WO2020105716A1 - 単結晶ｘ線構造解析装置と方法、及び、そのための試料ホルダ - Google Patents

単結晶ｘ線構造解析装置と方法、及び、そのための試料ホルダ

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Publication number
WO2020105716A1
WO2020105716A1 PCT/JP2019/045685 JP2019045685W WO2020105716A1 WO 2020105716 A1 WO2020105716 A1 WO 2020105716A1 JP 2019045685 W JP2019045685 W JP 2019045685W WO 2020105716 A1 WO2020105716 A1 WO 2020105716A1
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WO
WIPO (PCT)
Prior art keywords
sample
ray
sample holder
crystal
single crystal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/045685
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English (en)
French (fr)
Japanese (ja)
Inventor
佐藤　孝
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rigaku Denki Co Ltd
Rigaku Corp
Original Assignee
Rigaku Denki Co Ltd
Rigaku 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 Rigaku Denki Co Ltd, Rigaku Corp filed Critical Rigaku Denki Co Ltd
Priority to CN201980076225.6A priority Critical patent/CN113056669A/zh
Priority to US17/295,854 priority patent/US20220018791A1/en
Priority to EP19887578.3A priority patent/EP3885752A4/en
Priority to JP2020557640A priority patent/JPWO2020105716A1/ja
Publication of WO2020105716A1 publication Critical patent/WO2020105716A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
    • G01N23/20025—Sample holders or supports therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
    • G01N23/20016—Goniometers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/207—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions

Definitions

  • the present invention relates to a next-generation single-crystal X-ray structure analysis apparatus and method that enable analysis of the structure of a material by means of a microscopic aggregate structure such as the arrangement of atoms or molecules, and in particular, it is an object of analysis.
  • the present invention relates to a single crystal X-ray structure analysis apparatus and method including an instrument for performing processing including preparation of a single crystal sample, and a sample holder therefor.
  • this single crystal X-ray structure analysis had a major limitation that a single crystal had to be prepared by crystallizing a sample.
  • a material called “crystal sponge” for example, pores having an infinite number of pores having a diameter of 0.5 nm to 1 nm.
  • the present invention has been achieved in view of the above-mentioned problems in the conventional technique, and the object thereof is extremely minute and fragile even without specialized knowledge of X-ray structural analysis.
  • the single crystal X-ray structure analysis using a simple crystal sponge can be performed quickly, reliably and easily without the conventional fine and precise work that requires rapidity. In other words, the yield is good. It is an object of the present invention to provide a single crystal X-ray structural analysis device and method that are efficient, highly versatile, and user-friendly, and further provide a sample holder that is an instrument therefor. ..
  • a single crystal X-ray structure analyzing apparatus of the present invention is a single crystal X-ray structure analyzing apparatus for performing structural analysis of a substance, and an X-ray source for generating X-rays, A sample holder that holds a sample, a goniometer that attaches and rotates the sample holder, and an X that irradiates the sample held by the sample holder that is attached to the goniometer with X-rays from the X-ray source.
  • the sample holder includes a porous complex crystal capable of storing the sample in a plurality of micropores formed therein, and the porous complex crystal is the sample.
  • the holder is attached to the goniometer, and is fixed at a position where the X-ray is emitted from the X-ray irradiator of the sample holder.
  • the sample holder is detachably attached to the tip of the goniometer.
  • the sample holder of the present invention is a sample holder used in a single crystal X-ray structure analyzing apparatus, and includes a base part attached to a goniometer of the single crystal X-ray structure analyzing device, and the base part. And a holding portion for holding a porous complex crystal capable of storing a sample in a plurality of fine pores formed therein, and the porous complex crystal, the base portion in the goniometer. It is characterized in that, in the attached state, the sample holder is fixed to a position where X-rays from the X-ray irradiation unit are irradiated.
  • the sample holder of the present invention is characterized in that the base part is formed with a sample introduction structure for introducing the sample to be absorbed in the porous complex crystal.
  • the porous complex crystal is fixed to the tip of the holding portion.
  • the holding portion is formed with a sample introduction structure for introducing the sample to be absorbed in the porous complex crystal.
