nanotube aggregate including a plurality of carbon nanotubes.
  • the carbon nanotube has a plurality of layers, the distribution width of the number distribution of the carbon nanotubes is 10 or more, and the relative frequency of the mode value of the number distribution of the carbon nanotubes is 25% or less. .
  • the carbon nanotube has a length of 300 ⁇ m or more.
  • the carbon nanotube has a plurality of layers, the mode value of the number distribution of the carbon nanotubes is present in 10 or less layers, and the relative frequency of the mode value is 30% or more. .
  • the carbon nanotube has a length of 300 ⁇ m or more.
  • the material of the base material is a nonpolar resin or a metal.
  • the sample is a thin film sample.
  • the sample sampling material for high performance liquid chromatography of the present invention is a sampling material for sampling a sample of high performance liquid chromatography.
  • the sample sampling material for high performance liquid chromatography of the present invention is a sampling material for collecting a sample necessary for measuring high performance liquid chromatography by contacting the sample.
  • any suitable sample that needs to be analyzed by high performance liquid chromatography can be adopted.
  • the sample that can be sampled with the sample sampling material for high performance liquid chromatography of the present invention is preferably a thin film sample in that the effect of the present invention can be sufficiently exhibited.
  • Examples of such a thin film sample include human skin, various oil films such as roll-shaped foreign matters during production and bleeds on resin, powders, liquids, and the like.
  • the thickness of such a thin film sample is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.3 ⁇ m to 50 ⁇ m, still more preferably 0.5 ⁇ m to 30 ⁇ m, and particularly preferably 0.7 ⁇ m to It is 20 ⁇ m, and most preferably 1 ⁇ m to 10 ⁇ m.
  • the sample sampling material for high performance liquid chromatography of the present invention includes a base material and a fibrous columnar structure.
  • the sample sampling material for high-performance liquid chromatography of the present invention contains a base material and a specific fibrous columnar structure as described later, so that the sample can be sampled without damaging the sample and without being contaminated.
  • a sample sampling material for chromatography can be provided.
  • the sample sampling material for high-performance liquid chromatography of the present invention may have any appropriate other member as long as it includes a base material and a fibrous columnar structure, as long as the effects of the present invention are not impaired. good.
  • Such a substrate is preferably a substrate whose material is a nonpolar resin or metal.
  • nonpolar resins examples include polyethylene, polypropylene, fluorides thereof, and blends thereof.
  • the nonpolar resin is preferably a propylene-based resin, more preferably polypropylene, from the viewpoint that the effects of the present invention can be further expressed.
  • metals examples include aluminum, copper, gold, and nickel.
  • the metal is preferably aluminum from the viewpoint that the effects of the present invention can be further exhibited.
  • the thickness of the substrate can be set to any appropriate value depending on the purpose.
  • the thickness of such a substrate is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 5 ⁇ m to 700 ⁇ m, even more preferably 10 ⁇ m to 500 ⁇ m, and particularly preferably, from the viewpoint that the effects of the present invention can be further exhibited. Is 20 ⁇ m to 300 ⁇ m, and most preferably 10 ⁇ m to 100 ⁇ m.
  • the surface of the substrate is subjected to conventional surface treatments such as chromic acid treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, etc. in order to improve adhesion, retention, etc.
  • Coating treatment with a primer for example, the above-mentioned adhesive substance may be performed.
  • the base material may be a single layer or a multilayer body.
  • the fibrous columnar structure is a fibrous columnar structure including a plurality of fibrous columnar objects.
  • the size of the fibrous columnar structure may be any size as long as the sample necessary for measuring the high performance liquid chromatography can be collected by contacting the sample and the high performance liquid chromatography can be measured.
  • An appropriate size can be adopted.
  • the size when viewed from the upper surface (the surface side opposite to the substrate of the fibrous columnar structure) is preferably 1 mm 2 to 1000 mm 2 , more preferably 10 mm 2 to 700 mm 2 , more preferably 20 mm 2 to 500 mm 2 , particularly preferably 30 mm 2 to 300 mm 2 , and most preferably 50 mm 2 to 100 mm 2 .
  • the sample sampling material for high performance liquid chromatography of the present invention can effectively collect a sample necessary for measuring high performance liquid chromatography by contacting the sample. Liquid chromatography can be easily measured.
