JP2006076820A - Method for producing polymer crystal and apparatus for growing polymer crystal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a large size polymer crystal having no defective part. <P>SOLUTION: A single crystal of a chicken albumen lysozyme is grown in a culture fluid (a), and then a part of the grown single crystal is ablation removed by irradiating the part with solid-state ultraviolet short pulse laser light of wavelength of 193 nm (b). Thereafter, when cultivation is restarted, the crystal is again grown from a processed face as a starting point and a large crystal can be obtained (c). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a polymer crystal and a polymer crystal growing apparatus used therefor, and more specifically, by processing an unnecessary portion in the process of growing a polymer crystal, thereby obtaining a large size and high quality. The present invention relates to a polymer crystal, a method for producing a polymer crystal in which a substance other than the polymer crystal is inserted into the crystal, and a polymer crystal growing apparatus used therefor.

  In recent years, post-genome research called proteome has become popular. Of particular note is research that seeks to elucidate the three-dimensional structure of proteins, which is called structural genomics. Analysis of protein structure and function is an important research field in life science, and detailed three-dimensional structure analysis is indispensable because it is directly linked to disease treatment and drug discovery. One of the main means is X-ray crystal structure analysis. In order to apply X-ray crystal structure analysis, it is necessary to crystallize a polymer substance to be analyzed.

  In the growth of polymer crystals, crystals having a shape reflecting the molecular structure and growth conditions are grown in the same manner as in the growth of inorganic crystals and organic low-molecular crystals. In addition, since many polymer substances have not established crystallization conditions and growth conditions for obtaining high-quality single crystals, it is very difficult to control crystal precipitation and subsequent growth control. For this reason, there are many problems such as a problem in crystal quality or a problem that crystals deposited in close proximity adhere to each other to be polycrystallized.

  For example, when X-ray crystal structure analysis is performed, a single crystal having a desired shape and high quality is required. Therefore, it is general to optimize the crystallization and growth conditions to obtain the crystal. However, as described above, it is very difficult to obtain these crystals for the polymer substance. Therefore, there is a case where a size, shape, or a portion having a good crystal quality necessary for X-ray crystal structure analysis is taken out from the obtained crystal, or a single crystal is cut out from a polycrystal.

  However, polymer crystals are often much softer and more brittle than crystals of, for example, inorganic substances and organic low-molecular substances, and therefore, when subjected to a large impact during processing, damage such as cracks and cracks occurs in the periphery. In addition, it is often sensitive to changes in temperature, and it is known that denaturation is easily caused by applying heat.

  Since polymer crystals are very difficult to handle in this way, it is extremely difficult to apply processing techniques that are widely used in inorganic crystals and other materials as they are, and reliable crystal processing techniques have been established. It wasn't.

  A conventionally used processing technique for polymer crystals is a processing technique that requires mechanical contact with the crystal using a knife or a needle. This method is artificially processed under observation with a microscope or the like, and is mainly used for cutting polymer crystals.

    However, the polymer crystal is mechanically fragile as compared with a general crystal, and the cut surface may be collapsed due to the shearing force applied to the cut surface when processing with a knife or a needle. Therefore, the polymer crystal processing method currently used has many elements left to luck, and is a processing method with low success probability and low reproducibility, even for those who have artisan skills. Further, although this method can perform relatively simple processing such as crystal cutting, it is very difficult to adapt when complicated and precise processing is required.

  As a method for solving such a problem, the present inventors have performed an invention whose main point is to perform processing such as removing unnecessary portions of the polymer crystal by irradiation with ultraviolet short pulse laser light. Patent applications have been filed as Japanese Patent Application Nos. 2003-32090, 2004-19516, and 2004-137991 (these are referred to as “prior application inventions”).

  According to the invention of the prior application, it has become possible to process a polymer single crystal, which has been difficult to process without damaging the crystal structure, without damaging the crystal structure. It was possible to remove and observe the remaining part by X-ray diffraction or the like.

  However, since the unnecessary portion of the polymer crystal is processed when the invention of the prior application is used, for example, when there are many unnecessary portions of the polymer crystal, the size of the obtained normal polymer crystal is reduced. There was a problem that it was too much.