  • the porous complex crystal is fixed inside the sample introduction structure formed in the holding portion.
  • the single crystal X-ray structure analysis method of the present invention is a single crystal X-ray structure analysis method for performing structural analysis of a substance using a sample holder, and is used as a goniometer of a single crystal X-ray structure analysis device.
  • the method further comprises the step of introducing a sample to be measured into the sample holder and occluding the sample in the porous complex crystal. It has a feature.
  • the sample introduced using the sample introduction structure formed in the sample holder is occluded in the porous complex crystal. It is characterized by
  • the X-ray detection and measurement step irradiates the sample with the X-ray while rotating the sample holder attached to the goniometer. It has a feature.
  • a minute and fragile crystal sponge that does not involve the conventional minute and fine work that requires swiftness is also used.
  • a series of operations including occlusion of a sample in the device and subsequent mounting in a device can be performed quickly, reliably and easily. In other words, it has good yield and efficiency, and is also highly versatile.
  • a user-friendly single crystal X-ray structure analysis apparatus is provided.
  • a sample holder which is the method and an instrument therefor is provided. From this, single crystal X-ray structural analysis using a crystal sponge can be easily used and widely spread.
  • a or B means “at least one of A and B”, and includes “A and B” unless there is a special circumstance that A and B cannot exist.
  • FIG. 1 attached herewith shows an overall appearance configuration of a single crystal X-ray structure analysis apparatus including a single crystal X-ray diffraction apparatus according to an embodiment of the present invention.
  • the single crystal X-ray structure analysis apparatus 1 has a base 4 that stores a cooling device and an X-ray generation power supply unit, and an X-ray protection cover 6 that is placed on the base 4.
  • the anti-X-ray cover 6 has a casing 7 surrounding the single crystal X-ray diffraction device 9, a door 8 provided on the front surface of the casing 7, and the like.
  • the door 8 provided on the front surface of the casing 7 can be opened, and various operations can be performed on the internal single crystal X-ray diffraction device 9 in this opened state.
  • the present embodiment shown in the figure is a single crystal X-ray structure analyzing apparatus 1 including a single crystal X-ray diffracting apparatus 9 for performing structural analysis of a substance by using a crystal sponge which will be described later.
  • the single crystal X-ray diffractometer 9 has an X-ray tube 11 and a goniometer 12 as shown in FIG.
  • the X-ray tube 11 has a filament, a target (also referred to as “anticathode”) that is arranged to face the filament, and a casing that hermetically stores them, and the filament is It is energized by the X-ray generation power supply unit stored in the base 4 of FIG. 1 to generate heat and emit thermoelectrons. Further, a high voltage is applied between the filament and the target by the X-ray generation power supply unit, and the thermoelectrons emitted from the filament are accelerated by the high voltage and collide with the target.
  • the X-ray tube 11 is configured to include an optical element such as a microfocus tube and a multilayer film condensing mirror, and can emit a beam of higher brightness. It is also possible to select from radiation sources such as Cu, Mo and Ag.
  • the filament, the target arranged facing the filament, and the casing that hermetically stores them function as an X-ray source, and an optical element such as a microfocus tube and a multilayer film condensing mirror.
  • the configuration for X-ray irradiation including the above functions as an X-ray irradiation unit.
  • the goniometer 12 supports the sample S to be analyzed and is arranged around the ⁇ rotary table 16 and the ⁇ rotary table 16 which is rotatable around the sample axis ⁇ passing through the X-ray incident point of the sample S. And a 2 ⁇ rotary table 17 rotatable about the sample axis ⁇ .
  • the sample S is occluded in the inside of a crystal sponge previously attached to a part of the sample holder 250 which will be described in detail later.
  • a drive device (not shown) for driving the ⁇ rotary table 16 and the 2 ⁇ rotary table 17 described above is stored inside the base 18 of the goniometer 12, and is driven by these drive devices to drive ⁇
  • the rotary table 16 rotates intermittently or continuously at a predetermined angular velocity, so-called ⁇ rotation.
  • the 2 ⁇ rotation base 17 rotates intermittently or continuously, so-called 2 ⁇ rotation.
