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 that can be performed by anyone who is not 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 specifically as a method capable of catching a precise and highly accurate three-dimensional structure of molecules. In Patent Document <NUM> an X-ray spectroscopic analyzer is described that analyzes a single-crystal structure through the use of both X-ray diffraction analysis and energy-dispersive X-ray fluorescence analysis.

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 known from not only the following Non-Patent Documents <NUM> and <NUM> but also 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 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, the single-crystal sample as an analysis object was difficult to be prepared, and skillfulness of such as experience and intuition was further required for determining the crystal structure of the single-crystal from data obtained by analyzing the single-crystal sample of an analysis object 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, in recent years, as technological development of single-crystal X-ray structure analysis apparatus moves ahead, a person who is not skilled in crystal structure analysis technology would be able to analyze a single-crystal sample with the single-crystal X-ray structure analysis apparatus if only the single-crystal sample can be available, and thus the crystal structure of the single-crystal sample has been able to be relatively easily determined.

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 with 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, a method of surely attaching a sample soaked in a very small and fragile crystalline sponge and formed therein, to a sample holder, is not disclosed in the above-described conventional technique.

The present invention is to provide a soaking machine of a single-crystal X-ray structure analysis sample, that makes it possible to surely perform soaking by supplying an analysis sample into this crystalline sponge in a state where the very small and fragile crystalline sponge for making the analysis sample into single-crystal is held by the sample holder in the single-crystal X-ray structure analysis apparatus, and to a soaking method therefor, by solving problems of the above-described conventional technique.

The soaking machine according to the present invention makes it possible to surely perform soaking by supplying an analysis sample into the porous complex crystal in a state where a crystalline sponge that is a very small and fragile porous complex crystal for making the analysis sample into a single-crystal is held at a sample holder in the single-crystal X-ray structure analysis apparatus.

Next, a soaking machine of a single-crystal structure analysis sample for a single-crystal X-ray structure analysis apparatus, that makes it possible to soak an analysis sample in a sponge-shaped material (crystalline sponge or porous complex crystal) and surely supply the sample thereto as a sample holder of the single-crystal X-ray structure analysis apparatus, according to the present invention; and a soaking method therefor are described referring to the drawings. In addition, the expression of "A or B" in the present application means "at least one of A and B", and includes "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 system <NUM> comprising a single-crystal X-ray structure analysis apparatus relating 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 samples 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 prepared with the soaking machine <NUM> are stored; 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 a single-crystal X-ray structure analysis apparatus provided with 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> 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 opened 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 also 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 focal point, and X-rays are generated from the X-ray focal point, 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 makes it possible to irradiate beams with higher brightness, and can also be selected from radiation sources 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, the goniometer <NUM> supporting a sample S to be analyzed comprises a θ rotation table <NUM> that is rotatable centering a sample axis line ω passing through an X-ray incident point of the sample S, and a 2θ rotation table <NUM> that is arranged around the θ rotation table <NUM> and is rotatable centering the sample axis line ω. The goniometer <NUM> is provided with a goniometer head <NUM> with which the sample S is equipped. 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> also mentioned below.

Driving 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 driving 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 driving devices to be intermittently or continuously rotated so as to make a so-called 2θ rotation. The above-described driving 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 centering the sample axis line 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 focal point 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 connected mutually 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 comprising CPU <NUM>, RAM <NUM>, ROM <NUM>, and an analysis section <NUM> provided with a hard disk.

An inkjet plotter, a dot printer, an inkjet printer, an electrostatic transfer printer, or any other printing unit having arbitrary structure can be used for the printer <NUM>. In addition, the analysis section <NUM> can be constituted from a magneto-optical disk, a semiconductor memory, or any other storage medium having arbitrary structure in place of 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>, where a single-crystal structure analysis processing is performed, provided with the hard disk. These pieces of application software achieves a predetermined function after being read from the hard disk in the analysis section <NUM>, as needed, and being transferred 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 various 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 measured images obtained by the microscope, and further shown are for example, measurement results obtained via analysis performed with XRF, Raman rays or the like other than X-rays, and the other 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 connected to be able to communicate 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 in which "condition" is written are areas for storing every kind of information including device information and measurement conditions when the measurement data is able to be obtained.

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 attachments such as a sample high-temperature device and so forth are used, and various other conditions are conceivable.

In addition, information required for soaking thereof may be acquired via the cloud, and the information required for the soaking may be acquired from those stored inside a control section in the soaking machine. For example, the necessary soaking condition can be easily acquired and inputting/setting thereof can be automatically executed by searching for a soaking condition or the like provided via a cloud structure based on specific information of a sample holder or an applicator.

