Patent Description:
In research and development for new devices and materials, the materials are ordinarily synthesized and evaluated to determine the next research policy based on the foregoing. In a structure analysis of a material using X-ray diffraction for performing material development in a short period of time, a search method of a material structure centering on the material structure analysis capable of efficiently performing the structure analysis, and an X-ray structure analysis used therein are indispensable for efficiently searching the material structure that realizes the function/physical property of an object material.

However, it has been difficult for those other than X-ray specialists to perform the structure analysis based on the results obtained by the foregoing method. Therefore, an X-ray structure analysis system with which the structure analysis can be performed by anyone who is not even a specialist of X-rays has been demanded. In this regard, as is known from the following Patent Document <NUM>, the single-crystal X-ray structure analysis has gained attention as a method capable of catching a precise and highly accurate three-dimensional structure of molecules.

On the other hand, in this single-crystal X-ray structure analysis, there has been such a large constraint that a single-crystal needs to be prepared by crystallizing a sample. However, as is also known from the following Non-Patent Documents <NUM> and <NUM>, and further, as is also known from patent document <NUM>, the single-crystal X-ray structure analysis becomes widely applicable for those including a liquid compound that cannot be crystallized, a sample incapable of acquiring a sufficient amount for crystallization, and so forth via development of a material called "crystalline sponge" (for example, a porous complex crystal in which countless pores each having a diameter of <NUM> to <NUM> are formed).

In the field of single-crystal X-ray structure analysis, when analyzing a single-crystal sample with a single-crystal X-ray structure analysis apparatus to determine a crystal structure of the single-crystal, it is difficult to prepare the single-crystal sample to be analyzed, and skillfulness via experience and intuition was further required for determining the crystal structure of the single-crystal from data obtained by analyzing the single-crystal sample to be analyzed thereof with the single-crystal X-ray structure analysis apparatus; and thus this was able to be only performed by a very limited number of persons.

On the other hand, with progress in technology and development of single-crystal X-ray structure analysis apparatus, even a person who is not skilled in crystal structure analysis technology would be able to analyze a single-crystal sample by the single-crystal X-ray structure analysis apparatus if the single-crystal sample could be only available, and thus in recent years, the crystal structure of the single-crystal sample has been able to be relatively easily determined.

Further, as a high molecular complex having at least <NUM> species of pore groups capable of selectively incorporating and/or releasing a specific compound ranging a small gaseous molecule to a large molecule such as a protein, a biogenic molecule or the like; in Patent Document <NUM>, disclosed is the high molecular complex characterized by having at least <NUM> species of pore groups comprising mutually equal pores having unique affinity to a guest component in a three-dimensional lattice structure, that comprises a three-dimensional lattice structure including a stacked structure obtained by inserting the non-coordinating aromatic compound in between aromatic compound ligands, wherein the non-coordinating aromatic compound constituted from the stacked structure forms a main skeleton of the high molecular complex.

According to a conventional technique, as described in Non-Patent Document <NUM>, the crystal structure of a single-crystal can be relatively easily determined by forming a very small and fragile crystalline sponge in which a plurality of fine pores are formed and soaking a sample inside the fine pores of this crystalline sponge to analyze this by a single-crystal X-ray structure analysis apparatus.

In order to perform analysis using this crystalline sponge by the single-crystal X-ray structure analysis apparatus, it becomes necessary to surely attach a sample made into a single-crystal, that is soaked inside the fine pores of the crystalline sponge and is formed therein, to a part (a tip of a goniometer head pin) of a sample holder used for performing analysis by the single-crystal X-ray structure analysis apparatus. However, neither a method for surely attaching a sample soaked to be formed in a very small and fragile crystalline sponge to a measurement position in a single-crystal X-ray structure analysis apparatus, nor an apparatus therefor is disclosed in the above-described conventional technique.

The present invention that solves the problems of the conventional technology as described above is to provide a soaking machine according to claim <NUM> and a soaking method of a sample according to claim <NUM> for single-crystal X-ray structure analysis that enable surely soaking an analysis sample in the very small and fragile crystalline sponge attached to the sample holder, and quickly and easily supplying the sample to the single-crystal X-ray structure analysis apparatus, by using the sample holder proposed in connection with the present invention.

According to a soaking machine of a sample for single-crystal X-ray structure analysis of the present invention, it is made possible to surely soak a sample in a porous complex crystal that is a very small and fragile crystalline sponge held by a sample holder in a single-crystal X-ray structure analysis apparatus.

Next, a soaking machine of a sample for single-crystal X-ray structure analysis used for a single-crystal X-ray structure analysis apparatus, that is capable of surely performing supplying thereto as a sample holder in the single-crystal X-ray structure analysis apparatus to soak an analysis sample in a sponge-shaped material (crystalline sponge, or porous complex crystal); and a soaking method thereof according to the present invention are described referring to the drawings. In addition, the expression of "A or B" according to the present application means "at least one of A and B", and comprises "A and B" unless there are exceptional circumstances where there exists no possibility of A and B.