  In addition, in order to evaluate the physical properties of a crystal, a probe or the like that requires physical contact with the crystal may be inserted into the crystal. However, as described above, the polymer crystal is brittle and soft. It was difficult to insert such a probe into the crystal.

  The present invention has been made in view of such circumstances, and solves the problems of the invention of the prior application, a method for producing a high-quality large polymer crystal, and a substance other than the polymer is inserted into the crystal. It is an object of the present invention to provide a method for producing a polymer crystal and a polymer crystal growth apparatus used therefor.

  The first means for solving the above problem is that, in the process of producing a polymer crystal, during the growth of the polymer crystal or once the growth of the polymer crystal is stopped, the polymer crystal is unnecessary. The present invention includes a process in which the portion is processed by irradiation with ultraviolet short pulse laser light and then grown (claim 1).

  Currently, laser light is widely used as a processing tool. However, processing using a carbon dioxide laser (wavelength: 10.6 μm) or a YAG laser (wavelength: 1.06 μm) that is widely used is thermal processing, and the temperature of the material to be processed increases during laser light irradiation. Furthermore, it is desirable that the laser light applied to the material to be processed is not continuous light but pulsed light. This is because laser processing using continuous light has a far greater degree of heat generation than processing using pulsed light. Therefore, in the polymer crystal in which thermal denaturation must be avoided, the processing by the infrared laser, the visible laser, or the continuous laser processing is not suitable.

  Therefore, the inventors paid attention to the ultraviolet short pulse laser. That is, ultraviolet short pulse laser light has a high photon energy due to its short wavelength, and can be processed to directly cut a chemical bond of a polymer crystal. In this processing, high-precision and smooth processing can be achieved with much less influence of heat compared to processing using a normal carbon dioxide laser or YAG laser.

  The main chain of the polymer has a C—N bond and a C—C bond, and the bond energy of the C—N bond is about 70 kcal / mol, and the bond energy of the C—C bond is about 84 kJ / mol. For example, in the case of an ultraviolet short pulse laser beam having a wavelength of 300 nm, the photon energy corresponds to about 95 kcal / mol, so that these bonds can be broken.

  Since processing by this ultraviolet short pulse laser light irradiation basically cuts molecular bonds by photon energy and evaporates, no shear force acts on the cut surface during processing. Due to this excellent property, it is possible to process a very fragile material called a polymer crystal without breaking it and obtain a clean processed surface. In other words, the processing using the ultraviolet short pulse laser is particularly effective when the polymer crystal is brittle so that the processing surface is damaged by the mechanical processing method.

  When this means is used, for example, when it is found that a part of the crystal is damaged or polycrystallized during the growth of the polymer single crystal, the unnecessary part of the crystal to be grown is processed. Therefore, since growth of these unnecessary portions can be suppressed, it is possible to efficiently produce a high-quality and large polymer single crystal. The processing of the unnecessary portion is performed in the process of manufacturing the polymer crystal. However, it is unnecessary to process the unnecessary portion during the growth of the polymer crystal, that is, while continuing the growth, and to stop the growth once. There is a method of processing a part and then restarting the growth, and a preferable method can be selected as appropriate.

  The processed crystal can be grown by controlling the external environment such as temperature change, solvent evaporation, pressure change, concentration change, pH change, impurity change and the like.

  The second means for solving the above-mentioned problem is the first means, characterized in that the processing of the unnecessary portion is removal of the unnecessary portion using laser ablation with an ultraviolet short pulse laser beam. (Claim 2).

  Examples of processing of unnecessary portions of polymer crystals using ultraviolet short pulse laser light include removal, modification, and miniaturization of unnecessary portions. By removing unnecessary portions using laser ablation, the crystal can be removed from the processed surface. Easy to grow. In this means, since unnecessary portions are removed using an ultraviolet short pulse laser, even if the processed surface is damaged, the degree is small. Therefore, in the manufacturing process of the polymer crystal after processing, from the processed surface Crystal grows.

