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, there 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).

Non-Patent Document <NUM> illustrates a puck with a predetermined number of slots for receiving a sample holder.

Patent Document <NUM> describes a sample holder for X-ray crystallography of a cryogenically frozen biological sample. The sample holder comprises a base and a sample tube attached to the sample base. A sample loop is attached by adhesive to the sample tube. In the sample loop the cryogenically frozen biological sample is received.

A sample holder is also known from Patent Document <NUM>. The sample holder comprises a pin on which a sample can be placed. The pin extends a predetermined distance from a cap that mates with a magnetized base on a goniometer.

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 <NUM> 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 <NUM> 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 <NUM> rotation table <NUM> is driven by these drive devices to be intermittently or continuously rotated so as to make a so-called <NUM> 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 such as cyclohexane or the like, inside a container. Examples of the preserving solvent 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> and <NUM> representing a pair of put-out prevention parts (L-shaped swing levers) provided on side surfaces (side walls) of the applicator <NUM> swing in such a manner that their tips (lateral bars as described later) are moved to positions protruding and retracted to/from the inside of the opening <NUM>. The put-out prevention parts <NUM> and <NUM> each are formed from a lateral bar <NUM> and a vertically upright bar that are formed into an L-shape, and the vertically upright bar comprises an upper portion <NUM> and a lower portion (operation part) <NUM> that are formed into a dog-legged shape. The upper portion <NUM> is connected to the lateral bar <NUM>, and a boundary between the lower portion <NUM> and the upper portion <NUM> is supported by a lateral shaft <NUM> fixed on a side surface of the applicator <NUM> in a swingable manner. The put-out prevention parts <NUM> and <NUM> are energized in each direction (closing direction) where the tip of the lateral bar <NUM> protrudes toward the opening <NUM>, with a spring that is not shown in the figure. Normally, the lateral bar <NUM> protrudes toward the opening <NUM> and the operation part <NUM> of the vertically upright bar is separated from the side surface of the applicator <NUM> by this energization. The lateral bar <NUM> is moved to a retracted position (open state) by pressing the operation part <NUM> in the side surface direction of the applicator <NUM> with hand fingers or a manipulator.

When storing the sample holder <NUM> in the applicator <NUM>, the operation part <NUM> of the pull-out prevention part <NUM> is pressed in a horizontal arrow direction as shown in <FIG> with hand fingers or the like to insert the sample holder in the opening <NUM> in a state where the lateral bar <NUM> of the pull-out prevention part <NUM> is opened. Next, when releasing the pressing force in the horizontal arrow direction, that is applied to the operation part <NUM> of the pull-out prevention part <NUM> while pushing down the sample holder <NUM>, the pull-out prevention part <NUM> is rotated by force energized by a spring, and the lateral bar <NUM> protrudes toward the opening <NUM>.

When showing the above-described state in <FIG>, the lateral bar <NUM> of the pull-out prevention part <NUM> is engaged with the upper surface of the sample holder <NUM>, and thus the sample holder is prevented from being pulled out from the opening <NUM> of the applicator <NUM>. In addition, each position of engaging the lateral bar <NUM> with the upper surface of the sample holder <NUM> is a position avoiding through-holes <NUM> and <NUM>.

<FIG> shows a step of introducing a sample into the applicator <NUM>. Sample introduction pipes (hereinafter, also referred to simply as pipes) <NUM> and <NUM> each as a sample introduction structure are inserted into the respective through-holes <NUM> and <NUM> of the sample holder <NUM>. In <FIG>, symbol <NUM> represents a hydrophobic solvent (for example, cyclohexane) injected at the bottom part of 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) 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 (comprising a solvent or a carrier) excessively supplied thereto is discharged outside via the pipe <NUM>.

Thereafter, in the present example, the pipes <NUM> and <NUM> are simultaneously pulled out, 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 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 are mixed is supplied by flowing inside the sample introduction 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 a soaking machine, in a state where the sample is injected thereinto, the excessive sample or a solution in which the sample and the preserving solvent 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, the unnecessary preserving solvent or solution flows inside a sample introduction pipe <NUM> on the discharge side, and is discharged. Accordingly, it is possible that no sample flows through the sample instruction pipe <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.

Next, attaching a sample holder unit into a single-crystal X-ray structure analysis apparatus is described, the sample holder unit comprising a crystalline sponge in which the sample according to the Example <NUM> is soaked.