<FIG> shows an outline configuration of the entire single-crystal X-ray structure analysis apparatus system <NUM> comprising a soaking machine of a sample for X-ray structure analysis according to the present Example. The single-crystal X-ray structure analysis system <NUM> relating to the preset Example comprises a chromatography apparatus <NUM> that extracts an analysis object sample from inside a sample such as a gas sample, a liquid sample or the like; a soaking machine <NUM> for a single-crystal X-ray structure analysis apparatus (hereinafter, also referred to simply as a soaking machine <NUM>), that prepares a sample for single-crystal X-ray structure analysis from the sample obtained via extraction thereof with the chromatography apparatus <NUM>; a sample tray <NUM> in which single-crystal X-ray structure analysis samples each prepared by the soaking machine <NUM> are stored and moved; and a single-crystal X-ray structure analysis apparatus <NUM> that analyzes each of the samples stored in the sample tray <NUM>, using X-rays.

In addition, the sample may be made to singly move from the soaking machine <NUM> to the single-crystal X-ray structure analysis apparatus <NUM> without using the sample tray <NUM>.

The attached <FIG> shows the entire appearance configuration of the single-crystal X-ray structure analysis apparatus comprising a single-crystal X-ray diffractometer according to one embodiment of the present invention, and as is clear from the figure, the single-crystal X-ray structure analysis apparatus <NUM> comprises a base stand <NUM> in which a cooling device and an X-ray generation power supply unit are stored, and an X-ray protection cover <NUM> placed on the base stand <NUM>.

The X-ray protection cover <NUM> is provided with a casing <NUM> for surrounding the single-crystal X-ray diffractometer <NUM>, a door provided in front of the casing <NUM>, and so forth. The door provided in front of the casing <NUM> is openable, and in this open state, various operations can be performed for the internal single-crystal X-ray diffractometer <NUM>. In addition, the present embodiment as shown in the figure is directed to the single-crystal X-ray structure analysis apparatus <NUM> provided with the single-crystal X-ray diffractometer <NUM> for performing a structure analysis of a material using the crystalline sponge mentioned below.

The single-crystal X-ray diffractometer <NUM> comprises an X-ray tube <NUM> and a goniometer <NUM>, as shown in <FIG> as well. The X-ray tube <NUM> comprises a filament, a target (referred to also as "anticathode") arranged so as to be opposed to the filament, and a casing for airtightly storing them, though not shown in the figure herein. This filament subjected to current applied by the X-ray generation power supply unit stored in the base stand <NUM> of <FIG> generates heat to emit thermal electrons.

Further, a high voltage is applied between the filament and the target by the X-ray generation power supply unit, and the thermal electrons emitted from the filament are accelerated by the high voltage, and collide with the target. This collision area forms an X-ray focus, and X-rays are generated from the X-ray focus, and are spread out. In more detail, though not shown in the figure herein, the X-ray tube <NUM> comprising a microfocus tube and an optical element such as a multilayer focusing mirror or the like enables irradiation with higher brightness beam, and can also be selected from a radiation source such as Cu, Mo, Ag or the like. As exemplified above, the filament, the target arranged so as to be opposed to the filament, and the casing for airtightly storing them serve as an X-ray source, and a configuration for X-ray irradiation comprising the microfocus tube and the optical element such as the multilayer focusing mirror or the like serves as an X-ray irradiation section.

Further, a goniometer <NUM> supporting a sample S to be analyzed comprises a θ rotation table <NUM> that is rotatable with a sample axis line ω passing through an X-ray incident point of the sample S as a center, and a 2Θ rotation table <NUM> that is arranged around the θ rotation table and is rotatable with the sample axis line ω as a center. A goniometer head <NUM> onto which the sample S is attached is provided to the goniometer <NUM>. In addition, according to the present embodiment, the sample S is soaked inside a crystalline sponge previously attached to a part of the sample holder <NUM> mentioned below.

Drive devices (not shown in the figure) for driving the above-described θ rotation table <NUM> and 2Θ rotation table <NUM> are stored inside a base <NUM> of the goniometer <NUM>, and the θ rotation table <NUM> is driven by these drive devices to be intermittently or continuously rotated at a predetermined angular speed so as to make a so-called θ rotation. Further, the 2Θ rotation table <NUM> is driven by these drive devices to be intermittently or continuously rotated so as to make a so-called 2Θ rotation. The above-described drive devices can be constituted from any structure, and for example, can be constituted from a power transmission structure comprising a worm and a worm wheel.

An X-ray detector <NUM> is placed on a part of the outer periphery of the goniometer <NUM>, and the X-ray detector <NUM> is constituted from for example, CCD type and CMOS type two-dimensional pixel detectors, a hybrid type pixel detector, or the like. In addition, an X-ray detection measurement section means a configuration in which X-rays diffracted or scattered by the sample are detected and measured, and comprises the X-ray detector <NUM> and a control section that controls the same.