  • the length of the fibrous columnar material is preferably 50 ⁇ m to 3000 ⁇ m, more preferably 200 ⁇ m to 2000 ⁇ m, still more preferably 300 ⁇ m to 1500 ⁇ m, particularly preferably 400 ⁇ m to 1000 ⁇ m, and most preferably 500 ⁇ m to 1000 ⁇ m. It is. By keeping the length of the fibrous columnar material within the above range, it is possible to more effectively provide a sample sampling material for high performance liquid chromatography that can be sampled without damaging the sample and without being contaminated.
  • FIG. 1 shows a schematic sectional view of an example of a sample sampling material for high performance liquid chromatography in a preferred embodiment of the present invention.
  • a sample sampling material 1000 for high performance liquid chromatography has a base material 100 and a fibrous columnar structure 10.
  • the fibrous columnar structure 10 includes a plurality of fibrous columnar objects 2. One end of the fibrous columnar object 2 is fixed to the substrate 100.
  • the fibrous columnar body 2 is oriented in the direction of the length L.
  • the fibrous columnar body 2 is oriented in a substantially vertical direction with respect to the substrate 100.
  • the “substantially perpendicular direction” means that the angle with respect to the surface of the substrate 100 is preferably 90 ° ⁇ 20 °, more preferably 90 ° ⁇ 15 °, and further preferably 90 ° ⁇ 10 °. And particularly preferably 90 ° ⁇ 5 °.
  • any appropriate material can be adopted as the material for the fibrous columnar material.
  • examples thereof include metals such as aluminum and iron; inorganic materials such as silicon; carbon materials such as carbon nanofibers and carbon nanotubes (CNT); and high modulus resins such as engineering plastics and super engineering plastics.
  • the resin include polystyrene, polyethylene, polypropylene, polyethylene terephthalate, acetyl cellulose, polycarbonate, polyimide, polyamide, and the like.
  • Any appropriate physical properties can be adopted as the physical properties such as the molecular weight of the resin as long as the object of the present invention can be achieved.
  • the diameter of the fibrous columnar material is preferably 0.3 nm to 2000 nm, more preferably 1 nm to 1000 nm, still more preferably 2 nm to 500 nm, particularly preferably 2 nm to 200 nm, and most preferably 2 nm to 100 nm.
  • the fibrous columnar structure is preferably a carbon nanotube aggregate including a plurality of carbon nanotubes.
  • the fibrous columnar product is preferably a carbon nanotube.
  • a sample column for high performance liquid chromatography that can sample without damaging and contaminating the sample more effectively because the fibrous columnar structure is an aggregate of carbon nanotubes including a plurality of carbon nanotubes. Can be provided.
  • One preferred embodiment of the aggregate of carbon nanotubes includes a plurality of carbon nanotubes, the carbon nanotubes having a plurality of layers, and the carbon nanotube layer.
  • the distribution width of the number distribution is 10 layers or more, and the relative frequency of the mode value of the layer number distribution is 25% or less.
  • the distribution width of the number distribution of the carbon nanotubes is preferably 10 or more, more preferably 10 to 30 layers, still more preferably 10 to 25 layers, particularly The number of layers is preferably 10 to 20 layers.
  • the “distribution width” of the number distribution of carbon nanotubes refers to the difference between the maximum number and the minimum number of carbon nanotube layers.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and further, the carbon nanotubes have excellent adhesive properties. It can be the carbon nanotube aggregate shown. Therefore, the sample sampling material for high performance liquid chromatography having such an aggregate of carbon nanotubes can be sampled without sufficiently damaging the sample and without being sufficiently contaminated.
  • the number of layers and the number distribution of carbon nanotubes may be measured by any appropriate apparatus. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, at least 10, preferably 20 or more carbon nanotubes may be taken out from the aggregate of carbon nanotubes and measured by SEM or TEM to evaluate the number of layers and the number distribution of the layers.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the maximum number of carbon nanotube layers is preferably 5 to 30 layers, more preferably 10 to 30 layers, and even more preferably 15 to 30 layers. Particularly preferred are 15 to 25 layers.