After soaking the sample in the crystalline sponge <NUM> as shown in <FIG>, the pipes <NUM> and <NUM> are pulled out, and the sample holder unit <NUM> formed from the sample holder <NUM> comprising the crystalline sponge <NUM> in which the sample is soaked, and the applicator <NUM> for storing the sample holder is attached to the goniometer head <NUM> at the tip of the goniometer <NUM> in the single-crystal X-ray diffractometer <NUM> in the upside-down attitude (in the state where the crystalline sponge <NUM> is directed upward) by being held with hand fingers, a manipulator <NUM> or the like, as shown in <FIG>. At this time, a portion of the attachment part <NUM> of the sample holder <NUM> is attached to the goniometer head <NUM>.

Next, as shown in <FIG>, the operation parts <NUM> of the pull-out prevention parts <NUM> on both sides are pressed in the horizontal arrow directions by hand fingers or the like to open the lateral bars <NUM>. The pull-out prevention of the sample holder <NUM> is released by disengaging the pull-out prevention parts <NUM> from the sample holder <NUM>. The applicator <NUM> is separated from the sample holder <NUM> by elasticity of the seal part <NUM>, and thus rises in the vertical arrow direction. Then, only the sample holder <NUM> is to be a state of being attached to the goniometer head <NUM> at the tip of the goniometer <NUM> by holding and raising the applicator <NUM> with hand fingers, a manipulator <NUM> or the like. At this time, the sample holder <NUM> is easily and precisely attached to the goniometer head <NUM> at the tip thereof by a magnet or the like at the attachment part <NUM>.

In addition, as described above, when the pull-out prevention parts are released, it is so constituted that the applicator <NUM> is separated from the sample holder <NUM> by the elasticity of the seal part <NUM>, and thus the seal part <NUM> serves as separation means of separating (pulling apart) the applicator <NUM> from the sample holder <NUM>, together with a sealing function. The other means such as a spring or the like energized so as to separate between the applicator <NUM> and the sample holder <NUM>, other than the seal part <NUM> may be provided for this separation means. This separation means is similarly applied to Example <NUM> and Example <NUM> as well as described later.

<FIG> is a perspective view showing the applicator <NUM> of Example <NUM>, according to the present invention; <FIG> shows a cross-section of a sample holder unit according to the same; 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 protrudes toward the opening <NUM> by sliding in the lateral direction along an opening surface <NUM> of the applicator <NUM>. 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 <NUM> from being pulled out from the opening <NUM>. Symbols <NUM> and <NUM> represent 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>. The pull-out prevention part <NUM> whose both side ends (engagement parts) are engaged with the guide rails <NUM> and <NUM> is slidably guided in both directions of each arrow.

The pull-out prevention part <NUM> having a U-shaped opening part <NUM> in the central part is provided with an operation part <NUM> on the U-shaped circular arc side of the opening part <NUM> that is opened on the other side <NUM>. Attaching the pull-out prevention part <NUM> to the applicator <NUM> is performed by pressing the operation part <NUM> with hand fingers or a manipulator while pushing down the upper surface of the sample holder <NUM>, and sliding the pull-out prevention part <NUM> (Refer to <FIG>).

The pull-out prevention part <NUM> whose opening part <NUM> has an inner diameter smaller than an outer diameter of the 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>, when it is attached into 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 engaging therewith, and sliding between the upper surface of the sample holder <NUM> and the opening surface <NUM> of the applicator <NUM> is smoothly performed.

When soaking the sample in the crystalline sponge <NUM>, the sample introduction pipes <NUM> and <NUM> are inserted into the through-holes <NUM> and <NUM> of the sample holder <NUM>, that are exposed to the opening part <NUM> of the pull-out prevention part <NUM> in the state where the pull-out prevention part <NUM> is attached thereto to introduce the sample similarly to Example <NUM>.

<FIG> shows a sectional view at the time when a sample holder unit according to Example <NUM> is attached to a goniometer in a single-crystal X-ray structure analysis apparatus. The sample holder unit <NUM> as shown in <FIG> is attached to the goniometer head <NUM> at the tip of the goniometer <NUM> in the upside-down attitude with hand fingers, a manipulator <NUM> or the like as shown in <FIG>. At this time, the attachment part <NUM> portion of the sample holder <NUM> is attached to the goniometer head <NUM> at the tip of the goniometer <NUM>.