  • the above drive device can be configured by any structure, for example, a power transmission structure including a worm and a worm wheel.
  • An X-ray detector 22 is mounted on a part of the outer circumference of the goniometer 12, and the X-ray detector 22 is, for example, a CCD type or CMOS type two-dimensional pixel detector or a hybrid type pixel detector. Composed.
  • the X-ray detection and measurement unit refers to a configuration that detects and measures X-rays diffracted or scattered by the sample, and includes the X-ray detector 22 and a control unit that controls the X-ray detector 22.
  • the sample S rotates ⁇ around the sample axis ⁇ by the ⁇ rotation of the ⁇ rotary table 16 of the goniometer 12.
  • X-rays generated from the X-ray focal point in the X-ray tube 11 and directed toward the sample S are incident on the sample S at a predetermined angle and are diffracted / diverged. That is, the incident angle of the X-ray incident on the sample S changes according to the ⁇ rotation of the sample S.
  • the sample S When the Bragg diffraction condition is satisfied between the incident angle of the X-ray incident on the sample S and the crystal lattice plane, the sample S generates diffracted X-rays. This diffracted X-ray is received by the X-ray detector 22 and its X-ray intensity is measured. As described above, the angle of the X-ray detector 22 with respect to the incident X-ray, that is, the intensity of the diffracted X-ray corresponding to the diffraction angle is measured, and the crystal structure or the like of the sample S is analyzed from the measurement result.
  • FIG. 3 (A) shows an example of details of an electrical internal configuration of the control unit 110 in the single crystal X-ray structure analysis apparatus.
  • the present invention is not limited to the embodiments described below.
  • This single crystal X-ray structure analyzing apparatus 1 includes the above-mentioned internal structure, and further, a measuring apparatus 102 for measuring an appropriate substance as a sample, an input apparatus 103 composed of a keyboard, a mouse, etc., and a display.
  • An image display device 104 as a means, a printer 106 as a means for printing and outputting an analysis result, a CPU (Central Processing Unit) 107, a RAM (Random Access Memory) 108, and a ROM (Read Only Memory) 109 and a hard disk 111 as an external storage medium.
  • CPU Central Processing Unit
  • RAM Random Access Memory
  • ROM Read Only Memory
  • the image display device 104 is composed of an image display device such as a CRT display or a liquid crystal display, and displays an image on the screen according to an image signal generated by the image control circuit 113.
  • the image control circuit 113 generates an image signal based on the image data input thereto.
  • the image data input to the image control circuit 113 is formed by the operation of various calculation means implemented by a computer including a CPU 107, a RAM 108, a ROM 109 and a hard disk 111.
  • the printer 106 may be an ink plotter, a dot printer, an inkjet printer, an electrostatic transfer printer, or any other type of printing device.
  • the hard disk 111 may be composed of a magneto-optical disk, a semiconductor memory, or a storage medium having any structure.
  • analysis application software 116 that controls the overall operation of the single crystal X-ray structure analysis apparatus 1
  • measurement application software 117 that controls the operation of measurement processing using the measurement apparatus 102
  • image display The display application software 118 that controls the operation of the display process using the device 104 is stored.
  • These application software realizes a predetermined function after being read from the hard disk 111 and transferred to the RAM 108 as needed.
  • the single crystal X-ray structure analyzing apparatus 1 further includes, for example, a database placed in a cloud area for storing various measurement results including the measurement data obtained by the measuring apparatus 102.
  • a database placed in a cloud area for storing various measurement results including the measurement data obtained by the measuring apparatus 102.
  • an XRDS information database 120 that stores the XRDS image data obtained by the measuring device 102
  • a microscope image database 130 that stores an actually measured image obtained by a microscope, and further, for example, , An XRF, a Raman ray, and the like, and a measurement result obtained by analysis other than X-rays
  • another analysis database 140 that stores physical property information.
  • these databases do not necessarily have to be installed inside the single crystal X-ray structure analysis apparatus 1, and may be provided outside and connected to each other via a network 150 or the like so that they can communicate with each other. ..
  • a method of storing each measurement data in an individual file can be considered, but in the present embodiment, as shown in FIG.