  • the minimum number of carbon nanotube layers is preferably 1 to 10 layers, and more preferably 1 to 5 layers.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, Furthermore, the carbon nanotube can be a carbon nanotube aggregate exhibiting excellent adhesive properties. Therefore, the sample sampling material for high performance liquid chromatography having such an aggregate of carbon nanotubes can be sampled without sufficiently damaging the sample and without being sufficiently contaminated.
  • the relative frequency of the mode value of the number distribution of carbon nanotubes is preferably 25% or less, more preferably 1% to 25%, and even more preferably 5% to 25%. Particularly preferred is 10% to 25%, and most preferred is 15% to 25%.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area. It can be an aggregate of carbon nanotubes exhibiting excellent adhesive properties. Therefore, the sample sampling material for high performance liquid chromatography having such an aggregate of carbon nanotubes can be sampled without sufficiently damaging the sample and without being sufficiently contaminated.
  • the mode of the number distribution of the carbon nanotubes is preferably present from 2 layers to 10 layers, more preferably from 3 layers to 10 layers. .
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and the carbon nanotubes have excellent adhesive properties. It can become the carbon nanotube aggregate which shows. Therefore, the sample sampling material for high performance liquid chromatography having such an aggregate of carbon nanotubes can be sampled without sufficiently damaging the sample and without being sufficiently contaminated.
  • the carbon nanotubes may have any appropriate shape in cross section.
  • the cross section may be substantially circular, elliptical, n-gonal (n is an integer of 3 or more), and the like.
  • the length of the carbon nanotube is preferably 50 ⁇ m or more, more preferably 100 ⁇ m to 3000 ⁇ m, still more preferably 300 ⁇ m to 1500 ⁇ m, still more preferably 400 ⁇ m to 1000 ⁇ m, particularly
  • the thickness is preferably 500 ⁇ m to 1000 ⁇ m.
  • the diameter of the carbon nanotube is preferably 0.3 nm to 2000 nm, more preferably 1 nm to 1000 nm, and further preferably 2 nm to 500 nm.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area.
  • the carbon nanotube aggregates exhibit excellent adhesive properties. Can be. Therefore, the sample sampling material for high performance liquid chromatography having such an aggregate of carbon nanotubes can be sampled without sufficiently damaging the sample and without being sufficiently contaminated.
  • the specific surface area and density of the carbon nanotubes can be set to any appropriate values.
  • Another preferred embodiment of the aggregate of carbon nanotubes includes a plurality of carbon nanotubes, the carbon nanotubes having a plurality of layers, and the carbon nanotubes.
  • the mode value of the number distribution of layers exists in 10 layers or less, and the relative frequency of the mode value is 30% or more.
  • the distribution width of the number distribution of the carbon nanotubes is preferably 9 or less, more preferably 1 to 9 layers, further preferably 2 to 8 layers, particularly Three to eight layers are preferred.
  • the “distribution width” of the number distribution of carbon nanotubes refers to the difference between the maximum number and the minimum number of carbon nanotube layers.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and furthermore, the carbon nanotubes have excellent adhesive properties. It can be the carbon nanotube aggregate shown. Therefore, the sample sampling material for high performance liquid chromatography having such an aggregate of carbon nanotubes can be sampled without sufficiently damaging the sample and without being sufficiently contaminated.
  • the number of layers and the number distribution of carbon nanotubes may be measured by any appropriate apparatus. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, at least 10, preferably 20 or more carbon nanotubes may be taken out from the aggregate of carbon nanotubes and measured by SEM or TEM to evaluate the number of layers and the number distribution of the layers.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the maximum number of carbon nanotube layers is preferably 1 to 20 layers, more preferably 2 to 15 layers, and further preferably 3 to 10 layers. .
  • sample sampling materials for high-performance liquid chromatography that can be sampled without damaging or contaminating the sample are provided more effectively. can do.
  • the minimum number of carbon nanotube layers is preferably 1 to 10 layers, more preferably 1 to 5 layers.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, Furthermore, the carbon nanotube can be a carbon nanotube aggregate exhibiting excellent adhesive properties. Therefore, the sample sampling material for high performance liquid chromatography having such an aggregate of carbon nanotubes can be sampled without sufficiently damaging the sample and without being sufficiently contaminated.