The single-crystal X-ray diffractometer <NUM> is constituted as described above, and thus the sample S is θ-rotated with the sample axis line ω as a center by the θ rotation of the θ rotation table <NUM> in the goniometer <NUM>. During the θ rotation of this sample S, X-rays generated from the X-ray focus inside the X-ray tube <NUM>, that is directed to the sample S enter the sample S at a predetermined angle, and are diffracted/scattered. That is, the incident angle of X-rays entering the sample S changes depending on the θ rotation of the sample S.

When the Bragg diffraction condition between an incident angle of X-rays entering the sample S and a crystal lattice plane is satisfied, diffraction X-rays are generated from the sample S. The diffraction X-rays are received by the X-ray detector <NUM> to measure an X-ray intensity thereof. From those described above, an angle of the X-ray detector <NUM> with respect to the incident X-rays, that is, an intensity of the diffraction X-rays corresponding to a diffraction angle is measured, and a crystal structure concerning the sample S and so forth are analyzed from this measurement result.

Next, <FIG> shows one example of the detail of an electrical internal configuration constituting a control section <NUM> in the above-described single-crystal X-ray structure analysis apparatus <NUM>. In addition, as a matter of course, the present invention is not limited to the following embodiments according to the present invention.

This single-crystal X-ray structure analysis apparatus <NUM> includes the above-described internal configuration and further comprises a measurement device <NUM> for measuring a suitable material used as a sample; an input device <NUM> constituted from a keyboard, a mouse and so forth; an image display device <NUM> as display means; a printer <NUM> as means for printing and outputting the analysis result; CPU (Central Processing Unit) <NUM>; RAM (Random Access Memory) <NUM>; ROM Read Only Memory) <NUM>; a hard disk as an external storage medium, and so forth. These elements are mutually connected by a bus <NUM>.

The image display device <NUM> constituted from an image display unit such as a CRT display, a liquid-crystal display or the like displays an image on a screen in accordance with an image signal generated by an image control circuit <NUM>. The image control circuit <NUM> generates the image signal based on image data input therein. The image data input in the image control circuit <NUM> is generated by an operation of every kind of calculation means, achieved by a computer that includes an analysis section <NUM> comprising CPU <NUM>, RAM <NUM>, ROM <NUM>, and a hard disk.

An inkjet plotter, a dot printer, an inkjet printer, an electrostatic transfer printer, or any other printing unit having arbitrary structure is usable for the printer <NUM>. In addition, the analysis section <NUM> can also constitute from a magneto-optical disk, a semiconductor memory, or any other storage medium having arbitrary structure other than the hard disk.

Analysis application software <NUM> for managing the overall operation of the single-crystal X-ray structure analysis apparatus <NUM>, measurement application software <NUM> for managing the operation of the measurement processing using the measurement device <NUM>, and display application software <NUM> for managing the operation of the display processing using the image display device <NUM> are stored inside the analysis section <NUM> for performing structure analysis processing of the single-crystal by providing the hard disk. A predetermined function is achieved after reading these pieces of application software from the hard disk in the analysis section <NUM>, as needed, to transfer them to RAM <NUM>.

This single-crystal X-ray structure analysis apparatus <NUM> further comprises for example, a database placed in a cloud area, the database for storing every kind of measurement results including measurement data obtained by the above-described measurement device <NUM>. Referring to an example of the figure, as is explained below, shown are an XRDS information database <NUM> that stores XRDS image data obtained by the above-described measurement device <NUM>, and a microscope image database <NUM> that stores actually observed images obtained by the microscope, and further shown are for example, measurement results obtained via analysis performed with XRF, not X-rays but Raman ray or the like, and another analysis database <NUM> that stores physical property information. In addition, these databases are not necessarily stored inside the single-crystal X-ray structure analysis apparatus <NUM>, and for example, they may be provided outside and be communicably connected mutually via a network <NUM> or the like.

A method of storing individual measurement data inside an individual file is also taken into account as a file management method for storing a plurality of pieces of measurement data inside a data file, but according to the present embodiment, as shown in <FIG>, the plurality of pieces of measurement data are set to be continuously stored inside one data file. In addition, referring to <FIG>, storage areas each in which "condition" is written are an area for storing every kind of information including device information and measurement conditions when obtaining the measurement data.

As such measurement conditions, (<NUM>) name of measurement object material, (<NUM>) type of measurement device, (<NUM>) measurement temperature range, (<NUM>) measurement start time, (<NUM>) measurement end time, (<NUM>) measurement angle range, (<NUM>) moving speed in scanning movement system, (<NUM>) scanning condition, (<NUM>) type of X-rays incident on sample, (<NUM>) whether or not to use attachments such as a sample high-temperature device, and so forth, are conceivable and every kind of other conditions is also conceivable.

