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, here has been a demand for 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 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 each having a diameter of <NUM> to <NUM> are formed).

Patent Document <NUM> describes an integrated crystal mounting and alignment system for high-throughput biological crystallography. For this purpose a sample assembly is taught which comprises a sample captured in a sample loop which, in turn, is attached to a sample tube. The sample tube is attached to a sample base having. A sample cassette and a cassette cover are further provided to receive and keep a plurality of sample assemblies immersed in liquid nitrogen.

From Patent Document <NUM> a sample holder with an extension element is known. The sample holder comprises a tube for holding a sample and a base element that holds the tube. The extension element can be connected to the back side of the base element so that the height of the sample holder can be adjusted depending on whether the sample holder is received by a high-pressure freezing unit or attached to a goniometer.

Patent Document <NUM> describes an apparatus for growing crystal by vaporizing biological macromolecular solution into an oversaturated state. The apparatus comprises a sealed room that receives a crystallizing agent solution, and a communicating tube that communicates with the sealed room and has a small sectional area for suppressing convection of air. A plurality of droplets of solution dissolving a biological macromolecule and a crystallizing agent therein are held in the communicating tube with the plurality of droplets being separated from each other.

However, in the single-crystal X-ray structure analysis as becoming a conventional technique in which the above-described crystalline sponge is used, it is necessary to quickly and accurately perform a step of soaking a sample of a very small amount of approximately several ng to several µg separated by every kind of devices in a framework of a very small and fragile crystalline sponge having a size of approximately <NUM>, and further a step of accompanying fine and precise operations in which the very small crystalline sponge in which the sample is soaked is taken out; is attached to a tool; and is installed at the X-ray irradiation position inside a single-crystal X-ray structure analysis apparatus. In addition, these fine and precise operations carried out in a short period of time largely affect the measurement result of the sample after being soaked in the crystalline sponge, thereby being very important operations.

Accordingly, the present invention has been achieved in view of problems in the above-described conventional technique, and the objective is, specifically, to provide a sample holder unit capable of quickly, surely and easily performing single-crystal X-ray structure analysis with a crystalline sponge without conventionally fine and precise operations for which rapidness is required being accompanied, the operations including a removal operation of a sample soaked in a very small and fragile crystalline sponge and an attachment operation to an apparatus, even if not having specialized knowledge of X-ray structure analysis, in other words, to provide the sample holder unit used in a single-crystal X-ray structure analysis in order to realize a high-yield, efficient, very versatile and user-friendly single-crystal X-ray structure analysis apparatus.

According to a sample holder unit for a single-crystal X-ray structure analysis apparatus of the present invention as described above, an operation of soaking a sample in a fragile crystalline sponge in the single-crystal X-ray structure analysis apparatus, followed by an operation of attaching it to a goniometer tip can be quickly, precisely and easily carried out without accompanying conventionally precise and fine operations, and thus single-crystal X-ray structure analysis with a crystalline sponge can be quickly, precisely and easily carried out. Thus, it becomes possible to make the single-crystal X-ray structure analysis with the crystalline sponge be easily usable, and to widely spread it.

Next, the sample holder unit used in the single-crystal X-ray structure analysis apparatus in which a crystalline sponge is utilized, according to one embodiment of the present invention, are described in detail referring to the attached 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.

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> for surrounding the single-crystal X-ray diffractometer <NUM>, a door <NUM> provided in front of the casing <NUM>, and so forth. The door <NUM> 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, the 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 <NUM> and is rotatable with the sample axis line ω as a center. 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.

Then, <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. 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 <NUM> as an external storage medium, and so forth. These elements are electrically 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 the hard disk <NUM>. 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 hard disk <NUM> can also be constituted from a magneto-optical disk, a semiconductor memory, or any other storage medium having arbitrary structure.

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 hard disk <NUM>. A predetermined function is achieved after reading these pieces of application software from the hard disk <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 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 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, 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 single-crystal X-ray diffractometer, more specifically, to a tip 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 unit comprising a sample holder for the crystalline sponge (also referred to simply as a sample holder), the sample holder supporting the crystalline sponge 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 at the tip of the goniometer <NUM> in a short and quick period of time in such an extent that the crystalline sponge is not broken due to drying, 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 preciseness.

