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

However, it has been difficult for those other than X-ray specialists to perform the structure analysis based on the results obtained by the foregoing method. Therefore, an X-ray structure analysis system with which the structure analysis can be performed by anyone who is not even a specialist of X-rays has been demanded. In this regard, particularly, 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 by 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 that automates the transport of cryogenically frozen biological samples and the attachment of a sample assembly comprising such a biological sample to a goniometer mounting post. The system comprises a gripper that comprises a split collet for gripping the sample assembly stored in a storage Dewar. Thereafter the gripper is rotated by <NUM>° in order to attach the sample assembly with the sample to the mounting post.

However, in the single-crystal X-ray structure analysis as 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 various 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 enable quickly, surely and easily performing an operation of taking out a very fine and fragile crystalline sponge in which the sample for the single-crystal X-ray structure analysis with the crystalline sponge is soaked and attaching it to the X-ray irradiation position inside the apparatus, that is inclusive of utilizing the proposed sample holder according to the present invention, even if not having specialized knowledge of X-ray structure analysis, in other words, to provide a high-yield, efficient, very versatile and user-friendly single-crystal X-ray structure analysis apparatus that is inclusive of automatization of attaching the sample holder thereinto.

According to the above-described present invention, a series of operations including soaking a sample in a very small and fragile crystalline sponge, followed by installing it in an apparatus, after soaking a small amount of sample therein can be quickly, surely and easily carried out by using an attaching mechanism thereof, together with a sample holder and an applicator that are proposed according to the present invention, without accompanying conventional precise and fine operations for which rapidness is also required; in other words, a high-yield, efficient, very versatile and user-friendly single-crystal X-ray structure analysis apparatus that is inclusive of automatization of attaching the sample holder thereinto is provided. Thus, it becomes possible to make a single-crystal X-ray structure analysis with a crystalline sponge be easily usable, and to widely spread it.

Next, the single-crystal X-ray structure analysis apparatus in which a crystalline sponge is utilized, according to one embodiment of the present invention, is 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 no possibility of A and B exists.

The attached <FIG> shows the entire appearance configuration of a single-crystal X-ray structure analysis apparatus including 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 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 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 centering on a sample axis line ω passing through an X-ray incident point of the sample S, and a <NUM> rotation table <NUM> that is arranged around the θ rotation table <NUM> and is rotatable centering on the sample axis line ω. 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. Driving devices (not shown in the figure) for driving the above-described θ rotation table <NUM> and <NUM> 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 <NUM> rotation table <NUM> is driven by these driving device to be intermittently or continuously rotated so as to make a so-called <NUM> rotation. The above-described driving device 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 on the sample axis line ω by the θ rotation of the θ rotation table <NUM> in the goniometer <NUM>. During the θ rotation of this sample S, X-rays generated from the X-ray focus inside the X-ray tube <NUM>, that is directed to the sample S enter the sample S at a predetermined angle, and are diffracted/scattered. That is, the incident angle of X-rays entering the sample S changes depending on the θ rotation of the sample S.

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

Next, <FIG> shows one example of the detail of an electrical internal configuration constituting a control section <NUM> in the above-described single-crystal X-ray structure analysis apparatus. 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 and mutually connected by a bus <NUM>.

The image display device <NUM> constituted from an image display unit such as a CRT display, a liquid-crystal display or the like displays an image on a screen in accordance with an image signal generated by an image control circuit <NUM>. The image control circuit <NUM> generates the image signal based on image data input therein. The image data input in the image control circuit <NUM> is generated by an operation of various 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 can be used for the printer <NUM>. In addition, the hard disk <NUM> can also be constituted from a magnetooptical 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 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, 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, for example, measurement results obtained by analysis performed with not X-rays but XRF, Raman ray or the like, and another analysis database <NUM> that stores physical property information are shown. 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 mutually connected to be able to communicate through a network <NUM> or the like. In this manner, the single-crystal X-ray structure analysis apparatus <NUM> receives and manages various measurement results including measurement data obtained by detecting X-rays diffracted or scattered by a sample with the X-ray detection measurement section while controlling a measurement processing operation using the measurement apparatus <NUM>. Further, structure analysis of the sample is performed with a structure analysis section, based on various measurement results including the measurement data obtained by detecting the X-rays diffracted or scattered by the sample.