Next, the pull-out prevention part <NUM> is pulled out in the direction (right direction in <FIG>) opposite to that at the time of its attachment thereto by operating the operation part <NUM> with hand fingers, a manipulator <NUM> or the like. When the pull-out prevention part <NUM> is pulled out from the applicator <NUM>, the applicator <NUM> is separated from the sample holder <NUM> by elasticity of the seal part <NUM> by releasing the pull-out prevention of the sample holder <NUM>, and thus rises in the vertical arrow direction. Then, only the sample holder <NUM> remains attached to the goniometer head <NUM> at the tip of the goniometer <NUM> by holding and raising the applicator <NUM> with hand fingers, a manipulator <NUM> or the like. Similarly to Example <NUM>, the sample holder <NUM> is easily and precisely attached to the goniometer head <NUM> at the tip of the goniometer <NUM> by a magnet or the like at the attachment part <NUM>. The sample holder <NUM> is freely attached to the tip portion of the goniometer <NUM> in an attachable/detachable manner by this positioning mechanism.

According to Example <NUM>, the pull-out prevention can be easily and surely performed since a pull-out prevention part is attached thereto by sliding; and the sample holder <NUM> can be quickly, easily and precisely attached to the goniometer <NUM> while protecting the crystalline sponge <NUM>, since the sample holder <NUM> together with the applicator <NUM> is carried and attached to the goniometer <NUM>, and only the applicator <NUM> is subsequently separated therefrom.

<FIG> is a perspective view in which a sample holder unit <NUM> is shown with a partial cross-section according to Example <NUM> of the present invention, and the same symbols are given the same portions as those in Example <NUM>. <FIG> shows a state of attachment thereof into an applicator by the pull-out prevention part <NUM>, and it is omitted to show a U-shaped opening part (Refer to symbol <NUM> in <FIG>) of a pull-out prevention part according to 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>, that is formed of a resin 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 the lateral direction at both side portions above the applicator <NUM> exhibit high mechanical strength, the guide rails each whose face is 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 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 <NUM>. 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>.

During attachment thereof into a single-crystal X-ray structure analysis apparatus, the sample holder unit <NUM> shown in <FIG> is held by hand fingers, a manipulator or the like, and is attached to the goniometer head <NUM> at the tip of the goniometer <NUM> in the upside-down attitude. At this time, the attachment part <NUM> of the sample holder <NUM> is attached to the goniometer head <NUM> at the tip of the goniometer <NUM>. Next, in the state of pressing the applicator <NUM>, the pull-out in the direction (right direction in <FIG>) opposite to that at the time of attachment thereto is performed by operating the operation part <NUM> with hand fingers, a manipulator <NUM> or the like. The applicator <NUM> is separated from the sample holder <NUM>, and raised with elasticity of the seal part <NUM> by pulling out the pull-out prevention part <NUM>. Then, when the applicator <NUM> is held and raised by hand fingers, a manipulator or the like, only the sample holder <NUM> remains attached to the goniometer head <NUM> at the tip of the goniometer <NUM>.

According to Example <NUM>, similarly to Example <NUM> and Example <NUM>, the sample holder <NUM> together with the applicator <NUM> is carried and attached to the goniometer <NUM>, and only the applicator <NUM> is subsequently separated therefrom, and thus the sample holder <NUM> can be quickly, easily and precisely attached to the goniometer <NUM> while protecting the very small and fragile crystalline sponge <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. 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 correspondingly deal with various temperatures and pressures. 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 the foregoing.

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.

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 (<NUM>), and an applicator (<NUM>, <NUM>, <NUM>) in which the sample holder (<NUM>) is stored,
the sample holder (<NUM>) comprising:
a base part (<NUM>) attached to a goniometer (<NUM>) in the single-crystal X-ray structure analysis apparatus (<NUM>), the base part (<NUM>) formed to have a sample introduction structure (<NUM>-<NUM>) into which a sample tc be contained within a framework of the porous complex crystal (<NUM>) having a plurality of fine pores formed therein is introduced; and
a holding part (202b) that holds the porous complex crystal, the holding part (202b) formed on the base part (<NUM>), and
the applicator (<NUM>, <NUM>, <NUM>) comprising:
an opening (<NUM>) and a storing space (<NUM>) in which the sample holder (<NUM>) is stored, and
a pull-out prevention part (<NUM>, <NUM>, <NUM>) that selectively prevents and releases the sample holder (<NUM>) stored in the storing space (<NUM>) from being pulled out from the opening (<NUM>),
wherein the pull-out prevention part (<NUM>, <NUM>, <NUM>) comprises an operation part (<NUM>, <NUM>, <NUM>) that releases pull-out prevention thereof in a state where the sample holder (<NUM>) stored in the applicator (<NUM>, <NUM>, <NUM>) is attached to the goniometer (<NUM>); and
the porous complex crystal (<NUM>) is attached to the sample holder (<NUM>) and capable of being immersed in a solution containing the sample.