  • a plurality of measurement data are continuously stored in one data file.
  • the storage area described as “condition” in FIG. 3B is an area for storing various pieces of information including device information when the measurement data is obtained and measurement conditions.
  • Such measurement conditions include (1) measurement target substance name, (2) measurement device type, (3) measurement temperature range, (4) measurement start time, (5) measurement end time, and (6) measurement angle. Range, (7) moving speed of the scanning movement system, (8) scanning conditions, (9) type of X-rays incident on the sample, (10) whether or not an attachment such as a sample high temperature device is used, and various other conditions Can be considered.
  • An XRDS (X-ray Diffraction and Scattering) pattern or image (see FIG. 4) is used to detect an X-ray received on a plane that is a two-dimensional space of the X-ray detector 22 that constitutes the measurement apparatus 102. It is obtained by receiving / accumulating light for each pixel arranged in a plane which constitutes the container and measuring the intensity thereof. For example, by detecting the intensity of the received X-ray by integration for each pixel of the X-ray detector 22, a pattern or image in a two-dimensional space of r and ⁇ can be obtained.
  • the XRDS pattern or image in the observation space obtained by diffraction or scattering of X-rays by the target material with respect to the irradiated X-rays reflects the information of the electron density distribution in the real space of the target material.
  • the XRDS pattern is a two-dimensional space of r and ⁇ , and does not directly express the symmetry in the real space of the target material, which is a three-dimensional space. Therefore, it is generally difficult to specify the (spatial) arrangement of the atoms and molecules that make up the material using only the existing XRDS image, and requires specialized knowledge of X-ray structural analysis. Therefore, in the present embodiment, the measurement application software described above is adopted for automation.
  • the single crystal X-ray structure analyzing apparatus 1 controls the operation of the measurement process using the measuring apparatus 102 by the X-ray detecting and measuring unit, and detects the X-rays diffracted or scattered by the sample. Receive and manage various measurement results including the measurement data obtained in. Further, the structural analysis unit performs structural analysis of the sample based on various measurement results including measurement data obtained by detecting X-rays diffracted or scattered by the sample.
  • X-ray diffraction data measurement / processing software called “CrysAlis Pro ”, which is a platform for single crystal structure analysis, is installed, Performs preliminary measurement, setting of measurement conditions, main measurement, data processing, etc. Further, by mounting an automatic structural analysis plug-in called “AutoChem”, structural analysis and structural refinement are executed in parallel with X-ray diffraction data acquisition. Then, the structure analysis program called “Olex 2 ” also shown in FIG. 6 performs space group determination, phase determination, molecular model construction and modification, structure refinement, final report, and CIF file creation.
  • a “crystal sponge” which is an extremely minute and fragile porous complex crystal with a number of pores with a diameter of 0.5 nm to 1 nm opened innumerably and having a size of about several tens ⁇ m to several hundreds ⁇ m, Due to the development of the so-called material, single crystal X-ray structural analysis is widely applied to liquid compounds that do not crystallize, or very small samples such as several ng to several ⁇ g that cannot be secured in sufficient amounts for crystallization. It is possible to do.
  • a skeleton of an extremely minute and fragile crystal sponge with an outer diameter of about 100 ⁇ m provided by impregnating a very small amount of sample in a storage solvent (carrier) such as cyclohexane in a container.
  • a storage solvent such as cyclohexane
  • the storage solvent includes a liquid, a gas (gas), and a supercritical fluid in the middle thereof.
  • the present invention has been achieved based on the findings of the inventor as described above, and a single crystal X-ray structural analysis using a crystal sponge that is extremely minute and fragile is performed by the following sample holder for crystal sponge ( (Also referred to as a sample holder) makes it possible to perform the process quickly, reliably and easily. In other words, the yield is high, the efficiency is high, the versatility is excellent, and the user friendliness is high.
  • the present invention realizes a single crystal X-ray structure analyzing apparatus.