The present invention described below in detail resolves such a problem, that is, provides a sample holder unit for a single-crystal X-ray structure analysis apparatus as a tool for enabling performing an operation of soaking a sample in the crystalline sponge, followed by an operation including attaching it to an apparatus in a high-yield efficient, very versatile and user-friendly manner, by anyone while also using a very small, fragile and difficultly handleable crystalline sponge, and for making it possible to realize the single-crystal X-ray structure analysis apparatus.

<FIG> shows a tip of the goniometer <NUM> in an enlarged view, and this figure shows a state that, the sample holder <NUM>, being in an enlarged view as <FIG>, as a tool where the crystalline sponge <NUM> soaking a sample to be analyzed that is proposed according to the present invention is attached (mounted) to the goniometer head <NUM> as a tip of the goniometer <NUM> in advance. In addition, the sample holder <NUM>, for example, can be attached/detached to/from the goniometer head <NUM> at the tip of the goniometer <NUM> by an attaching/positioning mechanism for which magnetic force or the like is used, and can be attached easily and accurately at an exact position by anyone.

<FIG> shows a sectional view of the sample holder <NUM> according to Example <NUM>. The sample holder <NUM> comprises a disk-shaped base part <NUM> made of metal or the like, attached to the goniometer head <NUM> (Refer to <FIG>) at the tip of the goniometer <NUM>, and a protrusion part <NUM> formed in a protrusion shape extending downward from one surface thereof (the lower surface in the figure). The protrusion part <NUM> comprises s conical part 202a, and a sample holding part (corresponding to the so-called goniometer head pin) 202b formed in a protrusion shape. The crystalline sponge <NUM> in which the above-described sample to be analyzed is soaked is combinedly attached to the sample holder <NUM> beforehand at a predetermined position of the tip of the sample holding part 202b.

Further, an attachment part <NUM> in a recessed truncated cone shape is formed on the other surface (upper surface in the figure) of the base part <NUM>, and a magnet that is not shown in the figure or a projected engagement part (or recessed part) 203a is provided on a contact surface with the goniometer head <NUM> at the tip of the foregoing goniometer <NUM> in this attachment part <NUM>. By having this mechanism, the sample holder <NUM> can be attached/detached to/from the goniometer head <NUM> at the tip of the goniometer <NUM>, and can be easily and accurately attached thereto by anyone.

The outer diameter on the base part side of the conical part 202a of the sample holder <NUM> is set to be smaller than the outer diameter of the base part <NUM>, and an annular-shaped step part <NUM> is formed. Further, through-holes <NUM> and <NUM> passing from the base part <NUM> to the protrusion part <NUM> are formed as a sample introduction structure, and seal parts <NUM> and <NUM> each for airtightly sealing a hole interior are provided in respective through-holes <NUM> and <NUM>.

<FIG> shows a perspective view of an applicator <NUM> as a tool for storing the sample holder <NUM>, and soaking a sample in a crystalline sponge <NUM>, that is attached beforehand to the sample holder <NUM>. <FIG> is a sectional diagram of a sample holder unit <NUM> comprising an applicator <NUM>, and a sample holder <NUM> stored inside it.

The applicator <NUM>, in whose inside a storing space <NUM> for storing the sample holder <NUM> is formed, and further at whose upper portion the sample holder <NUM> is fitted in and an opening <NUM> for taking it out is formed, is formed of a transparent or opaque member such as for example, glass, a resin, metal or the like. On an annular bottom surface of the opening <NUM>, provided is, for example, an annular seal part (O-ring) <NUM>, and during storing of the sample holder <NUM>, the step part <NUM> of the sample holder <NUM> is airtightly maintained between the sample holder <NUM> and the applicator <NUM> by coming into contact with the seal part <NUM>.

The inner diameter of the opening <NUM> of the applicator <NUM> is set to be slightly larger than the outer diameter of the base part <NUM> of the sample holder <NUM>, and thus the inner wall of the opening <NUM> can be made to be a guide surface when inserting/ejecting the sample holder <NUM> thereinto/therefrom. Thus, preparation can be easily made without giving any damage to the sample S when removing the sample holder <NUM> comprising the crystalline sponge <NUM> in which a very small amount of a sample is soaked, from the applicator <NUM>.

Symbols <NUM> are a pair of pull-out prevention parts (rotary levers) provided onto an opening surface <NUM> of the applicator <NUM> comprising the opening <NUM>, and their ends <NUM> each are rotatably supported by a support point <NUM>, between a retracted position shown by a solid line and a position shown by a dashed line protruding to an inside of the opening <NUM> from the side.