  A third means for solving the problem is the second means, wherein after removing the unnecessary portion, a substance other than the polymer crystal is inserted into at least a part of the removed portion. This is a characteristic (claim 3).

  Since a polymer crystal is brittle and soft, when an object is inserted into the crystal, breakage such as cleavage occurs due to the stress generated when the substance physically contacts the crystal. In this means, the stress applied to the crystal at the time of insertion can be prevented by removing unnecessary portions by irradiation with an ultraviolet short pulse laser and inserting a substance into the removed region. Furthermore, when the crystal is grown after insertion, the crystal can continue to grow until it comes into contact with the inserted substance, so that an insert that requires physical contact with the crystal can be inserted into the polymer crystal with low damage. It becomes possible.

  A fourth means for solving the above problem is any one of the first to third means, and the processing of the unnecessary portion is performed by using an ultraviolet short pulse laser beam efficiently on the polymer crystal surface. It is carried out by performing an operation for reaching the target and then irradiating the surface of the polymer crystal with ultraviolet short pulse laser light (claim 4).

  Many growth solutions generally do not transmit ultraviolet light. Therefore, in this means, before the unnecessary portion is processed during the growth of the polymer crystal, an operation for efficiently reaching the ultraviolet short pulse laser beam on the surface of the polymer crystal is performed. Irradiation with ultraviolet short pulse laser light is performed. Therefore, even if the growing solution does not transmit ultraviolet rays, unnecessary portions can be processed.

  The operations for efficiently reaching the surface of the polymer crystal with the ultraviolet short pulse laser light include removing the growth solution to expose the surface of the polymer crystal, and changing the growth solution to another solution that efficiently transmits ultraviolet light. Replacement, moving the polymer crystal to expose the crystal surface, propagating ultraviolet short pulse laser light using a light guide such as an optical fiber, and placing the tip in the vicinity of the polymer crystal surface, etc. However, it is not limited to this.

  A fifth means for solving the problem is any one of the first to fourth means, wherein the polymer crystal is at least one of resin, protein, saccharide, lipid and nucleic acid. (Claim 5).

  Polymer crystals made of these materials are particularly fragile, and many of them are easily destroyed even when subjected to a little shearing force. Therefore, when the first to fourth means are applied, the material is particularly effective.

  A sixth means for solving the above problem is any one of the first to fifth means, wherein the wavelength of the ultraviolet short pulse laser beam is 400 nm or less ( Claim 6).

  In many cases, a C—N bond is present in a polymer crystal. In such a case, in order to reliably cut the C—N bond, the wavelength of the irradiated ultraviolet short pulse laser beam is 400 nm or less. It is preferable. Further, considering that the C—C bond is surely broken, the wavelength is desirably 340 nm or less. In terms of energy, there is no need to particularly limit the lower limit of the wavelength of the ultraviolet short pulse laser beam. In addition, since an optical element that is readily available does not transmit light having a wavelength of less than 150 nm, it is preferable to use an ultraviolet short pulse laser beam having a wavelength of 150 nm or more.

A seventh means for solving the problem is any one of the first to sixth means, wherein an energy density per pulse of the ultraviolet short pulse laser beam is 1 mJ / cm ² or more. There is a feature (claim 7).

  In the processing process using ultraviolet short pulse laser light, the processing characteristics are greatly affected by the energy density (fluence) per pulse of ultraviolet short pulse laser light to be irradiated. Generally, the processing amount (processing rate) per pulse of ultraviolet short pulse laser light does not show linearity with respect to the fluence. When the fluence is too small, even if the chemical bond is broken, the subsequent transpiration becomes insufficient and the processing cannot be performed. That is, in order to cause the processing, a fluence exceeding a certain threshold is required. At the fluence above the threshold, the processing rate increases as the fluence increases. Therefore, in order to obtain good processing characteristics, it is necessary to appropriately adjust the fluence of the ultraviolet short pulse laser beam to be irradiated.