An XRDS (X-ray Diffraction and Scattering) pattern or an image (Refer to <FIG>) is obtained by receiving/accumulating X-rays received on a flat plane that is a two-dimensional space of the X-ray detector <NUM> constituting the above-described measurement device <NUM> for each pixel arranged in planar array (for example, CCD or the like), that constitutes the detector, and by measuring an intensity thereof. For example, a pattern or an image on a two-dimensional space of r and θ can be obtained by detecting the intensity of X-rays received via an integral, for each pixel of the X-ray detector <NUM>.

The XRDS pattern or the image on an observation space, that is obtained by diffraction and scattering of X-rays caused by an object material for irradiation of the X-rays reflects information of an electron density distribution in an actual space of the object material. However, the XRDS pattern being on the two-dimensional space of r and θ does not directly represents symmetry in the actual space of the object material as a three-dimensional space. Accordingly, it is generally difficult to specify the (spatial) arrangement of atoms and molecules that constitute the material with only the existing XRDS image, and thus a specialized knowledge of X-ray structure analysis is required. Therefore, according to the present Example, automatization is achieved by adopting the above-described measurement application software.

For one example, as shown in the execution screens of <FIG>, X-ray diffraction data measurement/processing software called "CrysAlisPro" that is a platform for single-crystal structure analysis is installed to execute preliminary measurement, setting of measurement conditions, main measurement, data processing and so forth. Further, structure analysis and structure refinement are executed in parallel with X-ray diffraction data collection by installing an automatic structure analysis plug-in called "AutoChem". Then, from space group determination to phase determination, construction and correction of molecular modelling, structure refinement, final reporting, and preparation of a CIF file are executed by a structure analysis program called "Olex<NUM>" as also shown in <FIG>.

The whole structure of the single-crystal X-ray structure analysis apparatus <NUM>, and its function have been described as above, and a crystalline sponge according to the present invention, and devices and tools related thereto are specifically described below in detail, referring to the attached drawings.

As described above, the single-crystal X-ray structure analysis has become widely applicable for those including a liquid compound that cannot be crystallized, a very small amount of a sample with several ng to several µg that is incapable of acquiring a sufficient amount to perform crystallization, or the like via development of a material called "crystalline sponge" as a very small and fragile porous complex crystal having an approximate size of several <NUM> to several <NUM>, in whose inside countless pores each having a diameter of <NUM> to <NUM> are formed.

However, in the current situation, in order to perform soaking (post-crystallization) as crystallization of a sample into a framework of the above-described crystalline sponge, as previously described, required is a step of soaking a very small amount of a sample, approximately several ng to several µg, separated by every kind of pretreatment (separation) devices in a framework of a very small and fragile crystalline sponge having an outer diameter of approximately <NUM> provided via immersion in a preserving solvent (carrier) such as cyclohexane or the like, inside a container. Examples of the preserving solvent (carrier) include liquid, a gaseous body (gas), and a supercritical fluid in the middle of them. Subsequently, further required is a step of taking out, from a container, a very small, fragile and difficultly handleable crystalline sponge in a quick manner (in a short period of time in such an extent that the crystalline sponge is not broken due to drying), and accurately attaching it to an X-ray irradiation position inside a diffractometer, more specifically, to a tip portion of a sample axis of the goniometer <NUM> (so-called goniometer head pin) while performing centering.

These steps are not only fine operations for which high preciseness is required but also those for which rapidness is required for the operator, regardless of presence/absence of a specialized knowledge of X-ray structure analysis, thereby resulting in having a large influence on the measurement result of a sample after being soaked in the crystalline sponge. That is, these operations make single-crystal X-ray structure analysis using a very small crystalline sponge result in low yield, and thus this becomes one of the causes of suppressing the single-crystal X-ray structure analysis using the crystalline sponge from being widely used.

The present invention that has been accomplished based on the above-described inventor's knowledge enables quickly, surely and easily performing a single-crystal X-ray structure analysis with a very small and fragile crystalline sponge by using a sample holder for the crystalline sponge (also referred to simply as a sample holder) as described below, in other words, achieves a high-yield, efficient, very versatile and user-friendly single-crystal X-ray structure analysis apparatus.

That is, as to the next-generation single-crystal X-ray structure analysis apparatus according to the present invention, there is a large constraint that the very small and fragile crystalline sponge in which a very small amount of a sample S is soaked is prepared, and further the sample S (crystalline sponge) needs to be taken up from a soaking container and precisely and attached to a predetermined position at the tip portion of the goniometer, but specifically in order to achieve the very versatile and user-friendly apparatus, such operations need to be made quickly and easily executable without requiring highly specialized knowledge as well as operation precision (preciseness).

The present invention described below in detail resolves such a problem, that is, provides an apparatus and a method for performing a high-yield efficient, very versatile and user-friendly single-crystal X-ray structure analysis in a quick, sure and easy manner by anyone while also using a very small, fragile and difficultly handleable crystalline sponge; and further provides a sample holder as a tool therefor.