  • the relative frequency of the mode value of the number distribution of the carbon nanotubes is preferably 30% or more, more preferably 30% to 100%, and further preferably 30% to 90%. Particularly preferred is 30% to 80%, and most preferred is 30% to 70%.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area. It can be an aggregate of carbon nanotubes exhibiting excellent adhesive properties. Therefore, the sample sampling material for high performance liquid chromatography having such an aggregate of carbon nanotubes can be sampled without sufficiently damaging the sample and without being sufficiently contaminated.
  • the mode value of the number distribution of the carbon nanotubes is preferably present in the number of layers of 10 or less, more preferably in the number of layers from 1 to 10, and more preferably The number of layers is from 2 to 8 and particularly preferably from 2 to 6 layers.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and the carbon nanotubes have excellent adhesive properties. It can become the carbon nanotube aggregate which shows. Therefore, the sample sampling material for high performance liquid chromatography having such an aggregate of carbon nanotubes can be sampled without sufficiently damaging the sample and without being sufficiently contaminated.
  • the shape of the carbon nanotube it is sufficient that its cross section has any appropriate shape.
  • the cross section may be substantially circular, elliptical, n-gonal (n is an integer of 3 or more), and the like.
  • the length of the carbon nanotube is preferably 50 ⁇ m or more, more preferably 100 ⁇ m to 3000 ⁇ m, still more preferably 300 ⁇ m to 1500 ⁇ m, still more preferably 400 ⁇ m to 1000 ⁇ m, and particularly
  • the thickness is preferably 500 ⁇ m to 1000 ⁇ m.
  • the diameter of the carbon nanotube is preferably 0.3 nm to 2000 nm, more preferably 1 nm to 1000 nm, and further preferably 2 nm to 500 nm.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area.
  • the carbon nanotube aggregates exhibit excellent adhesive properties. Can be. Therefore, the sample sampling material for high performance liquid chromatography having such an aggregate of carbon nanotubes can be sampled without sufficiently damaging the sample and without being sufficiently contaminated.
  • the specific surface area and density of the carbon nanotubes can be set to any appropriate values.
  • Any appropriate method can be adopted as a method for producing a carbon nanotube aggregate.
  • a method for producing a carbon nanotube aggregate for example, a catalyst layer is formed on a smooth substrate, a carbon source is filled in a state where the catalyst is activated by heat, plasma, etc., and carbon nanotubes are grown.
  • a method of producing an aggregate of carbon nanotubes oriented almost vertically from a substrate by a vapor deposition method (Chemical Vapor Deposition: CVD method).
  • CVD method Chemical Vapor Deposition: CVD method
  • any appropriate substrate can be adopted as the substrate that can be used in the method for producing a carbon nanotube aggregate.
  • the material which has smoothness and the high temperature heat resistance which can endure manufacture of a carbon nanotube is mentioned.
  • examples of such materials include quartz glass, silicon (such as a silicon wafer), and a metal plate such as aluminum.
  • any appropriate apparatus can be adopted as an apparatus for producing the carbon nanotube aggregate.
  • a thermal CVD apparatus as shown in FIG. 2, a hot wall type configured by surrounding a cylindrical reaction vessel with a resistance heating type electric tubular furnace can be cited.
  • a heat-resistant quartz tube is preferably used as the reaction vessel.
  • Any suitable catalyst can be used as a catalyst (catalyst layer material) that can be used in the production of the carbon nanotube aggregate.
  • metal catalysts such as iron, cobalt, nickel, gold, platinum, silver, copper, are mentioned.
  • an alumina / hydrophilic film may be provided between the substrate and the catalyst layer as necessary.
  • any appropriate method can be adopted as a method for producing the alumina / hydrophilic film.
  • it can be obtained by forming a SiO 2 film on a substrate, depositing Al, and then oxidizing it by raising the temperature to 450 ° C.
  • Al 2 O 3 interacts with the SiO 2 film hydrophilic, different Al 2 O 3 surface particle diameters than those deposited Al 2 O 3 directly formed.
  • Al is deposited and heated to 450 ° C. and oxidized without forming a hydrophilic film on the substrate, Al 2 O 3 surfaces having different particle diameters may not be formed easily.
  • a hydrophilic film is prepared on a substrate and Al 2 O 3 is directly deposited, it is difficult to form Al 2 O 3 surfaces having different particle diameters.