The preferred fluence depends on the absorption coefficient of the work material with respect to the irradiation light. The larger the absorption coefficient, the more photons are absorbed per unit volume and the chemical bonds are efficiently broken, so the fluence value that is the threshold for processing becomes smaller. Since the absorption coefficient of the polymer greatly varies depending on the wavelength in the ultraviolet region, the preferable fluence varies depending on the wavelength of the irradiation light. In the wavelength range of 400 nm or less, a fluence of 1 mJ / cm ² or more can be adopted. By performing ultraviolet short pulse laser irradiation at the appropriate fluence, it is possible to influence the processing over a region of a depth of 1 nm or more from the crystal surface per pulse of ultraviolet short pulse laser light.

  The eighth means for solving the above problems includes a growth container in which a growth solution is placed to grow a polymer crystal, a stage on which the growth container is placed and movable in a three-dimensional direction, and the growth solution. A solution injection and suction device for injecting into or aspiration from the growth vessel, and an ultraviolet irradiation device for irradiating ultraviolet short pulse laser light for processing polymer crystals in the growth vessel; A polymer crystal growing device comprising: an observation device for observing the polymer crystal in the growth vessel; and a constant temperature and humidity device for keeping the temperature and humidity of the growth vessel constant. is there.

  In this means, the growth solution can be placed in a growth vessel and maintained at a predetermined temperature and humidity to grow a polymer crystal. Then, the growing polymer crystal is observed with an observation device, and if an unnecessary part is generated, the growing solution is sucked with a solution injection and suction device as necessary to expose the polymer crystal from the growing solution, and the ultraviolet light is irradiated. The polymer crystal is processed by the ultraviolet short pulse laser light emitted from the irradiation device to process unnecessary portions, and then the growth solution is injected into the growth container by the solution injection suction device to grow the polymer crystal. You can continue. When observing and processing a sample, the stage can be moved in a three-dimensional direction to observe the polymer crystal in the field of view, and any part of the polymer crystal can be irradiated with ultraviolet short pulse laser light. can do.

  According to the present invention, there are provided a method for producing a large, high-quality polymer crystal, a method for producing a polymer crystal in which a substance other than the polymer crystal is inserted into the crystal, and a polymer crystal growing apparatus. Can do.

  Hereinafter, an example of a polymer crystal growth apparatus according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a diagram showing an outline of a polymer crystal growth apparatus as an example of an embodiment of the present invention.

  An xyz stage 2 is provided in the constant temperature / humidity tank 1, and a growth container 3 can be placed thereon. By driving the xyz stage 2, the growth container 3 can be moved in the x direction (left and right direction on the paper surface), the y direction (front of the paper surface, the depth direction), and the z direction (up and down direction on the paper surface) It can be rotated around the z-axis.

  In addition, an injection / suction device 4 is provided so that the growth solution 5 can be injected into the growth container 3 or the growth solution 5 can be sucked from the growth container 3. The polymer single crystal 6 is grown in the growth container 3.

  The growing polymer single crystal 6 is observed by the observation device 7 through the beam splitter 8. Then, when the occurrence of unnecessary portions is observed, the growth solution 5 is sucked from the growth vessel 3 by the injection and suction device 4 to expose the polymer crystal 6 from the surface of the growth solution 5, and the ultraviolet short pulse laser is generated. An ultraviolet short pulse laser beam is irradiated from the apparatus 9 and is condensed on the polymer crystal 6 by the condenser lens 10, and an unnecessary portion of the polymer crystal 6 is processed. The ultraviolet short pulse laser beam is reflected by the beam splitter 8 and focused on the polymer crystal 6.

  After the unnecessary portion of the polymer crystal 6 is processed in this way, the growth solution 5 is injected from the injection suction device 4 into the growth container 3, and the polymer crystal 6 is again immersed in the growth solution 5 for growth. Start.

  When removing the unnecessary portion of the polymer crystal 6, while observing the processed portion with the observation device 7, the stage 2 is driven to perform processing such as removal of the target portion. Although the portion irradiated with ultraviolet rays may not be visible, for example, the optical axis of the observation device 7 is aligned with the portion where the ultraviolet rays are condensed so that a virtual image of the mark can be formed at that position. By superimposing the virtual image of the mark and the polymer crystal 6 and observing, the position irradiated with ultraviolet rays can be observed. Further, with respect to the z-direction position, the position where the ultraviolet light is focused and the position where the observation device 7 is focused are made to coincide with each other, and the stage 2 is driven so that the processed portion is focused when irradiated with ultraviolet light. As a result, the ultraviolet rays can be condensed at the target position.