  • next-generation single-crystal X-ray structure analysis apparatus an extremely minute and fragile crystal sponge that occludes an extremely small amount of sample S is prepared, and further, the sample S (crystal sponge ) Has to be taken out from the occlusion container and attached to the predetermined position of the tip of the goniometer 12 accurately and promptly in a short time so that the crystal sponge is not destroyed by drying, but there is a major limitation.
  • the sample S (crystal sponge ) Has to be taken out from the occlusion container and attached to the predetermined position of the tip of the goniometer 12 accurately and promptly in a short time so that the crystal sponge is not destroyed by drying, but there is a major limitation.
  • it is necessary to perform such work quickly and easily without requiring a high degree of specialized knowledge and work precision. is there.
  • the present invention solves such a problem, that is, anyone can use a micro sponge, which is fragile and difficult to handle, and is quick, reliable, easy, yield efficient, and user-friendly.
  • the present invention provides an apparatus and method for performing a single crystal X-ray structural analysis that is capable of performing the above and is also highly versatile, and a sample holder that is an instrument therefor, which will be described in detail below.
  • FIG. 7 (A) shows the tip of the goniometer 12 in an enlarged manner.
  • a crystal sponge 200 for occluding the sample to be analyzed proposed by the present invention is attached to the tip in advance.
  • FIG. 7B shows an enlarged view of a so-called sample holder 250 mounted (mounted) on the goniometer head 121 at the tip of the goniometer 12.
  • the sample holder 250 is attachable / detachable to / from the goniometer head 121 at the tip of the goniometer 12 by, for example, a mounting / positioning mechanism using magnetic force, and anyone can easily and accurately mount the sample holder 250 at an accurate position. It is possible.
  • FIG. 8 shows a cross section of the sample holder 250 described above.
  • the sample holder 250 includes a pin (cylindrical) sample on the base portion 251 of a disc-shaped or conical holder made of metal or the like that is attached to the goniometer head 121 (see FIG. 7A) at the tip of the goniometer 12.
  • a holding portion (hereinafter, also simply referred to as a holding portion) 252 (corresponding to a so-called gonio head pin) is planted in the center of one surface (lower surface in the figure) of the pin-shaped holding portion.
  • the crystal sponge 200 for storing the above-described sample to be analyzed is previously fixed integrally with the sample holder 250. Further, a positioning mechanism such as a magnet (not shown) is provided on the other surface (upper surface in the drawing) of the disk-shaped base portion 251. The sample holder 250 is detachably attached to the tip of the goniometer 12 by this positioning mechanism.
  • FIG. 8 shows a so-called applicator 300, which is a handling (manipulation) instrument for use with the sample holder 250 to occlude the sample in the crystal sponge 200 previously attached to the sample holder 250.
  • the applicator 300 is formed of, for example, a transparent or opaque member such as glass, resin, or metal, and a storage space 301 for storing the sample holder 250 is formed therein. Further, an opening portion 302 for inserting and removing the sample holder 250 is formed on the upper portion thereof.
  • a seal portion is provided in a part of the opening 302 of the applicator 300 so that the sample holder 250 is housed in the housing space 301 inside thereof so as to be kept airtight from the outside.
  • a pair of penetrating pores 253, 253 for introducing the sample to be analyzed into the crystal sponge 200 located inside the applicator 300 (storage space 301). are formed in the base portion 251 of the sample holder 250.
  • the pores 253 and 253 are a preferable example of the sample introduction structure, and other structures can be adopted.
  • these pores 253, 253 are also provided with a seal portion, which allows a sample introduction tube (hereinafter, simply referred to as a sample introduction tube for introducing the sample into the crystal sponge 200, as shown in the figure.
  • a sample introduction tube hereinafter, simply referred to as a sample introduction tube for introducing the sample into the crystal sponge 200, as shown in the figure.
  • the storage space 301 inside the applicator 300 is kept airtight even when the introduction pipes 254 and 254 are inserted into the pores 253 and 253.
  • a part of the sample holder 250 is configured.
  • the crystal sponge 200 attached to the tip of the pin-shaped holding portion 252 (corresponding to a goniometer head pin) can be safely and easily handled without being damaged or departing from the sample holder 250. That is, the crystal sponge 200 that has occluded a very small amount of sample is taken out from the occluding container as a single unit as in the conventional case and is not damaged, and is safe, simple and easy, and in a short time not to be destroyed by drying. , Can be quickly prepared on the gonio head 121.