As shown in <FIG>, when the sample holder <NUM> is inserted from the opening <NUM> of the applicator <NUM>, the step part <NUM> of the sample holder <NUM> comes into contact with the seal part <NUM> in the storing space <NUM>, and the upper end of the sample holder <NUM> protrudes from the opening surface <NUM> of the applicator <NUM>. Next, the ends <NUM> of the pull-out prevention parts <NUM> each are rotated in a direction of protruding toward the inside of the opening <NUM> while pushing the upper end of the sample holder <NUM> in an arrow direction by hand fingers or the like. As shown in <FIG>, the ends <NUM> of the pull-out prevention parts <NUM> each are engaged with the upper end of the sample holder <NUM> to suppress floating-up, and the step part <NUM> of the sample holder <NUM> is simultaneously brought into pressure contact with the seal part <NUM> by this rotation operation to maintain airtightness between the sample holder <NUM> and the applicator <NUM>.

<FIG> is an explanatory diagram showing a process of inserting sample introduction pipes (hereinafter, referred to simply as pipes) <NUM> and <NUM> as a sample introduction structure in through-holes <NUM> and <NUM> (Refer to <FIG>) of the sample holder, and <FIG> is an explanatory diagram in a state where the above-described pipes have been inserted therein. The pipes <NUM> and <NUM> each are airtightly maintained between the through-holes <NUM> and <NUM> by the seal parts <NUM> and <NUM> (Refer to <FIG>). Symbol <NUM> representing a support part for supporting the sample introduction pipes <NUM> and <NUM> supports both pipes in a state of being approximately parallel to each other at an interval equal to the interval between the through-holes <NUM> and <NUM>. A support part <NUM> whose height H is set to be higher than height h of the attachment part <NUM> in the sample holder <NUM> has approximately the same shape as that of the attachment part <NUM> formed into a recessed shape, as being truncated cone-shaped.

The sample introduction pipes <NUM> and <NUM> are simultaneously inserted in the through-holes <NUM> and <NUM> by pushing down the support part <NUM> with hand fingers, a manipulator or the like. The support part <NUM> whose lower end enters into a recessed part of the attachment part <NUM>, and comes into contact with the bottom surface of the recessed part, followed by stopping after lowering to stably support the pipes <NUM> and <NUM>.

As shown in <FIG>, the support part <NUM> protrudes upward (Refer to symbol <NUM>) by a difference of height H and height h from the attachment part <NUM> in a stopping state. This projected portion <NUM> is useful as a tool when pulling out the pipes <NUM> and <NUM>, after soaking a sample in the crystalline sponge <NUM>. That is, the pipes <NUM> and <NUM> can be efficiently pulled out at the same time by holding the projected portion <NUM> of the support portion <NUM> therebetween with hand fingers, a manipulator or the like to pull it up.

In <FIG>, symbol <NUM> represents a hydrophobic solvent (for example cyclohexane) injected at the bottom part of the storing space <NUM> in the applicator <NUM>, and setting is made to a level at which the crystalline sponge <NUM> at the tip part of the sample holding part 202b is immersed to fill it therewith. The pipe <NUM> is a sample injection pipe, and the pipe <NUM> is a discharge pipe. The tip of the pipe <NUM> extending to the vicinity of the crystalline sponge <NUM> is dipped in the solvent <NUM>, and the tip of the pipe <NUM> extends to a position of not being immersed in the solvent <NUM>.

In <FIG>, when a sample (for example, gas) to be measured is injected from the injection pipe <NUM>, the sample is penetrated in the solvent <NUM>, and soaked into the crystalline sponge <NUM> inside the solvent. The sample (a solvent, a carrier or the like) excessively supplied is discharged outside via the pipe <NUM>.

Thereafter, in the present example, the pipes <NUM> and <NUM> are pulled out at the same time by holding the projected portion <NUM> of the support portion <NUM> therebetween with hand fingers, a manipulator or the like to pull it up, and the sample holder <NUM> comprising the crystalline sponge <NUM> in which the sample is soaked is subsequently attached to the goniometer head <NUM> at the tip of the goniometer <NUM>. In addition, the sample holder <NUM> and the applicator <NUM> as a tool to be handled therefor are used together in combination as a sample holder unit <NUM>, and are prepared by the number required for an analysis operation and stored in a box-shaped container, that is, are also possible to be provided as a set.