  • the thickness of the catalyst layer that can be used in the production of the carbon nanotube aggregate is preferably 0.01 nm to 20 nm, more preferably 0.1 nm to 10 nm in order to form fine particles.
  • the formed carbon nanotubes can have both excellent mechanical properties and a high specific surface area. It can be a carbon nanotube aggregate exhibiting excellent adhesive properties. Therefore, the sample sampling material for high performance liquid chromatography having such an aggregate of carbon nanotubes can be sampled without sufficiently damaging the sample and without being sufficiently contaminated.
  • Any appropriate method can be adopted as a method for forming the catalyst layer.
  • a method of depositing a metal catalyst by EB (electron beam), sputtering, or the like, a method of applying a suspension of metal catalyst fine particles on a substrate, and the like can be mentioned.
  • any appropriate carbon source can be used as the carbon source that can be used for the production of the carbon nanotube aggregate.
  • hydrocarbons such as methane, ethylene, acetylene, and benzene
  • alcohols such as methanol and ethanol
  • Arbitrary appropriate temperature can be employ
  • the temperature is preferably 400 ° C to 1000 ° C, more preferably 500 ° C to 900 ° C, and further preferably 600 ° C to 800 ° C. .
  • ⁇ Evaluation of the number and distribution of carbon nanotubes in a carbon nanotube aggregate The number of carbon nanotube layers and the number distribution of carbon nanotubes in the aggregate of carbon nanotubes were measured by a scanning electron microscope (SEM) and / or a transmission electron microscope (TEM). From the obtained carbon nanotube aggregate, at least 10 or more, preferably 20 or more carbon nanotubes were observed by SEM and / or TEM, the number of layers of each carbon nanotube was examined, and a layer number distribution was created.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • Example 1 An Al thin film (thickness: 10 nm) was formed on a silicon wafer (manufactured by Silicon Technology) as a substrate by a sputtering apparatus (manufactured by ULVAC, RFS-200). On this Al thin film, an Fe thin film (thickness 1 nm) was further vapor-deposited by a sputtering apparatus (ULVAC, RFS-200). Thereafter, this substrate was placed in a 30 mm ⁇ quartz tube, and a mixed gas of helium / hydrogen (90/50 sccm) maintained at 600 ppm in water was allowed to flow through the quartz tube for 30 minutes to replace the inside of the tube.
  • a mixed gas of helium / hydrogen 90/50 sccm
  • the inside of the tube was heated to 765 ° C. using an electric tubular furnace and stabilized at 765 ° C. While maintaining the temperature at 765 ° C., the tube was filled with a mixed gas of helium / hydrogen / ethylene (85/50/5 sccm, moisture content 600 ppm) and left for 5 minutes to grow carbon nanotubes on the substrate.
  • a mixed gas of helium / hydrogen / ethylene 85/50/5 sccm, moisture content 600 ppm
  • Example 2 In Example 1, except that the thickness of the Fe thin film was changed to 2 nm and the standing time was changed to 15 minutes, the same procedure as in Example 1 was performed, and the carbon nanotube aggregate (2) in which the carbon nanotubes were oriented in the length direction Got.
  • the carbon nanotubes included in the carbon nanotube aggregate (2) had a length of 300 ⁇ m.
  • the mode value was present in three layers, and the relative frequency was 72%.
  • a sample sampling material (2) for high performance liquid chromatography was obtained in which a carbon nanotube aggregate having a length of 10 mm ⁇ width of 10 mm and a length of 300 ⁇ m was placed on a 30 ⁇ m thick substrate.
  • the evaluation results are shown in Table 1.
  • Example 3 A carbon nanotube aggregate (3) in which the carbon nanotubes were oriented in the length direction was obtained in the same manner as in Example 1, except that the standing time was changed to 25 minutes.
  • the length of the carbon nanotube with which the carbon nanotube aggregate (3) is provided was 500 ⁇ m.
  • the mode value was present in two layers, and the relative frequency was 75%.
  • a sample sampling material (3) for high performance liquid chromatography was obtained in which a carbon nanotube aggregate having a length of 10 mm, a width of 10 mm and a length of 500 ⁇ m was placed on a 30 ⁇ m thick substrate.
  • the evaluation results are shown in Table 1.