  • the sample holder 250 whose occlusion of the sample has been completed is removed from the applicator 300 and attached to the goniometer head 121 (see FIG. 7A) at the tip of the goniometer 12.
  • the sample S occluded in the crystal sponge 200 can be easily, accurately and quickly arranged at a predetermined position in the single crystal X-ray diffractometer 9 without requiring highly specialized knowledge or precise work. Will be done.
  • the sample holder 250 is integrated (unitized) with the applicator 300 which is a handling (operating) instrument, and further, as shown in FIG. It could be housed in a case and provided as a so-called set.
  • sample holder 250 and the applicator 300 may be provided as a unit (unit) or as a set, as described above.
  • FIG. 10 conceptually shows a single crystal X-ray structure analysis method using a sample holder 250, which is an embodiment of the present invention.
  • a very small amount of sample is introduced into the sample holder 250 provided integrally (unit) with the applicator 300, and necessary occlusion is performed.
  • a pair of sample introductions are made to the pair of penetrating pores 253 and 253 (see FIG. 8) formed in the sample holder 250.
  • the tubes 254 and 254 the sample can be occluded in the crystal sponge 200 attached to the tip of the sample holder 250.
  • LC liquid chromatography
  • GC gas chromatography
  • SCF supercritical fluid chromatography
  • the sample is sent from the supply-side pipe to the supply-side sample introduction pipe 254, and is supplied from the tip portion of the supply-side sample introduction pipe 254 to the sample holder 250 inside the applicator 300.
  • a sample alone or a solution in which a sample and a storage solvent (carrier) are mixed is supplied through the sample introduction tube 254 on the supply side.
  • the introduced minute amount of the sample S comes into contact with the crystal sponge 200 attached to the tip of the pin-shaped holding portion 252 of the sample holder 250 in the storage space 301 of the applicator 300 to occlude the sample. Is done.
  • the electrophoresis device here includes various electrophoresis devices such as capillary electrophoresis and isoelectric focusing.
  • an excess sample or a solution in which a sample and a storage solvent (carrier) are mixed is discharged from the sample introduction pipe 254 on the discharge side after a predetermined time has elapsed while the sample is injected. To be done.
  • unnecessary storage solvent (carrier) or solution flows in the sample introduction pipe 254 on the discharge side and is discharged. Therefore, the sample may not flow into the sample introduction pipe 254 on the discharge side.
  • gas or supercritical fluid is used as the carrier, the carrier containing the sample is discharged.
  • the sample holder 250 that has completed this occlusion process is removed from the applicator 300, and is placed at a predetermined position in the single crystal X-ray diffractometer 9, that is, at the gonio head 121 at the tip of the goniometer 12, for example, as described above. It can be attached accurately using a positioning mechanism such as magnetic force. According to this, the crystal sponge 200 attached to a part (tip) of the pin-shaped holding portion 252 of the sample holder 250 has the tip of the goniometer 12, that is, the X-ray tube, after the occlusion of the sample is completed.
  • the X-ray beam from 11 is arranged at a position where it is focused and irradiated.
  • the sample S stored in the crystal sponge 200 is accurately placed at a predetermined position in the single crystal X-ray diffractometer 9, and then the X-ray detector 22 detects the diffracted X-rays from the sample S. The strength is measured and the crystal structure and the like are analyzed.
  • the sample holder 250 of the present invention by using the sample holder 250 of the present invention, anyone can easily and safely put a very small amount of sample on the crystal sponge 200 having an extremely small size that is integrally attached to the sample holder 250 in advance. It becomes possible to store the sample S in the goniometer 12 in a highly accurate and accurate position in a short time, quickly and safely while the crystal sponge is not destroyed by drying while being occluded. After that, while irradiating the sample S with X-rays of a required wavelength by the above-mentioned single-crystal X-ray diffractometer 9, X-ray diffraction and scattering measurement by the target material are performed to configure the above-mentioned single-crystal X-ray structure analysis device.