  The reason why the growth container 3 is placed in the constant temperature / humidity chamber 1 is to minimize the influence of changes in temperature and humidity on the growth conditions of the polymer crystals. For example, a change in temperature is not preferable because the degree of supersaturation of the solution changes. Further, since the inside of the growth container is covered with the cover 11 and is in a saturated state, if the outside of the container is dry, the evaporation amount of the growth solution 5 increases when the cover 11 is removed during the processing operation. .

  As described above, the stage 2 is driven when the polymer crystal 6 is observed or processed. In addition, the stage 2 is moved temporarily or intermittently during the growth of the polymer crystal 6 so that the growth solution 5 is moved. Stirring can suppress the generation of unnecessary nuclei and improve the quality of crystals.

  Ultraviolet rays are irradiated into the constant temperature / humidity chamber 1 through the window 12, and the window 12 is made of a material having a high transmittance with respect to the ultraviolet rays, such as quartz and fluorite. In FIG. 1, the ultraviolet rays are incident (vertical) irradiation, but may be oblique irradiation, and an optical fiber may be used as a propagation path.

  As described above, the injection and suction device 4 has a function of injecting the growth solution 5 into the growth container 3 and sucking it from the growth container 3, but in addition to this, the processing of the polymer single crystal 6 is performed. Operation to suck and remove debris (scattered matter generated by laser ablation) generated inside, take out unnecessary crystals, and remove processed polymer single crystal 6 to another growth vessel Operations, such as adding or replacing a solution, can also be performed. The injection / suction device 4 has a position control mechanism (not shown), and can be set to a position where the tip of the injection / suction device 4 enters the growth container 3 and further the growth solution 5 as necessary.

  The cover 11 may be one that manually closes the upper portion of the growth vessel 3, but may also have an automatic opening / closing mechanism. Further, even when the tip of the injection / suction device 4 is inserted into the growth vessel 3, it is connected to the tip of the injection / suction device 4 by, for example, a bellows mechanism so as to maintain hermeticity. Also good.

  In FIG. 1, the illumination device of the observation device 7 is omitted, but a device as shown in FIG. 2 shown later can be used.

  In order to investigate the basic characteristics of crystal growth according to the present invention, a protein single crystal is irradiated with an ultraviolet short pulse laser beam using an apparatus as shown in FIG. Removed. The laser-processed crystal was regrown, and the X-ray diffraction pattern of the grown crystal was measured.

  In this apparatus, the ultraviolet short pulse laser beam from the ultraviolet short pulse laser system 21 is condensed at a predetermined point via the condensing optical system 22. The stage 23 can move in the three-dimensional directions of the x-axis, y-axis, and z-axis in the xyz orthogonal coordinate system with the optical axis direction of the optical microscope described later as the z-axis, and the z-axis. It can be rotated around. A sample container 25 containing the polymer crystal 24 is placed on the stage 23. Visible light from the illumination light source 26 is reflected by the reflecting mirror 27, and the sample container 25 is Koehler illuminated. The polymer crystal 24 is visually observed by the eye 30 through the objective lens 28 and the eyepiece lens 29 of the optical microscope.

  A cross-shaped mark is formed at the optical axis position of the optical microscope so that the optical axis position can be visually observed. The focus position of the optical microscope (the in-focus position, that is, the object surface that is in focus when viewed) is fixed. The ultraviolet short pulse laser beam condensed by the condensing optical system 22 is condensed at the optical axis position of the optical microscope and at the focal position of the optical microscope. Therefore, when a workpiece is placed on the stage 23 and its image is observed with an optical microscope, the ultraviolet short pulse laser system 21 from the ultraviolet short pulse laser system 21 is in focus and at the center of the cross mark. Pulse laser light is condensed. In addition, the relative positional relationship of the ultraviolet short pulse laser system 21, the condensing optical system 22, and the optical microscope unit is fixed, and only the stage 23 is movable relative to these fixed systems.