The configuration of a soaking machine <NUM> by which an analysis object sample is soaked in a crystalline sponge in a configuration of a single-crystal X-ray structure analysis system <NUM> comprising a single-crystal X-ray structure analysis apparatus <NUM> relating the first Example according to the present invention as shown in <FIG> is described referring to <FIG>.

<FIG> is a block diagram showing a configuration of the soaking machine <NUM> for the single-crystal X-ray structure analysis apparatus <NUM> relating to Example according to the present invention. The soaking machine <NUM> relating to the present Example comprises a supply side piping <NUM>, a supply side first actuator <NUM>, a supply side analysis section <NUM>, a supply side second actuator <NUM>, a supply side pipe <NUM>, an injection needle (injection pipe) <NUM>, an applicator <NUM> into which a sample holder <NUM> (corresponding to the sample holder <NUM> in <FIG>) is attached, a temperature controller (thermostat) <NUM>, a discharge needle (discharge pipe) <NUM>, a discharge pipe <NUM>, a discharge side first actuator <NUM>, a discharge side analysis section <NUM>, a discharge side second actuator <NUM>, a discharge side piping <NUM>, a control section <NUM>, and a reading section <NUM>.

According to the soaking machine <NUM>, a carrier or a solvent (hereinafter, referred to as a sample, inclusive of each of these) containing an analysis object sample (gas, liquid, supercritical fluid, or the like) that has been supplied from a separation apparatus (for example, gas chromatography, liquid chromatography or the like) <NUM> is supplied through the supply side piping <NUM>, and a flow rate, a pressure and so forth of the sample are adjusted by the supply side first actuator <NUM>.

Next, the carrier containing the sample is sent to the supply side analysis section <NUM>, and components of the sample whose pressure, concentration and temperature are adjusted are analyzed. One example of the analysis results is shown in <FIG>. The graph of <FIG> shows that the sample sent from the separation apparatus <NUM> has a peak <NUM> in signal intensity at a specific component.

The sample that has been analyzed by the supply side analysis section <NUM> is sent from the supply side pipe <NUM> to the injection needle <NUM> whose tip portion is inserted in the sample holder <NUM> attached into the applicator <NUM>, and is supplied to the sample holder <NUM> inside the applicator <NUM> from the tip portion of the injection needle <NUM>. The injection needle <NUM> is driven by drive means that is not shown in the figure, and is inserted in the sample holder <NUM> attached into the applicator <NUM>.

The temperature controller <NUM> is controlled by the control section <NUM> in this state, and the applicator <NUM> is heated or cooled in such a manner that the applicator <NUM> comprising the sample holder <NUM> reaches a desired temperature.

An excessive sample out of the sample supplied to the inside of the applicator <NUM> is discharged via the discharge pipe <NUM> from the discharge needle <NUM> inserted into the sample holder <NUM> whose tip portion is attached into the applicator <NUM> by operating the discharge side first actuator <NUM>, after elapse of a predetermined time in a state where the sample is injected from the injection needle <NUM> into the sample holder <NUM> attached into the applicator <NUM> whose temperature is controlled by the temperature controller <NUM>. That is, the excessive sample means a sample discharged according to the length of the discharge needle <NUM>. The discharge needle <NUM> is driven by the drive means that is not shown in the figure, and is inserted into the sample holder <NUM>.

In this manner, the sample is sent to the injection needle <NUM> on the supply side from the supply side piping, and is supplied to the sample holder <NUM> inside the applicator <NUM> from the tip portion of the injection needle <NUM> on the supply side. Only the sample, or a solution in which the sample and the preserving solvent (carrier) are mixed is supplied by flowing inside the injection needle <NUM> on the supply side. Accordingly, a very small amount of the sample S introduced thereto comes into contact with the crystalline sponge attached to the tip of the pin-shaped holding part of the sample holder <NUM> inside the storing space <NUM> of the applicator <NUM>, and the sample is soaked therein. In addition, examples of the electrophoresis device herein include various electrophoresis devices concerning capillary electrophoresis, isoelectric point electrophoresis, and so forth. When using the soaking machine <NUM>, in a state where the sample is injected there into, the excessive sample or a solution in which the sample and the preserving solvent (carrier) are mixed is discharged from the discharge needle <NUM> on the discharge side, after a predetermined time has elapsed. When not using the soaking machine <NUM>, the unnecessary preserving solvent (carrier) or solution flows inside the discharge needle <NUM> on the discharge side, and is discharged. Accordingly, it is possible that no sample flows through the discharge needle <NUM> on the discharge side. When using gas or supercritical fluid as a carrier, the carrier containing the sample is discharged.

As to a sample discharged from the inside of the applicator <NUM> by the discharge side first actuator <NUM>, its component is analyzed by the discharge side analysis section <NUM>. One example of the result obtained by the analysis is shown in <FIG>. The sample discharged from inside the applicator <NUM>, whose component is analyzed by the discharge side analysis section <NUM> is sent to a mass spectrometer <NUM> from the discharge side piping <NUM> by adjusting a pressure, a flow rate, or a concentration with the discharge side second actuator <NUM> to analyze the mass component.