According to the sample holder unit <NUM> with the above-described configuration, the crystalline sponge <NUM> attached to the tip of the pin-shaped holding part 202b (corresponding to a goniometer head pin) constituting part of the sample holder <NUM> can be safely and easily handled without damage, or deviation from the sample holder <NUM>. That is, the opening <NUM> becomes a guide surface even when it is removed from the applicator <NUM>, and thus the crystalline sponge <NUM> in which a very small amount of the sample is soaked can be safely, simply and easily prepared on the goniometer head <NUM> in a short and quick period of time in such an extent that no damage occurs due to drying, without any damage due to taking only it out from a soaking container unlike a conventional manner. According to the present Example, the sample holder <NUM> with which soaking of the sample is completed is removed from the applicator <NUM>, and is attached to the goniometer head <NUM> (Refer to <FIG>) at the tip portion of the goniometer <NUM>. In this manner, the sample S soaked in the crystalline sponge <NUM> is easily, precisely and quickly arranged at a predetermined position inside the single-crystal X-ray diffractometer <NUM> without requiring highly specialized knowledge and precise operations.

Next, described is soaking a sample in the crystalline sponge <NUM> inside the sample holder unit <NUM> (Refer to <FIG>) with the above-described configuration, that is performed using a soaking machine.

In <FIG>, a very small amount of the sample S extracted by LC (liquid chromatography) <NUM>, GC (gas chromatography) <NUM>, and further, SCF (supercritical fluid chromatography) <NUM>, CE (electrophoresis) <NUM> and so forth that constitute a pretreatment device <NUM> is supplied to a pair of the sample introduction pipes <NUM> and <NUM> inserted in the through-holes <NUM> and <NUM> of the sample holder <NUM> via the soaking apparatus (soaking machine) <NUM> provided with every kind of a switching valve and a pressure adjustment device, that supplies a fluid under the necessary conditions (flow rate and pressure), and the sample is selectively introduced into the storing space <NUM> inside the applicator <NUM>. That is, the sample is sent to the sample introduction pipe <NUM> on the supply side from the supply side pipe, and is supplied to the sample holder <NUM> inside the applicator <NUM> from the tip portion of the sample introduction pipe <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 pipe <NUM> on the supply side. In this manner, a very small amount of the sample S introduced thereinto comes into contact with the crystalline sponge <NUM> attached to the tip of the pin-shaped holding part 202b 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 thereinto, the excessive sample or a solution in which the sample and the preserving solvent (carrier) are mixed is discharged from the sample introduction pipe <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 a sample introduction tube <NUM> on the discharge side, and is discharged. Accordingly, it is possible that no sample flows through the sample instruction tube <NUM> on the discharge side. In addition, when a gas and a supercritical fluid each are set as a carrier, the carrier containing a sample is discharged.

Then, the sample holder <NUM> with which the step of soaking is completed is removed from the applicator <NUM>, and is precisely attached to a predetermined position inside the single-crystal X-ray diffractometer <NUM>, that is, to the goniometer head <NUM> at the tip of the goniometer <NUM>, for example, by using a positioning mechanism such as the above-described magnetic force or the like. According to the foregoing, the crystalline sponge <NUM> attached to a part (tip) of the pin-shaped holding part 202b of the sample holder <NUM> is to be arranged to the tip of the goniometer <NUM>, that is, to a position where X-ray beam is focused and irradiated from the X-ray tube <NUM> after soaking the sample is completed. In other words, the sample S soaked in the crystalline sponge <NUM> is precisely arranged at a predetermined position inside the single-crystal X-ray diffractometer <NUM>, and the intensity of X-rays diffracted from the sample S is subsequently measured by the X-ray detector <NUM> to analyze a crystal structure thereof, and so forth.

In this manner, by the sample holder unit <NUM> according to the present invention, it becomes possible that a very small amount of sample is soaked in the crystalline sponge <NUM> in very small size, that is combinedly attached beforehand to the sample holder <NUM> in an easy and safe manner by anyone, and subsequently, the sample S is quickly and safely installed to the goniometer <NUM> as a precise position with high accuracy in a short period of time in such an extent that the crystalline sponge is not broken due to being dried. In addition, then, it is identical to those in the current condition that X-rays diffracted and scattered by an object material are measured while irradiating X-rays having a required wavelength to the sample S by the above-described single-crystal X-ray diffractometer <NUM>, and the structure analysis is performed by a measurement application software constituting the above-described single-crystal X-ray structure analysis apparatus to carry out construction of molecular modelling, preparation of a final report, and so forth. That is, the present example brings quick, safe and easy check of the molecular structure/aggregative structure (actual space) of a newly discovered or designed structure at sites and so forth of not only drug development and life science but also every kind of material research.