  Therefore, by processing while moving the stage 23 so that the place where processing is desired is the optical axis position of the optical microscope and the in-focus position, processing at a desired place and processing of a desired shape can be performed. Can do.

  A protein chicken egg white lysozyme was selected as a model polymer, and a single crystal of the protein was grown in a sample container by vapor diffusion. The crystal growth solution was adjusted to a concentration of 80 mg / ml sodium chloride in a 0.1 M acetic acid buffer solution adjusted to pH 4.5 after preparing a 25 mg / ml solution of chicken egg white lysozyme sample re-purified 6 times. A 5 μl solution mixed with a 1: 1 ratio was used. 400 μl of a solution adjusted to a sodium chloride concentration of 80 mg / ml was added to a 0.1 M acetate buffer solution adjusted to pH 4.5 as an external solution.

  When this sample container was allowed to stand at a constant temperature of 20 ° C. for 20 hours, a chicken egg white lysozyme single crystal having a size of about 0.1 mm × 0.2 mm × 0.03 mm was grown. Laser processing was performed on this growing crystal. A part of the growth solution in which the crystal was present was removed, and the growth solution was left in the vicinity of the crystal so that the crystal was not denatured by drying. A crystal photograph before irradiation with ultraviolet short pulse laser light is shown in FIG.

  As the ultraviolet short pulse laser system 21, a solid ultraviolet short pulse laser light source having a wavelength of 193 nm was used. The configuration of the light source is as follows. A laser diode of vertical and horizontal single mode is directly modulated to generate pulsed light having a wavelength of 1547 nm and a repetition frequency of 1 kHz. This pulsed light is amplified about 2 million times by a total of three stages of erbium-doped fiber amplifiers connected in series. Next, the output light from the fiber amplifier is converted into the eighth harmonic by a five-step wavelength conversion process using a nonlinear optical crystal, and light having a wavelength of 193 nm is generated.

The ultraviolet short pulse laser light emitted from the ultraviolet short pulse laser system 21 passes through the shutter, and then is condensed on a synthetic quartz lens having a focal length of 100 mm, which is a condensing optical system 22, so that it is arranged on the stage 23. The sample was irradiated in the Z-axis direction from the upper surface of the sample container 25 containing the egg white lysozyme crystal (polymer crystal) 24. The crystal irradiation position was finely adjusted while observing with an optical microscope. The pulse energy of the irradiation light on the crystal was 0.25 μJ, the spot diameter was 25 μm, the fluence was 50 mJ / cm ² , the average intensity was 0.25 mW, and the pulse time width was 1 ns.

The spot position on the crystal was changed by reciprocating the stage 23 linearly in the XY plane at a moving speed of 0.5 mm / sec. By continuously carrying out the above reciprocating operation, the same location was irradiated with the ultraviolet short pulse laser beam a plurality of times. Irradiation was continued while observing the state of processing with a microscope, and a part of the chicken egg white lysozyme crystal was ablated by irradiation with a total of about 20,000 pulses. The total volume of the crystal excised by this irradiation was about 3 × 10 ⁻⁴ mm ³ . FIG. 3 (b) shows a stereomicrograph of a chicken egg white lysozyme crystal immediately after processing by irradiation with an ultraviolet short pulse laser beam. It was confirmed that laser processing could be carried out without causing mechanical damage such as cracks to the unirradiated site.

  The growth solution removed immediately after the completion of laser processing was returned to resume the growth. When the sample container was allowed to stand at a constant temperature of 20 ° C., it was confirmed that the laser-processed crystal became a seed crystal and the crystal grew again. A photograph of the crystal when 24 hours have elapsed after laser processing is shown in FIG. The size of the laser-processed chicken egg white lysozyme crystal was about 0.3 mm × 0.4 mm × 0.1 mm. It was found that the crystal grew on both the non-laser processed surface and the laser processed surface. When the growth was further observed after standing at 20 ° C., crystal growth ended when the final size was about 0.35 mm × 0.45 mm × 0.12 mm.