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 various other conditions are 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 by 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, a step of soaking a very small amount of a sample, approximately several ng to several µg, separated by various pretreatment (separation) devices in a framework of a very small and fragile crystalline sponge having an outer diameter of approximately <NUM> provided after being immerged in a preserving solvent (carrier) such as cyclohexane or the like, inside a container, is required. Further, subsequently, 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 portion of a sample axis of the goniometer <NUM> (so-called goniometer head) while performing centering, is required. 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 whether having a specialized knowledge of X-ray structure analysis, thereby resulting in having a large influence on the measurement result of a sample after being soaked in the crystalline sponge. That is, these operations make single-crystal X-ray structure analysis using a very small crystalline sponge result in low yield, and thus this becomes one of the causes of suppressing the single-crystal X-ray structure analysis using the crystalline sponge from being widely used.

The present invention that has been accomplished based on the above-described inventor's knowledge enables quickly, surely and easily performing a single-crystal X-ray structure analysis with a very small and fragile crystalline sponge by using a sample holder for the crystalline sponge (also referred to simply as a sample holder) as described below, and a sample holder attaching mechanism together with a sample holder for the crystalline sponge (also referred to simply as a sample holder) as described below and an applicator that is a handling (operating) tool as also 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 portion of the goniometer <NUM> in a short 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 that is inclusive of automatization of attaching the sample holder thereinto, 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 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, including an operation of attaching a sample soaked in the crystalline sponge into an apparatus, while also using a very small, fragile and difficultly handleable crystalline sponge; and further provides a tool therefor.

<FIG> shows a tip portion 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> at the tip portion 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 portion 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 whole perspective view of the above-described sample holder <NUM>, and <FIG> shows a sectional view thereof. In the sample holder <NUM>, a pin (cylinder)-shaped sample holding part (hereinafter, referred to simply as a holding part) <NUM> (corresponding to the so-called goniometer head pin) is implanted vertically in the center of one surface (the lower surface in the figure) of the base part <NUM> of a disk or corn-shaped holder made of metal or the like attached to the goniometer head <NUM> {Refer to <FIG>} at the tip portion of the goniometer <NUM>, and the crystalline sponge <NUM> in which the above-described sample to be analyzed is soaked is combinedly attached and fixed to the sample holder <NUM> beforehand at a predetermined position of the tip of the pin-shaped holding part <NUM>. Further, the positioning mechanism or the like such as a magnet that is not shown in the figure, or the like is provided on the other surface (upper surface in the figure) of the disk-shaped base part <NUM>. The sample holder <NUM> is detachably attached to the tip portion of the goniometer <NUM> by this positioning mechanism.

Further, in <FIG> as well as <FIG>, the so-called applicator <NUM> used with the sample holder <NUM> is shown as a handling (operating) tool for soaking the sample in the crystalline sponge <NUM> attached to the sample holder in advance. This applicator <NUM> is, for example, formed from a transparent or non-transparent member made of glass, a resin, metal or the like, and a storing space <NUM> for storing the above-described sample holder <NUM> is formed inside thereof, and the opening <NUM> through which the sample holder <NUM> is fitted and taken out is further formed at the upper portion thereof.

Further, for example, seal portions (shown in <FIG> by hatched line parts) are provided at part of the opening <NUM> of the applicator <NUM> so as to be airtightly maintained from outside in a state of storing the sample holder <NUM> in the storing space <NUM> inside thereof. On the other hand, a pair of fine through holes <NUM>, <NUM> for introducing a sample to be analyzed into the crystalline sponge <NUM> located inside (storing space <NUM>) the applicator <NUM> are formed at the base part <NUM> of the sample holder <NUM>. The fine holes <NUM>, <NUM> exhibit preferable one example of a sample introduction structure, and other structures may be adopted. In addition, though not shown in the figure, seal portions are provided for these fine holes <NUM>, <NUM>. In this manner, as shown in the figure, the storing space <NUM> inside the applicator <NUM> is kept airtight even in a state where sample introduction tubes (hereinafter, referred to simply as introduction tubes) <NUM>, <NUM> for introducing the sample into the crystalline sponge <NUM> are inserted in the fine holes <NUM>, <NUM>.

According to the sample holder <NUM> with such a configuration, alternatively, further by being combinedly provided (unified) with the applicator <NUM> as a handling (operating) tool thereof, the crystalline sponge <NUM> attached to the tip portion of the pin-shaped holding part <NUM> (corresponding to a goniometer head pin) constituting a part of the sample holder <NUM> can be safely and easily handled without damage or deviation from the sample holder <NUM>. That is, 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 like 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.

Further, when introducing the sample to be analyzed into the crystalline sponge <NUM>, by using a soaking apparatus (soaking machine) with which one example is described below, more specifically, by inserting a pair of sample introduction tubes <NUM>, <NUM> from the apparatus in fine through holes <NUM>, <NUM>, and introducing a very small amount of the sample into the above-described very small crystalline sponge <NUM>, it is possible to soak the sample in the necessary crystalline sponge <NUM>. Further, the sample holder <NUM> can be integrated (unified) with the applicator <NUM> as a handling (operating) tool thereof, and further can be provided as a so-called set by preparing the required number of them for the analysis operation and storing them in a box-shaped case, as also shown in <FIG>.