Herein, it is understood that the peak <NUM> at the component in the graph of <FIG>, that corresponds to the component signal at which the intensity peak <NUM> is shown in <FIG> is lowered when comparing the graph of <FIG> obtained via analysis performed by the discharge side analysis section <NUM> with the graph of <FIG> obtained via analysis performed by the supply side analysis section <NUM>. This means that a part of component at which the peak is shown in <FIG> is consumed inside the applicator <NUM>.

It is determined that an analysis object sample is soaked in a crystalline sponge attached to a tip portion of the sample holder <NUM> attached into the applicator <NUM> at the time when the difference or ratio between both the peak values becomes a predetermined value by comparing data as shown in the <FIG> with data as shown in <FIG> via the control section <NUM>, followed by completing a series of operations.

A sectional view when the sample holder <NUM> is viewed from the front surface is shown in <FIG>. The sample holder <NUM> is formed with a flat surface <NUM> at one end of the base portion <NUM> supported by a handling operator. A trunk portion <NUM> whose outer diameter is smaller than that of the base portion <NUM> is formed at a tip of the flat surface <NUM>; a guide surface 310D processed into a taper shape is formed at a tip of the trunk portion <NUM>; and a thin pin <NUM> is formed in the tip portion.

A recess portion <NUM> as a positioning member for attaching the sample holder to the goniometer head <NUM> in the single-crystal X-ray structure analysis apparatus <NUM> is formed to the upper surface 310A of the figure, that is another end surface of the base portion <NUM>. Further, an injection needle hole <NUM> and a discharge needle hole <NUM> each passing through the trunk portion <NUM> from the base portion <NUM> are formed in the sample holder <NUM>.

The taper portions 310B and 310C each processed into a taper shape are formed on the respective end surfaces on the recess portion <NUM> side in the injection needle hole <NUM> and the discharge needle hole <NUM>.

The taper portions 310B and 310C become guide surfaces when inserting the injection needle <NUM> and the discharge needle <NUM>. Further, the area around which the taper surface 310B is formed and the area around which the taper surface 310C is formed out of the recess portion <NUM> become seal surfaces when the injection needle <NUM> and the discharge needle <NUM> are inserted into the injection needle hole <NUM> and the discharge needle hole <NUM>, respectively, as described later.

The entire sample holder <NUM> or the recess portion <NUM> as a part of the base portion <NUM> is formed of a magnetic material for magnetic connection with the magnetic material in the tip portion of the goniometer head <NUM>.

The crystalline sponge <NUM> in which an analysis sample is soaked is attached (adheres) to the tip portion of the pin <NUM>. This crystalline sponge <NUM> is formed of a different component depending on a type of analysis object sample.

<FIG> shows a sectional view of a needle insertion part <NUM> where the injection needle <NUM> and the discharge needle <NUM> are inserted into the sample holder <NUM>. This needle insertion part <NUM> comprises a holding block <NUM> that holds an injection needle <NUM> and a discharge needle <NUM>, and a drive section <NUM> that drives the holding block <NUM> in an upward-downward direction (Refer to an arrow in the figure).

The injection needle <NUM> and the discharge needle <NUM> each are closely attached and held to/by the holding block <NUM> via welding or the like, for example.

A protrusion portion <NUM> is formed on a tip portion side (lower side in the <FIG>) of the injection needle <NUM> and the discharge needle <NUM> in the holding block <NUM>. Further, grooves <NUM> and <NUM> for O-ring insertion are formed to an end surface of the protrusion portion <NUM>, and O-rings <NUM> and <NUM> are attached into the grooves <NUM> and <NUM>, respectively.

Further, an outer diameter dimension of the protrusion portion <NUM> is formed to be slightly smaller than an inner diameter dimension of the recess portion <NUM> formed to the sample holder <NUM>.

The drive section <NUM> constituted by using for example, an electric motor, or an air cylinder or a hydraulic cylinder and the like drives the holding block <NUM> in the upward-downward direction, without going into detail.

<FIG> shows a cross-section of the applicator <NUM>. An opening <NUM> as a portion in which the base portion <NUM> of the sample holder <NUM> is inserted, a cylindrical space portion <NUM> in which the trunk portion <NUM> of the sample holder <NUM> is inserted, and a tip space portion <NUM> in which the pin <NUM> of the sample holder <NUM> is inserted are formed in the applicator. The tip space portion <NUM> in which the pin <NUM> is inserted has its diameter becoming smaller toward the tip, thereby having a so-called conical shape. Further, according to the applicator <NUM>, in a state where the sample holder <NUM> is attached thereto, an O-ring groove <NUM> is formed to a surface <NUM> brought into contact with the flat surface <NUM> of the base portion <NUM>.