  • Example 4 An Al thin film (thickness 10 nm) was formed on a silicon substrate (made by KST, wafer with thermal oxide film, thickness 1000 ⁇ m) using a vacuum deposition apparatus (made by JEOL, JEE-4X Vacuum Evaporator), and then oxidized at 450 ° C. for 1 hour. Treated. In this way, an Al 2 O 3 film was formed on the silicon substrate. On this Al 2 O 3 film, an Fe thin film (thickness 2 nm) was further deposited by a sputtering apparatus (manufactured by ULVAC, RFS-200) to form a catalyst layer.
  • a sputtering apparatus manufactured by ULVAC, RFS-200
  • the obtained silicon substrate with a catalyst layer was cut and placed in a 30 mm ⁇ quartz tube, and a helium / hydrogen (120/80 sccm) mixed gas maintained at a moisture content of 350 ppm was allowed to flow into the quartz tube for 30 minutes. Was replaced. Thereafter, the inside of the tube was gradually raised to 765 ° C. in 35 minutes using an electric tubular furnace, and stabilized at 765 ° C. While maintaining the temperature at 765 ° C., a mixed gas of helium / hydrogen / ethylene (105/80/15 sccm, moisture content 350 ppm) is filled in the tube, and left for 5 minutes to grow carbon nanotubes on the substrate.
  • an aggregate of carbon nanotubes (4) in which is oriented in the length direction was obtained.
  • the length of the carbon nanotube provided in the carbon nanotube aggregate (4) was 100 ⁇ m.
  • the distribution width of the number distribution is 17 layers (4 to 20 layers), and the mode value is present in 4 layers and 8 layers, The frequencies were 20% and 20%, respectively.
  • a sample sampling material (4) for high performance liquid chromatography was obtained, in which a carbon nanotube aggregate having a length of 10 mm, a width of 10 mm, and a length of 100 ⁇ m was placed on a 30 ⁇ m thick substrate.
  • the evaluation results are shown in Table 1.
  • Example 5 In Example 4, a carbon nanotube aggregate (5) in which the carbon nanotubes were oriented in the length direction was obtained in the same manner as in Example 4 except that the standing time was changed to 15 minutes.
  • the length of the carbon nanotube provided in the carbon nanotube aggregate (5) was 300 ⁇ m.
  • the distribution width of the number distribution is 17 layers (4 to 20 layers), and the mode value is present in the 4th and 8th layers.
  • the frequencies were 20% and 20%, respectively.
  • Example 6 In Example 4, a carbon nanotube aggregate (6) in which the carbon nanotubes were aligned in the length direction was obtained in the same manner as in Example 4 except that the standing time was changed to 25 minutes.
  • the length of the carbon nanotube with which the carbon nanotube aggregate (6) is provided was 500 ⁇ m.
  • the distribution width of the number distribution is 17 layers (4 to 20 layers), and the mode values are present in the 4th and 8th layers.
  • the frequencies were 20% and 20%, respectively.
  • sample sampling material for high performance liquid chromatography of the present invention can be used for analysis by high performance liquid chromatography.
  • Sample sampling material for high performance liquid chromatography 100 Base material 10 Fibrous columnar structure 2 Fibrous columnar material

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Abstract

L'invention fournit un matériau d'échantillonnage pour chromatographie liquide à haute performance qui permet de réaliser un échantillonnage sans endommagement ni contamination d'un échantillon. Le matériau d'échantillonnage pour chromatographie liquide à haute performance de l'invention est destiné à préparer des échantillons de chromatographie liquide à haute performance, et contient un matériau de base et une structure colonnaire fibreuse qui est équipée d'une pluralité d'objets colonnaires fibreux. Ces objets colonnaires fibreux sont orientés dans une direction sensiblement orthogonale par rapport au matériau de base.
PCT/JP2015/073084 2014-08-25 2015-08-18 Matériau d'échantillonnage pour chromatographie liquide à haute performance Ceased WO2016031616A1 (fr)

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JP2014170156A JP2016045102A (ja) 2014-08-25 2014-08-25 高速液体クロマトグラフィー用試料サンプリング材

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107727751A (zh) * 2017-10-09 2018-02-23 北京军秀咨询有限公司 一种化妆品中美白祛斑成分的检测方法和装置

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