<FIG> is a perspective view of the applicator <NUM> of Example <NUM>; <FIG> is a sectional view of the sample holder unit <NUM> obtained by storing the sample holder <NUM> in the applicator <NUM>; and the same symbols are given the same portions as those in Example <NUM>. Symbol <NUM> represents a plate-shaped pull-out prevention part (sliding part) that slides so as to protrude to the opening <NUM> from a lateral direction along the opening surface <NUM> of the applicator <NUM> (or, to carry out covering thereof). The pull-out prevention part <NUM> is engaged with the upper surface of the sample holder <NUM> stored in the applicator <NUM> in an attached state thereof, and prevents the sample holder from being pulled out therefrom. Symbols <NUM> and <NUM> represent a pair of guide rails each whose cross-section is U-shaped, the guide rails are arranged so as to extend in parallel at both side portions of the opening surface <NUM>, and the pull-out prevention part <NUM> whose both side ends are engaged with the guide rails <NUM> and <NUM> is slidably guided in both directions of each arrow.

The pull-out prevention part <NUM> provided with a circle-shaped opening part <NUM> in the central part, wherein the opening part <NUM> has an inner diameter smaller than an outer diameter of the disk-shaped base part <NUM> of the sample holder <NUM>, is engaged with only the outer peripheral portions of the upper surface of the sample holder <NUM> so as not to cover the through-holes <NUM> and <NUM> to prevent the sample holder <NUM> from being pulled out therefrom, when its attachment to the applicator <NUM> (Refer to <FIG>). In addition, in the state where the sample introduction pipes <NUM> and <NUM> are inserted therein, the pull-out prevention part <NUM> is engaged with the sample holder <NUM> at the position away from the sample introduction pipes. In addition, being engaged therewith at the position away from the sample introduction pipes means being engaged with the sample holder <NUM> in a state where the sample introduction pipes are not prevented from being inserted/ejected thereinto/therefrom, when having attached the pull-out prevention part <NUM> to the applicator <NUM>. The pull-out prevention part <NUM>, at a front end of which an inclined surface <NUM> is provided to a sliding lower surface, is made to be attached thereto while pushing down the upper surface of the sample holder <NUM> by the inclined surface <NUM> via sliding, and sliding between the upper surface of the sample holder <NUM> and the opening surface <NUM> of the applicator <NUM> is smoothly performed by the inclined surface <NUM>.

When soaking a sample into the crystalline sponge <NUM>, the sample introduction pipes <NUM> and <NUM> are inserted into the through-holes <NUM> and <NUM> exposed to the opening part <NUM> in a state of attaching the pull-out prevention part <NUM> thereto.

According to the present Example <NUM>, the plate-shaped light-weight pull-out prevention part is used as a pull-out prevention part, and thus pull-out prevention can be easily and surely performed with an easy operation.

<FIG> is a perspective view of a sample holder unit <NUM> showing part of the Example <NUM> in cross-section, showing a state where the pull-out prevention part is attached to the applicator; it is omitted to show the opening part (Refer to symbol <NUM> in <FIG>) of the pull-out prevention part; and the same symbols are given the same portions as those in Example <NUM>.

Symbol <NUM> represents an applicator, and symbol <NUM> represents a pull-out prevention part (sliding part) for sliding an opening (that is not shown in the figure) of the applicator <NUM> in the arrow direction, that is formed of a resin, metal or the like in plate thickness exhibiting high mechanical strength (about <NUM> atmospheric pressure). Symbols <NUM> and <NUM> representing a pair of guide rails arranged in parallel so as to extend in a lateral direction at both side portions above the applicator <NUM> exhibit high mechanical strength, the guide rails each whose cross-section is channel-shaped (U-shaped), are formed in plate thickness exhibiting strength (about <NUM> atmospheric pressure). Symbols <NUM> and <NUM> representing engagement parts at both side ends <NUM> of the pull-out prevention part <NUM>, the engagement parts each whose cross-section is channel-shaped (U-shaped), are formed of a resin, metal or the like exhibiting high mechanical strength so as to be engaged with the guide rails <NUM> and <NUM>.