Thus, it becomes possible to unitarily manage data obtained by the subsequent structure analysis processing. Further, it can also be performed more easily to store, verify and manage the sample after measurement/analysis.

According to the above-described example, information is stored in the cloud, but may be stored in a memory (HDD) inside or outside a single-crystal X-ray structure analysis apparatus without being necessarily limited thereto. Further, when the order of samples to be measured is determined in advance, the specific information may be stored in the memory in advance without taking a configuration in which the specific information is acquired from the sample holder as well as the applicator and may be read in order to acquire corresponding information.

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 (for example, CCD or the like) arranged in planar array, 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 the X-rays to irradiate 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 represent symmetry in the actual space of the object material that is a three-dimensional space. Accordingly, it is generally difficult to specify the (spatial) arrangement of atoms and molecules that constitute the material only with 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, via development of a material called "crystalline sponge" that is a very small and fragile porous complex crystal having an approximate size of several <NUM> to several <NUM>, whose inside has countless pores having a diameter of <NUM> to <NUM> are formed, the single-crystal X-ray structure analysis has become widely applicable for those including a liquid compound that cannot be crystallized or a very small amount of a sample having several ng to several µg that is incapable of acquiring a sufficient amount to perform crystallization.

However, in the current situation, in order to perform soaking (post-crystallization) that is 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, having approximately several ng to several µg, separated by variouspretreatment (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 quickly (in a short period of time in such an extent that the crystalline sponge is not broken due to being dried), and accurately installing 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 wide use of the single-crystal X-ray structure analysis using the crystalline sponge being impeded.

The present invention that has been accomplished based on the above-described inventor's knowledge enables a single-crystal X-ray structure analysis with a very small and fragile crystalline sponge to be surely and easily performed by using a sample holder (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 quickly attached to a predetermined position in 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 quickly, surely and easily by anyone while using a very small, fragile and difficultly handleable crystalline sponge; and further provides a sample holder as a tool therefor.

The configuration of the soaking machine <NUM> for soaking an analysis object sample in a crystalline sponge according to the configuration of the single-crystal X-ray structure analysis system <NUM> comprising the single-crystal X-ray structure analysis apparatus <NUM> relating to Example <NUM> 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 <NUM> according to the present invention. The soaking machine <NUM> relating to the present Example comprises a supply side pipe <NUM>, a supply side first actuator <NUM>, a supply side analysis section <NUM>, a supply side second actuator <NUM>, a supply side piping <NUM>, an injection needle (injection pipe) <NUM>, an applicator <NUM> into which a sample holder <NUM> (corresponding to a sample holder <NUM> in <FIG>) is attached, a temperature adjustment unit (temperature adjustment vessel) <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 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 analysis object 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 piping <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>. At this time, only a sample or a solution in which the sample and the preserving solvent (carrier) are mixed flows inside a sample introduction pipe <NUM> on the supply side, and is supplied. 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 adjustment unit <NUM> is controlled by the control section <NUM> in this state, and the applicator <NUM> is heated or cooled so that the applicator <NUM> comprising the sample holder <NUM> reaches a desired temperature.

When using the soaking device <NUM>, an excessive sample or the solution in which the sample and the preserving solvent (carrier) are mixed 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 adjustment unit <NUM>. That is, the excessive sample means a sample discharged depending on 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>. When not using the soaking device <NUM>, the unnecessary preserving solvent (carrier) or solution flows inside the sample introduction pipe <NUM> on the discharge side, and is discharged. Accordingly, it is possible that no sample flows through the sample introduction pipe <NUM> on the discharge side. In addition, 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 the inside of 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 body part <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 body part <NUM>; and a thin pin <NUM> is formed in the tip portion.

A recessed portion <NUM> that is 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 on the upper surface 310A of the figure, that is another end surface of the base portion <NUM>. Further, a hole <NUM> for injection needle and a hole <NUM> for discharge needle passing through the body part <NUM> from the base portion <NUM> are formed in the sample holder <NUM>. The taper portions 310B and 310C processed into taper shape are formed on the respective end surfaces on the recessed portion <NUM> side in the hole <NUM> for injection needle and the hole <NUM> for discharge needle. The taper portions 310B and 310C become guide surfaces when inserting the injection needle <NUM> and the discharge needle <NUM>.

The entire sample holder <NUM> or the recessed portion <NUM> as a part of the base portion <NUM> is formed of a magnetic body to connect magnetically with the magnetic body in the tip portion of the goniometer head <NUM>.