  • the structural analysis is performed by the measurement application software to construct the molecular model and the final report. That is, according to this example, the molecular structure / aggregate structure (real space) of a new structure discovered or designed in a field of various material research as well as drug discovery and life science can be quickly, safely, And it becomes possible to confirm easily.
  • FIG. 12 shows a cross-sectional structure of a sample holder 250a according to another embodiment instead of the above structure.
  • a sample holder 250a according to another embodiment, one penetrating pore 253 is provided in the base portion 251 and the other pore 253a is a pin-shaped holding that is erected from the central portion of the base portion 251. It is provided so as to penetrate the center of the portion 252a.
  • a crystal sponge 200 for occluding the sample to be analyzed is integrally attached at a tip or in the middle of the other pore 253a at a predetermined position set in advance.
  • the sample to be analyzed is introduced from the through hole 253a formed in the center of the pin-shaped holding portion 252a which is erected from the central portion of the base portion 251. Except for the above structure, the crystal sponge 200 is occluded while being held inside the applicator 300, and the sample holder 250a, which has completed the occlusion, is removed from the applicator 300 and attached to the tip of the goniometer 12. Therefore, it is clear that the fine and precise work which has been conventionally required can be performed quickly, easily and surely.
  • the crystal sponge 200 is introduced through the pores 253a penetrating the pin-shaped holding portion 252a having the crystal sponge 200 attached to the inside or the tip end thereof, so that the trace amount of the sample can be further improved. It is possible to surely contact and occlude the crystal sponge 200 having an extremely small size. Furthermore, the crystal sponge 200 attached to the pin-shaped holding portion 252a is disposed inside the pores 253a which the pin-shaped holding portion 252a penetrates, and therefore is damaged from the outside or is lost to the outside. Can be handled more safely, easily, and quickly without the need for handling.
  • an extremely minute and fragile crystal sponge can be obtained without requiring any expertise in X-ray structural analysis.
  • the single crystal X-ray structure analysis used can be carried out quickly, reliably and easily without the need for precise and minute work conventionally required.
  • the single crystal X-ray structure using a crystal sponge A versatile and user-friendly single crystal X-ray structure analysis apparatus capable of performing an analysis efficiently with a high yield is realized, and further, a method and a sample holder therefor are provided.
  • the present invention is not limited to the above-described embodiments and includes various modifications.
  • the above-described embodiment is a detailed description of the entire system in order to explain the present invention in an easy-to-understand manner, and is not necessarily limited to one having all the configurations described.
  • part of the configuration of one embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of one embodiment. It would be possible to add, delete, or replace some of the example configurations with other configurations.
  • the present invention can be widely used in a method for searching a material structure, an X-ray structure analysis apparatus used for the method, and the like.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • General Physics & Mathematics (AREA)
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  • Analysing Materials By The Use Of Radiation (AREA)
  • Sampling And Sample Adjustment (AREA)
PCT/JP2019/045685 2018-11-21 2019-11-21 単結晶ｘ線構造解析装置と方法、及び、そのための試料ホルダ Ceased WO2020105716A1 (ja)

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CN201980076225.6A CN113056669A (zh) 2018-11-21 2019-11-21 单晶x射线构造解析装置和方法及用于其的试料保持器
US17/295,854 US20220018791A1 (en) 2018-11-21 2019-11-21 Single-crystal x-ray structure analysis apparatus and method, and sample holder therefor
EP19887578.3A EP3885752A4 (en) 2018-11-21 2019-11-21 APPARATUS AND METHOD FOR SINGLE CRYSTAL X-RAY STRUCTURE ANALYSIS AND SAMPLE HOLDER THEREFOR
JP2020557640A JPWO2020105716A1 (ja) 2018-11-21 2019-11-21 単結晶ｘ線構造解析装置と方法、及び、そのための試料ホルダ

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EP4148421A1 (en) * 2021-09-10 2023-03-15 Merck Patent GmbH Sample holder arrangement for structure elucidation with porous frameworks
CN116368379A (zh) * 2020-08-24 2023-06-30 马尔文帕纳科公司 用于x射线衍射分析装置的x射线检测器

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