Symbol <NUM> representing a protrusion-shaped operation part provided on a top plate <NUM> of the pull-out prevention part <NUM> is used for a sliding operation of the pull-out prevention part <NUM>. Further, it is omitted to show the figure, but similarly to Example <NUM>, an inclined surface is provided to a sliding lower surface at a front end of the pull-out prevention part <NUM>, and smooth sliding between the sample holder <NUM> and the applicator <NUM> is made possible.

The attachment thereof into the applicator <NUM> is performed by engaging the engagement parts <NUM> and <NUM> of the pull-out prevention part <NUM> with the guide rails <NUM> and <NUM>, and slidably operating the operation part <NUM> in the arrow direction with hand fingers, a manipulator or the like. The pull-out prevention part <NUM> is engaged with the upper surface of the sample holder <NUM> in the attached state thereof, and suppresses the pull-out thereof from the applicator. The removal of the pull-out prevention part <NUM> therefrom is carried out by operating the operation part <NUM> in the direction opposite to that at the time of attachment thereof to remove the pull-out prevention part <NUM> from the guide rails <NUM> and <NUM>.

As described above in detail, according to a sample holder unit for a single-crystal X-ray structure analysis apparatus of the present invention, the single-crystal X-ray structure analysis using a very small and fragile crystalline sponge can be quickly, surely and easily performed without accompanying the conventionally required fine and precise operation, even if not having specialized knowledge of X-ray structure analysis, in other words, there is provided the sample holder unit capable of realizing a very versatile and user-friendly single-crystal X-ray structure analysis apparatus that is capable of high-yield and efficient performance of the single-crystal structure analysis using the crystalline sponge, and further provided is a sample holder unit having a configuration more adaptable to the actual sample preparation operation.

In the step of soaking a sample into the crystalline sponge <NUM>, the sample is supplied to the sample holder unit <NUM> set to a temperature, a pressure and so forth that are suitable for soaking from the soaking apparatus (soaking machine) <NUM> (Refer to <FIG>) under the suitable conditions for soaking (a pressure, a flow rate and so forth). Thus, the inside of the sample holder unit <NUM> needs to endure various temperatures and pressures (about <NUM> atmospheric pressure). In the present Example <NUM>, the pull-out prevention part <NUM>, the engagement part <NUM> and the guide rails <NUM> in plate thickness exhibiting high mechanical strength (about <NUM> atmospheric pressure) are used, and further, the engagement part <NUM> and the guide rails <NUM> each are formed into its channel-shaped (U-shaped) cross-section type exhibiting high mechanical strength (about <NUM> atmospheric pressure), thereby being responsively and sufficiently endurable in mechanical strength.

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; 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 an X-ray structure analysis apparatus used for searching a material structure, a method thereof, and so forth.

In addition, the present international application claims priority under <CIT>.

Claim 1:
A sample holder unit (<NUM>) for single-crystal X-ray structure analysis using a porous complex crystal, the sample holder unit (<NUM>) comprising a sample holder (<NUM>) used in a single-crystal X-ray structure analysis apparatus, and an applicator (<NUM>, <NUM>, <NUM>) in which the sample holder (<NUM>) can be stored,
wherein the sample holder (<NUM>) comprises:
a base part (<NUM>) attachable to a goniometer (<NUM>) in the single-crystal X-ray structure analysis apparatus, the base part (<NUM>) formed to have a sample introduction structure (<NUM>, <NUM>) into which a sample to be soaked in the porous complex crystal is introduced; and
a holding part (202b) that can hold the porous complex crystal capable of soaking the sample in a plurality of fine pores formed therein, the holding part (202b) formed to the base part (<NUM>), and
the applicator (<NUM>, <NUM>, <NUM>) comprises:
an opening (<NUM>) and a storing space (<NUM>) in which the sample holder (<NUM>) that holds the porous complex crystal can be stored;
a seal part (<NUM>) provided on a contact surface with the sample holder (<NUM>) stored in the storing space (<NUM>); and
a pull-out prevention part (<NUM>, <NUM>) that can prevent the sample holder (<NUM>) from being pulled out from the opening (<NUM>), the pull-out prevention part (<NUM>, <NUM>) engaged with the sample holder (<NUM>) stored in the storing space (<NUM>).