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

In <FIG>, the appearance of the sample holder <NUM> is shown as a perspective view. The information storage section <NUM> for storing information (information about the type of crystalline sponge <NUM>, the lot number and so forth) about the crystalline sponge <NUM> attached (adhered) to the tip portion of the pin <NUM> is formed on the outer peripheral surface of the base portion <NUM>. The information storage section <NUM> is formed by for example, a bar-code, a QR code (registered trademark), an IC chip or the like.

Information stored in the information storage section <NUM> is read by the reading section <NUM> shown in <FIG>, and stored inside the control section <NUM>. The control section <NUM> controls the supply side first actuator <NUM>, the supply side analysis section <NUM>, the supply side second actuator <NUM>, the temperature adjustment unit <NUM>, the discharge side first actuator <NUM>, the discharge side analysis section <NUM> and the discharge side second actuator <NUM> based on the information stored in the information storage section <NUM>, that is read by the reading section <NUM>; and soaks the sample in the crystalline sponge <NUM> by supplying the analysis object sample from the injection needle <NUM> to the crystalline sponge <NUM> attached (adhered) to the tip portion of the pin <NUM> of the sample holder <NUM>.

The control section <NUM> stores the soaking condition (condition of including any of a temperature, a pressure, a concentration, a processing time and so forth of the sample supplied into the sample holder <NUM>) when inside the applicator <NUM>, the sample is soaked in the crystalline sponge <NUM>. The soaking condition stored in the control section <NUM> can be transferred to the other processing means via a communication line that is not shown in the figure.

In <FIG>, the appearance of the applicator <NUM> into which the sample holder <NUM> is attached is shown as a perspective view. The appearance of the applicator <NUM> has a shape of cuboid. Further, applicators <NUM> formed of a resin are differentiated by colors, depending on a type of crystalline sponge <NUM> attached to the tip portion of the pin <NUM> of the sample holder <NUM> attached therein. By this, the type of crystalline sponge <NUM> attached to the tip of the pin <NUM> of the sample holder <NUM> can be determined from the color of the applicator <NUM> in a state where the sample holder <NUM> is attached into the applicator <NUM>.

The A - A cross-section of the applicator <NUM> of <FIG> is shown in <FIG>. A portion <NUM> in which the base portion <NUM> of the sample holder <NUM> is inserted, a cylindrical portion <NUM> in which the body part <NUM> of the sample holder <NUM> is inserted, and a tip portion <NUM> in which the pin <NUM> of the sample holder <NUM> is inserted are formed in the applicator <NUM>. The conical shaped tip portion <NUM> in which the pin <NUM> is inserted has its diameter becoming smaller as it goes toward the tip. Further, an O-ring groove <NUM> is formed on an inner surface <NUM> where the applicator <NUM> comes into contact with the flat surface <NUM> of the base portion <NUM> of the sample holder <NUM>.

<FIG> shows a state where the sample holder <NUM> is attached into the applicator <NUM>; the injection needle <NUM> and the discharge needle <NUM> are further inserted inside the applicator <NUM>; and the crystalline sponge <NUM> is attached to the tip portion of the pin <NUM> of the sample holder <NUM>. Since the injection needle <NUM> supplies a sample near the crystalline sponge <NUM> attached to the tip portion of the pin <NUM>, it is inserted into the applicator <NUM> so as to become deeper than the discharge needle <NUM>.

In this state, the sample holder <NUM> is pressed to the applicator <NUM> by pressing means that is not shown in the figure, and thus the O-ring <NUM> is deformed by pressing the O-ring <NUM> attached to the O-ring groove <NUM> where the flat surface <NUM> of the base portion <NUM> of the sample holder <NUM> is formed on the inner surface <NUM> of the applicator <NUM>. Further, sealing by seal means that is not shown in the figure is applied respectively between the injection needle <NUM> and the hole <NUM> for the injection needle, and between the discharge needle <NUM> and the hole <NUM> for the discharge needle. By having such a configuration, the cylindrical portion <NUM> in the applicator <NUM> into which the sample holder <NUM> is attached, and the conical shaped tip portion <NUM> at the tip of the cylindrical portion 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 adjustment unit <NUM> to supply the sample sent out from the chromatography apparatus <NUM>, to the cylindrical portion <NUM> and its tip portion <NUM> in 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 the oversupplied samples out of the samples supplied into the inside of the cylindrical portion <NUM> in the applicator <NUM> from the discharge needle <NUM>.

The sample is soaked into the crystalline sponge <NUM> by maintaining the sample for a certain amount of time in a state of having been supplied to the cylindrical portion <NUM> and its tip portion <NUM> in the applicator <NUM>. At this time, the control section <NUM> controls the supply side first actuator <NUM>, the supply side analysis section <NUM>, the supply side second actuator <NUM> and the temperature adjustment unit <NUM> to control the soaking condition under which the sample is soaked in the crystalline sponge, including a temperature, a pressure, a concentration, a processing time and so forth of the sample supplied to the cylindrical tip portion <NUM> in the applicator <NUM> from the injection needle <NUM>.