<FIG> shows a state where the sample holder <NUM> is attached into the applicator <NUM>. In a state where the crystalline sponge <NUM> is attached to the tip portion of the pin <NUM> of the sample holder <NUM>, the trunk portion <NUM> of the sample holder <NUM> is inserted into the cylindrical space portion <NUM> of the applicator <NUM> with the guide surface processed into a taper shape at the tip of the trunk portion <NUM> as a guide.

Further, when pressing the sample holder <NUM> into the applicator <NUM>, the trunk portion <NUM> of the sample holder <NUM> inserted into the cylindrical space portion <NUM> of the applicator <NUM> becomes a guide to insert the base portion <NUM> of the sample holder <NUM> into the opening <NUM> of the applicator <NUM>.

In this manner, the sample holder <NUM> is attached to the applicator <NUM>; and in a state where the base part <NUM> of the sample holder <NUM> is inserted into the opening <NUM> of the applicator <NUM>, the injection needle <NUM> and the discharge needle <NUM> are inserted in the injection needle hole <NUM> and the discharge needle hole <NUM>, respectively, to supply a sample into the cylindrical space portion <NUM> and the tip space portion <NUM> of the applicator <NUM>.

<FIG> shows a state where the injection needle <NUM> and the discharge needle <NUM> are inserted into the cylindrical space portion <NUM> of the applicator <NUM> from the injection needle hole <NUM> and the discharge needle hole <NUM>. In this state, the applicator <NUM> is held by holding means that is not shown in the figure, and the posture where the injection needle <NUM> and the discharge needle <NUM> are inserted thereinto is kept. The injection needle <NUM> and the discharge needle <NUM> are inserted into the injection needle hole <NUM> and the discharge needle hole <NUM>, respectively, by downwardly pressing the holding block <NUM> that holds these needles by the drive section <NUM>.

As a procedure in which the injection needle <NUM> is inserted into the injection needle hole <NUM>, and the discharge needle <NUM> is inserted into the discharge needle hole <NUM>, these needles are pressed downward together with the holding block <NUM> by the drive section <NUM>. Thus, first, the tip portion of the injection needle <NUM> comes into contact with the taper surface 310B processed into a taper shape at the upper end portion of the injection needle hole <NUM> to enter the injection needle hole <NUM>, and next, the tip portion of the discharge needle <NUM> comes into contact with the taper surface 310C processed into a taper shape at the upper end portion of the discharge needle hole <NUM> to enter the discharge needle hole <NUM>.

The tip portion of the injection needle <NUM> moves downward through the inside of the injection needle hole <NUM> by continuing the state of being driven by the drive section <NUM>, and reaches the cylindrical space portion <NUM> of the applicator <NUM>. Following this, the tip portion of the discharge needle <NUM> moves downward through the inside of the discharge needle hole <NUM>, and reaches the cylindrical space portion <NUM> of the applicator <NUM>.

When continuing the state of being driven by the drive section <NUM> even after a tip portion of the injection needle <NUM> and another tip portion of the discharge needle <NUM> both reach the cylindrical space portion <NUM> of the applicator <NUM>, the protrusion portion <NUM> of the holding block <NUM> reaches the recess portion <NUM> formed to the sample holder <NUM>.

When continuing this state of being driven by the drive section <NUM>, the sample holder <NUM> is pressed onto the applicator <NUM> side, and an O-ring <NUM> attached into an O-ring groove <NUM> is pressed to ensure sealing between the sample holder <NUM> and the applicator <NUM>.

Further, the O-ring <NUM> attached into the O-ring groove <NUM>, and the O-ring <NUM> attached into the O-ring groove <NUM> that are formed to the protrusion portion <NUM> of the holding block <NUM> each are pressed by the recess portion <NUM> of the sample holder <NUM>. By this, sealing is ensured between the holding block <NUM> and the sample holder <NUM>.

By having such a configuration, the cylindrical space portion <NUM> inside the applicator <NUM> into which the sample holder <NUM> is attached, that is, the space surrounded by the sample holder <NUM> and the applicator <NUM> can be made to maintain an airtight state to the outside.

In this state, the control section <NUM> shown in <FIG> controls the supply side first actuator <NUM>, the supply side analysis section <NUM>, the supply side second actuator <NUM> and the temperature controller <NUM> to supply a sample fed from the chromatography apparatus <NUM> into the cylindrical space portion <NUM> and its tip space portion <NUM> of the applicator <NUM> from the injection needle <NUM>.

Further, the control section <NUM> controls the discharge side first actuator <NUM>, the discharge side analysis section <NUM> and the discharge side second actuator <NUM> to discharge an excessive sample out of the sample supplied to the inside of the cylindrical space portion <NUM> of the applicator <NUM> from the discharge needle <NUM>.

Further, the control section <NUM> accelerates soaking of a sample in the inside of the crystalline sponge <NUM> by controlling the temperature controller <NUM> in a state where the sample is supplied into the cylindrical space portion <NUM> and its tip space portion <NUM> of the applicator <NUM>.