Next, the single-crystal X-ray structure analysis method performed using the sample holder <NUM> to which the crystalline sponge <NUM> is previously attached is explained below. In addition, the sample holder <NUM> and the applicator <NUM> may be provided as an integral one (unit) or as a set, as described above.

<FIG> shows one Example according to the present invention given by conceptualizing the single-crystal X-ray structure analysis method using the sample holder <NUM>. According to such a method, as described above, a very small amount of the sample is introduced into the sample holder <NUM> provided with the applicator <NUM> as an integral one (unit) to perform soaking required therein. In this case, according to the above-described example, in the state where the sample holder <NUM> is stored inside the applicator <NUM>, the sample can be soaked in the crystalline sponge <NUM> attached to the tip of the sample holder <NUM> by inserting a pair of the sample introduction tubes <NUM>, <NUM> into a pair of the fine through holes <NUM>, <NUM> (Refer to <FIG>) formed in the sample holder <NUM>.

More specifically, as shown in <FIG>, for example, 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>, together with a carrier thereof is supplied to a pair of the sample introduction tubes <NUM>, <NUM> (Refer to <FIG>) to be inserted in the fine holes <NUM>, <NUM> of the sample holder <NUM> through the soaking device (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 tube <NUM> on the supply side from a tube on the supply side, and is supplied to the sample holder <NUM> inside the applicator <NUM> from the tip portion of the sample introduction tube <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 sample introduction tube <NUM> on the supply side. In this manner, a very small amount of the sample S introduced thereto comes into contact with the crystalline sponge <NUM> attached to the tip of the pin-shaped holding part <NUM> 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 device <NUM>, the excessive sample or a solution in which the sample and the preserving solvent (carrier) are mixed is discharged from the sample introduction tube <NUM> on the discharge side, after a predetermined time has elapsed in a state where the sample is injected. When not using the soaking device <NUM>, the unnecessary preserving solvent (carrier) or solution flows inside the 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. When using gas or supercritical fluid as a carrier, the carrier containing the 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 a position where an X-ray beam from the X-ray tube <NUM>, the position corresponding to the tip of the goniometer head pin of the goniometer head <NUM> at the tip portion of the goniometer <NUM>, is focused on and irradiated , for example, by using a sample holder attaching mechanism also described below and a positioning mechanism such as the above-described magnetic force or the like.

<FIG> shows one example of a configuration of a sample holder attaching mechanism <NUM> for removing a sample holder <NUM> to which a crystalline sponge <NUM> where soaking described above is completed is attached, from the applicator <NUM>; and for attaching (mounting) it to the goniometer head <NUM> at the tip portion of the goniometer <NUM>. As also shown in the figure, the sample holder attaching mechanism <NUM> comprises a sample holder support section <NUM> including a pair of bar-shaped support parts <NUM>, <NUM> that are arranged in parallel to each other and that move while approaching or separating to/from each other (Refer to an arrow in the figure) and hold/release the base part <NUM> of the sample holder <NUM> therebetween; and an applicator support section <NUM> including a pair of bar-shaped members <NUM>, <NUM> that are similarly arranged in parallel to each other and that are movable while approaching or separating to/from each other (Refer to an arrow in the figure) and hold/release the applicator <NUM> therebetween. Specifically, the former sample holder support section <NUM> itself is constituted as to be further rotatable, and the position thereof is movable toward the goniometer head <NUM> of the goniometer <NUM>, as shown in the figure by arrows. In addition, it is preferred that the sample holder attaching mechanism <NUM> is arranged at a position adjacent to the goniometer <NUM> inside the single-crystal X-ray diffractometer <NUM> in consideration of its function. In addition, the sample holder attaching mechanism <NUM> may be arranged outside the single-crystal X-ray diffractometer <NUM>, , for example, in the soaking machine <NUM> and between the soaking machine <NUM> and the single-crystal X-ray diffractometer <NUM>, and so forth.