In addition, the state shown in the above-described <FIG> exhibits a state where the injection needle <NUM> and the discharge needle <NUM> as shown in the above-described <FIG> are inserted in the sample holder <NUM> and the applicator <NUM>.

In addition, according to the configuration shown in <FIG> as described above, the mass spectrometer <NUM> has been described as a different configuration from the soaking machine <NUM> for a single-crystal X-ray structure analysis apparatus, but the mass spectrometer <NUM> may be a part of the soaking machine <NUM> for the single-crystal X-ray structure analysis apparatus by integrating the mass spectrometer <NUM> with the single-crystal X-ray structure analysis <NUM>.

<FIG> is a perspective view of a sample tray (well plate) <NUM>, showing a state where a plurality of applicators <NUM> are stored inside a tray <NUM>, the plurality of applicators into which a sample holder <NUM> is attached, the sample holder in a tip portion of which a sample is soaked by the soaking machine for the single-crystal X-ray structure analysis apparatus relating to the present Example. The plurality of applicators <NUM> 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 an analysis sample is soaked, and thus the type of sample soaked in the crystalline sponge <NUM> inside the applicator <NUM> of each color can be easily determined by color thereof.

According to the present Example, a sample can be more safely soaked into a very small and fragile crystalline sponge <NUM> attached to the tip portion 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>, the supply side second actuator <NUM>, the discharge side first actuator <NUM>, the discharge side analysis section <NUM>, the discharge side second actuator <NUM>, and further the temperature adjustment unit <NUM> to soak the sample into the crystalline sponge <NUM>; and thus it becomes easier to set the soaking condition of an analysis object sample than that in the case where soaking the sample was performed by a conventional manual operation.

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

The configuration in which the crystalline sponge <NUM> is attached to the tip portion of the pin <NUM> of the sample holder <NUM> has been described in Example <NUM>, but the case of using a sample holder <NUM> in the configuration as shown in <FIG> is described in the present Example.

According to the present Example, the configuration excluding the sample holder <NUM> is the same configuration as shown in <FIG> in Example <NUM> and the configuration of the applicator <NUM> is also the same as the shape of the applicator <NUM> that has been described using <FIG> in Example <NUM>, and thus detailed description is omitted.

In the sample holder <NUM> used in the present Example, as its cross-sectional shape being shown in <FIG>, a pipe <NUM> is newly attached and fixed to a recessed portion 710E formed in the tip portion of a guide surface 710D processed into a taper shape, ahead of the body part <NUM> of the sample holder <NUM>. A hole <NUM> connected to a hole <NUM> for injection needle, that is formed in the sample holder <NUM> is formed inside the pipe <NUM>. A crystalline sponge <NUM> in which a sample is soaked is formed (or attached) inside the hole <NUM> of the pipe <NUM>.

The body of the sample holder <NUM> is formed of magnetic metal, but its pipe <NUM> formed of a material transmitting X-rays such as, for example, borosilicate glass, quartz, kapton or the like is inserted in the recessed portion 710E formed in the tip portion of the guide surface 710D, and is further fixed with an adhesive or the like.

A base portion <NUM> of the sample holder <NUM>, a lower surface <NUM> of the base portion <NUM>, and a recessed portion <NUM> inside an upper surface 710A of the base portion <NUM>, respectively, are the same as the configuration of corresponding portions to the sample holder <NUM> described in Example <NUM>, and thus detailed description is omitted.

In the present Example, the injection needle <NUM> is inserted in the hole <NUM> for injection needle, and the discharge needle <NUM> is inserted in the hole <NUM> for discharge needle by attaching the sample holder <NUM> in such a configuration into the applicator <NUM> described in Example <NUM> referring to <FIG>. A taper portion 710B to be a guide surface, when inserting the injection needle <NUM>, is formed, at an end portion on an upper side of the hole <NUM> for injection needle. A taper portion 710C to be a guide surface, when inserting the discharge needle <NUM>, is formed, at an end portion on an upper side of the hole <NUM> for discharge needle.

The configuration in which a sample is supplied to a crystalline sponge <NUM> from the injection needle <NUM> inserted in the hole <NUM> for injection needle, at an upper end portion of which the taper portion 710B is formed; and from which gas or liquid inside the applicator <NUM> is discharged by the discharge needle <NUM> is the same as the case in Example <NUM>, and thus detailed description is omitted.