X-ray diffraction patterns were measured at room temperature for egg white lysozyme crystals regrown after laser processing and egg white lysozyme crystals not irradiated with laser grown under the same conditions. The X-ray generator used was ultraX18 (voltage 50 kV, current 100 mA) manufactured by Rigaku Corporation, and RAXIS IV ⁺⁺ was used as the detector. The distance between the crystal and the detector was 150 mm, the detection angle was 2 °, and the measurement time was 30 minutes / 2 °.

  45 frames of data were collected for each crystal. The diffraction resolution of the laser processed crystal was 0.19 nm, which was the same as the diffraction resolution of the unprocessed crystal. Moreover, only the diffraction pattern from one single crystal was measured for all the frames. From these, it was found that the egg white lysozyme crystal regrown after laser processing is a single crystal. Furthermore, the crystallinity of the laser-irradiated crystal was 0.300, and it was confirmed that no significant crystal quality degradation was caused by laser processing.

  In this example, the ablated and removed part is a normal crystal part, but from this example, when there is a defective part such as a damage, the defective part is removed by processing including the normal part and re-grown. By doing so, it can be seen that large crystals with few defective parts can be grown.

It is a figure which shows the outline | summary of the growth apparatus of the polymer crystal which is an example of embodiment of this invention. It is a figure which shows the outline | summary of the ultraviolet short pulse laser processing apparatus used for the Example of this invention. It is a microscope picture which shows the hen egg white lysozyme crystal | crystallization before ultraviolet irradiation, immediately after ultraviolet irradiation, and after re-growth.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Constant temperature / humidity tank, 2 ... Stage, 3 ... Growth container, 4 ... Injection suction apparatus, 5 ... Growth solution, 6 ... Polymer crystal, 7 ... Observation apparatus, 8 ... Beam splitter, 9 ... Ultraviolet short pulse laser Generating device, 10 ... condensing lens, 11 ... cover, 21 ... ultraviolet short pulse laser system, 22 ... condensing optical system, 23 ... stage, 24 ... polymer crystal, 25 ... sample container, 26 ... illumination light source, 27 ... Reflector, 28 ... objective lens, 29 ... eyepiece, 30 ... eye

Claims (8)

In the process of producing a polymer crystal, during the growth of the polymer crystal or once the growth of the polymer crystal is stopped, an unnecessary portion of the polymer crystal is processed by irradiation with an ultraviolet short pulse laser beam, A method for producing a polymer crystal, comprising a subsequent growing step. 2. The method for producing a polymer crystal according to claim 1, wherein the processing of the unnecessary portion is removal of the unnecessary portion using laser ablation with an ultraviolet short pulse laser beam. The method for producing a polymer crystal according to claim 2, wherein after removing the unnecessary portion, a substance other than the polymer crystal is inserted into at least a part of the removed portion. The unnecessary portion is processed by performing an operation for efficiently reaching the surface of the polymer crystal with the ultraviolet short pulse laser beam, and then irradiating the surface of the polymer crystal with the ultraviolet short pulse laser beam. It implements, The manufacturing method of the polymer crystal of any one of Claims 1-3 characterized by the above-mentioned. 5. The production of the polymer crystal according to claim 1, wherein the polymer crystal is at least one crystal selected from a resin, a protein, a saccharide, a lipid, and a nucleic acid. Method. The method for producing a polymer crystal according to any one of claims 1 to 5, wherein the wavelength of the ultraviolet short pulse laser beam is 400 nm or less. The method for producing a polymer crystal according to any one of claims 1 to 6, wherein an energy density per pulse of the ultraviolet short pulse laser beam is 1 mJ / cm ² or more. A growth container in which a growth solution is introduced to grow a polymer crystal, a stage on which the growth container is placed and movable in a three-dimensional direction, and the growth solution is injected into the growth container or from the growth container A solution injection and suction device for sucking, an ultraviolet irradiation device for irradiating an ultraviolet short pulse laser beam for processing the polymer crystal in the growth vessel, and an observation for observing the polymer crystal in the growth vessel A polymer crystal growing apparatus comprising: an apparatus; and a constant temperature and humidity apparatus that maintains a constant temperature and humidity of the growth container.

Images