Then, the base part <NUM> of the sample holder <NUM> is supported by the sample holder support section <NUM>, and the applicator <NUM> is simultaneously supported by the applicator support section <NUM>; and the sample holder support section <NUM> subsequently moves in a direction of removing the supported sample holder <NUM> from the applicator <NUM>, for example, in a vertical direction in this case, more specifically, along an extending direction of the pin-shaped holding part <NUM> as also shown in <FIG> by an arrow. According to those described above, the sample holder <NUM> can be safely removed from the applicator <NUM> with neither damage nor deviation caused by the crystal sponge <NUM> attached to the tip of the pin-shaped sample holding part <NUM>, that comes into contact with a part of the applicator <NUM>. Thereafter, the sample holder support section <NUM> itself rotates (Refer to the arrow in the figure) to attach the sample holder <NUM> to the goniometer head <NUM> of the goniometer <NUM> in a state of being flipped upside down of the sample holder <NUM>.

Alternatively, as also shown in <FIG>, the sample holder <NUM> integrated with the applicator <NUM> may be attached onto the goniometer head <NUM> by being moved to the position of the goniometer head <NUM>, and being rotated, in a state of supporting the outer periphery of the base part <NUM> (or the applicator <NUM>) by the sample holder support section <NUM> (or the applicator support section <NUM>). In addition, in this case, thereafter, the applicator support section <NUM> vertically moves in a stationary state after supporting the outer periphery of the applicator <NUM> with the applicator support section <NUM>, and simultaneously supporting the base part <NUM> with the sample holder support part <NUM> to enable safely removing the crystalline sponge <NUM> from the applicator <NUM> with neither damage nor deviation caused by the crystalline sponge that comes into contact with a part of the applicator <NUM> similarly to the foregoing, and attaching it to the tip of the goniometer head <NUM>. In addition, in those described above, it is explained that the sample holder support section <NUM> and the applicator support section <NUM> each are constituted from a pair of parallelly movable bar-shaped members, but it is obvious to one of ordinary skill in the art that these support sections are any means as long as they are capable of supporting a sample holder or an applicator, and may be alternatively constituted from other rotatable members or constituted by employing support means (support section) such as a so-called robot arm.

According to those described above, the crystalline sponge <NUM> attached to a part (tip) of the pin-shaped holding part <NUM> of the sample holder <NUM> attached to the tip of the goniometer head <NUM> of the goniometer <NUM> is to be precisely arranged at a position where an X-ray beam from the X-ray tube <NUM> is focused on and irradiated to, safely and quickly with neither damage nor deviation caused by the crystalline sponge that comes into contact with another region even when removing the sample holder <NUM> from the applicator <NUM> after soaking is completed. In other words, a sample soaked in the crystalline sponge <NUM> is precisely, quickly and safely arranged at a predetermined position inside the X-ray diffractometer <NUM>, and intensity of X-rays diffracted from the sample S is subsequently measured by the single-crystal X-ray diffractometer to analyze a crystal structure thereof, and so forth.

In this manner, by using not only the sample holder <NUM> and the applicator <NUM> but also the sample holder attaching mechanism <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> easily and safely 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 drying. 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, it becomes possible that 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.

As described above in detail, according to 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 by using not only newly proposed sample holder and applicator but also an attaching mechanism thereof even without having specialized knowledge of X-ray structure analysis, in other words, 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 is inclusive of automatization of attaching the sample holder thereinto, is provided.

In addition, although 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 of the configurations that are described above. 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 be added to a configuration of one Example; and with respect to a part of a configuration of each Example, addition/deletion/replacement of another configuration may be further performed.

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

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

Claim 1:
A sample holder attaching device configured to attach a sample holder (<NUM>) adapted to hold a sample into a single-crystal X-ray structure analysis apparatus (<NUM>) configured to perform a structure analysis of a material, the device comprising:
a sample holder attaching mechanism (<NUM>) adapted to attach the sample holder (<NUM>), said sample holder (<NUM>) being attached to an attachable/detachable applicator (<NUM>), to a goniometer (<NUM>) in the single-crystal X-ray structure analysis apparatus (<NUM>) in a state where the sample holder (<NUM>) is removed from the applicator (<NUM>);
wherein the sample holder (<NUM>) comprises a base part (<NUM>) that is detachably attached to the tip portion of the goniometer (<NUM>) and a holding part (<NUM>) to which a porous complex crystal (<NUM>) capable of soaking the sample in a plurality of fine pores formed therein can be attached,
the holding part (<NUM>) is formed on the base part (<NUM>),
the applicator (<NUM>) has a storing space (<NUM>) for storing the sample holder (<NUM>),
the sample holder attaching mechanism (<NUM>) has a sample holder support section (<NUM>) adapted to enable removal of the sample holder (<NUM>) from the applicator (<NUM>) and attachment of the sample holder (<NUM>) to the goniometer (<NUM>), and
the porous complex crystal (<NUM>) is fixed at a position of the sample holder (<NUM>), where X-rays are irradiated from the X-ray irradiation section, in a state where the sample holder (<NUM>) is attached to the goniometer (<NUM>).