In addition, according to the configuration shown in <FIG>, a case where a hole <NUM> formed into a pipe <NUM> has the same diameter from top to bottom is shown, but in <FIG>, the hole <NUM> may have a taper shape in such a manner the diameter becomes larger as it goes toward the lower side, or may be formed into a stepped shape in such a manner that the diameter becomes larger in the midway than that on the upper side.

According to the present Example, the sample can be more safely soaked into a very small and fragile crystalline sponge <NUM> attached into the hole <NUM> for injection needle, that is formed by passing through the pipe <NUM> at the center portion 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, similarly to the case in Example <NUM>, the control section <NUM> controls the supply side first actuator <NUM> and the supply side analysis section <NUM>, and further the supply side second actuator <NUM>; and the discharge side first actuator <NUM>, the discharge side analysis section <NUM>, the discharge side second actuator <NUM>, and further the temperature adjustment unit <NUM> to soak a sample in the very small and fragile crystalline sponge <NUM>; and thus it becomes easier to set the soaking condition of the sample than that in the case where soaking the sample in the crystalline sponge was performed by a conventional manual operation.

Furthermore, according to the present Example, similarly to the case in Example <NUM>, it can be easily confirmed with the control section <NUM> that the sample is surely soaked into the crystalline sponge <NUM>, by comparing data obtained via analysis with the supply side analysis section <NUM> with data obtained via analysis with the discharge side analysis section <NUM>.

According to the configuration comprising the soaking machine <NUM> of <FIG> as described in Example <NUM>, it is made to become a configuration in which gas or sample liquid discharged from the inside of the applicator <NUM> by the discharge needle <NUM> is sent to a mass spectrometer 600to be discharged. In contrast, according to the present Example, as shown in <FIG>, there is provided a return route <NUM> for sending the sample discharged from the mass spectrometer <NUM>, to a chromatography apparatus <NUM>.

The sample whose predetermined component is extracted again by chromatography apparatus <NUM>, that has been returned to the chromatography apparatus <NUM> from the mass spectrometer <NUM> through the return route <NUM> is supplied to the soaking machine <NUM>. By having such a configuration, the sample circulates between the chromatography apparatus <NUM> and the mass spectrometer <NUM> through the soaking machine <NUM>. The operation of the soaking machine <NUM> is identical to one described in Example <NUM>.

According to the present Example, by having the configuration as shown in <FIG>, it was made detectable that soaking of an object sample in the crystalline sponge <NUM> reached an end point thereof by comparing analysis waveform data (corresponding to <FIG> in Example <NUM>) of the component discharged from the applicator <NUM>, that was detected with the discharge side analysis section <NUM>, with waveform data (corresponding to <FIG> in Example <NUM>) that was detected with the supply side analysis section <NUM>.

That is, as to the duration of soaking the object sample in the crystalline sponge <NUM>, the peak value of a wave form of the sample component in the middle of being soaked in the crystalline sponge <NUM>, out of waveform data detected by the discharge side analysis section <NUM>, decreases with time. In contrast, no component corresponding to the object sample is consumed when it is completed to soak the analysis object sample in the crystalline sponge <NUM>, and thus the wave height value corresponding to an aimed sample component of waveform data detected by the discharge side analysis section <NUM> becomes identical value to the wave height value corresponding to an aimed sample component of waveform data detected by the supply side analysis section <NUM>.

In the present Example, by using this characteristic via the configuration as shown in <FIG>, a point of time when the peak levels are identical to each other is detected as an end point by comparing waveform data at the position corresponding to the single-crystal component detected by the supply side analysis section <NUM> with waveform data at the position corresponding to the single-crystal component detected by the discharge side analysis section <NUM>.

According to the present Example, a sample can be used while making it circulate between the chromatography apparatus <NUM> and the mass spectrometer <NUM> through the soaking machine <NUM>, and thus it can be surely detected that an analysis object sample is soaked in a very small and fragile crystalline sponge, even when the amount of sample is very small.

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, a part of a configuration of one Example may be replaced with a configuration of another 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>.

Claim 1:
A soaking machine (<NUM>) for soaking a sample, comprising:
a supply section configured to supply the sample into an applicator (<NUM>) in which a sample holder (<NUM>) that holds a porous complex crystal is inserted,
a temperature adjustment section (<NUM>) configured to control a temperature of the applicator (<NUM>),
a discharge section configured to discharge the sample from the inside of the applicator (<NUM>) in which the sample holder (<NUM>) is inserted, and
a control section (<NUM>) configured to control the supply section, the temperature adjustment section (<NUM>) and the discharge section.