In this manner, the control section <NUM> controls the drive section <NUM> to raise the holding block <NUM> after it is confirmed from data given from the supply side analysis section <NUM> and the discharge side analysis section <NUM> that the sample is soaked in the crystalline sponge <NUM> by controlling/maintaining the temperature of the applicator <NUM> with the temperature controller <NUM> by a prescribed time. By this, the injection needle <NUM> and the discharge needle <NUM> are removed from the injection needle hole <NUM> and the discharge needle hole <NUM> that are formed in the sample holder to end a step of soaking the sample in the crystalline sponge.

In addition, in the configuration shown in <FIG> as well as <FIG>, the injection needle <NUM> whose tip portion (on the lower side in <FIG> and <FIG>) protrudes from the holding block <NUM> has a so-called longer shape in length than that of the discharge needle <NUM>. However, in contrast, there are some cases where namely, the discharge needle <NUM> whose tip portion protrudes from the holding block <NUM> has a longer shape in length than that of the injection needle <NUM>, depending on a type of the handling sample.

In addition, the state shown in this <FIG> shows a state where the injection needle <NUM> and the discharge needle <NUM> that are shown in the above-described <FIG> are inserted into the sample holder <NUM> and the applicator <NUM>. However, in <FIG>, displaying the holding block <NUM> and the drive section <NUM> is omitted.

In addition, according to the configuration shown in <FIG>, the mass spectrometer <NUM> is described as a different configuration from the soaking machine <NUM>, but may be regarded as part of the soaking machine <NUM> by integrating the mass spectrometer <NUM> into the soaking machine <NUM>.

A perspective view of a sample tray (well plate) <NUM> in a state where a plurality of applicators <NUM> each into which a sample holder <NUM> is attached are stored inside a tray <NUM>, the sample holder at the tip portion of which a crystalline sponge where a sample is soaked is included, is shown in <FIG> according to the soaking machine <NUM> relating to the present Example. The plurality of applicators <NUM> each into which the sample holder <NUM> is attached are stored in the sample tray <NUM>, but color of the applicator <NUM> is differentiated depending on a type of the crystalline sponge <NUM> in which a sample is soaked, and thus the type of sample soaked in the crystalline sponge <NUM> can be easily determined.

According to the present Example, the sample can be safely soaked into a very small and fragile crystalline sponge <NUM> attached to the tip potion of the pin <NUM> of the sample holder <NUM> in a state where the sample holder <NUM> is attached into the applicator <NUM>.

Further, according to the present Example, the control section <NUM> controls the supply side first actuator <NUM>, the supply side analysis section <NUM> and the supply side second actuator <NUM>; the discharge side first actuator <NUM>, the discharge side analysis section <NUM> and the discharge side second actuator <NUM>; and further, the temperature controller <NUM> to soak the sample into the crystalline sponge <NUM>, and thus it becomes easier to set a soaking condition of an analysis object sample than the case where soaking of the sample is carried out by a conventionally manual operation.

Further, according to the present Example, it can be easily confirmed by the control section <NUM> that a single-crystal of the sample is formed inside the crystalline sponge <NUM> by comparing data obtained via analysis at the supply side analysis section <NUM> with data obtained via analysis at the discharge side analysis section <NUM>.

In addition, though various Examples according to the present invention are described above, the present invention is not limited to the above-described Examples and includes various modified examples. For example, the above-described Examples describe the entire system in detail in order to facilitate understanding of the present invention, but are not necessarily limited to those having all the configurations that have been described. Further, part of a configuration of one Example may be replaced with a configuration of another Example; further, a configuration of another Example may also be added to a configuration of one Example; and with respect to a part of a configuration of each Example, further performed may be addition/deletion/replacement of another configuration.

The present invention is widely applicable for a searching method of a material structure, an X-ray structure analysis apparatus used for the same, and so forth.

In addition, the present international application claims priority under <CIT>, and the entire content of <CIT> is applied to the present international application.

Claim 1:
A soaking machine (<NUM>) for soaking a sample, comprising:
a supply section configured to supply the sample to a porous complex crystal (<NUM>) held by a sample holder (<NUM>),
a temperature control section configured to control a temperature of the porous complex crystal (<NUM>),
a drive section (<NUM>) configure to drive the supply section, and
a control section (<NUM>) configured to control the supply section, the temperature control section and the drive section (<NUM>),
characterised in that when the sample holder (<NUM>) is set in the soaking machine (<NUM>) in a state where the sample holder (<NUM>) is attached to an applicator (<NUM>);
the supply section is adapted to supply the sample to the porous complex crystal (<NUM>) held by the sample holder (<NUM>) inside the applicator (<NUM>); and
the temperature control section is adapted to control the temperature of the porous complex crystal (<NUM>) held by the sample holder (<NUM>), inside the applicator (<NUM>) into which the sample is supplied.