Highly polarized object, and manufacturing method thereof, high polarization method and high polarization device

Abstract

To provide a highly polarized object containing a molecule, the target of high polarization by triplet DNP, to which a polarization source can be added and in which a sufficient longitudinal relaxation time can be achieved, and a manufacturing method thereof, a high polarization method and a high polarization device.SOLUTION: A highly polarized object 100 includes a first molecule 102, a second molecule 104, and a polarization source 108, where at least one of the first molecule and the second molecule is a target molecule whose nuclear spin is to be highly polarized by triplet DNP, a molecule that is not the target molecule out of the first molecule and the second molecule is a coformer molecule, the first molecule and the second molecule comprise a co-crystalline crystal structure including a binding part 106, the supramolecular synthon with a hexagonal structure, and the polarization source is arranged at a position to displace a part of the crystal structure.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a highly polarized object which is a target for highly polarizing nuclear spins, and a method for manufacturing the same, a highly polarizing method, and a highly polarizing apparatus.

Background Art

[0002] NMR (Nuclear Magnetic Resonance) spectroscopy is an essential tool in chemical analysis, and MRI (Magnetic Resonance Imaging) is an essential tool in medical diagnosis. Dynamic nuclear polarization (hereinafter also referred to as DNP), which is one method for improving these sensitivities, has been actively studied in recent years.

[0003] In NMR spectroscopy and MRI, the nuclear spins in a substance (hereinafter simply also referred to as nuclear spins) are precisely controlled under a strong static magnetic field, and rich information at the molecular level is read from an electromagnetic wave signal (NMR signal) modulated by the interaction between nuclear spins and the like. The sensitivity of the NMR signal is proportional to the polarization rate. However, even under a strong magnetic field of several T (tesla) to several tens of T applied by a superconducting magnet, the Zeeman energy of the nuclear spins is very low. Since this Zeeman energy is five orders of magnitude smaller than the thermal energy at room temperature, the ratio (polarization rate) at which the directions of the nuclear spins are biased in the direction of the static magnetic field is extremely low, on the order of 10 -5 ~10 -6 (0.001 to 0.0001%), and the ratio of the nuclear spins contributing to the detection signal among the resonating nuclear spins is extremely small. Therefore, in order to improve the sensitivities of NMR spectroscopy and MRI, it is important to increase the polarization rate of the nuclear spins. In this specification, "high polarization" means a state in which the polarization rate of the nuclear spins exceeds the polarization rate at room temperature.

[0004] By performing DNP at extremely low temperatures close to 1 K and high magnetic fields exceeding 3 T, nuclear spin polarization rates of several percent to several tens of percent can be achieved. However, the devices for this purpose have the problems of being expensive and large. In contrast, Patent Document 1 and Non-Patent Document 1 below disclose forming a eutectic by mixing benzoic acid added with pentacene as a polarization source and a target molecule, and performing triplet DNP using this. As a result, high polarization can be realized in a room temperature environment without cooling the sample to an extremely low temperature.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Non-Patent Documents

[0006]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] For polarization to diffuse in a solid added with a polarization source, it is necessary for the longitudinal relaxation time to be sufficiently long (for example, from 10 seconds to 100 seconds or more). Also, if various molecules used in the active ingredient can be highly polarized, it is effective for pharmaceutical development. However, pentacene, which is a polarization source, has the problem of being poorly soluble and having a limited variety of molecules that can be added.

[0008] Accordingly, an object of the present invention is to provide a highly polarizable object containing a molecule that can be a target for high polarization by triplet DNP, to which a polarization source can be added and a sufficient longitudinal relaxation time can be realized, and a method for producing the same, a high polarization method, and a high polarization apparatus.

Means for Solving the Problems

[0009] (1) The highly polarizable object according to the first aspect of the present invention contains a first molecule, a second molecule, and a polarization source. At least one of the first molecule and the second molecule is a target molecule that is a target for highly polarizing nuclear spins by triplet DNP. Among the first molecule and the second molecule, the molecule that is not a target molecule is a co-former molecule. The first molecule and the second molecule constitute a crystal structure of a co-crystal containing a supramolecular synthon having a hexagonal structure, and the polarization source is arranged at a position substituting a part of the crystal structure. Thereby, the polarization source can be incorporated into the crystal structure. Therefore, the nuclear spins of the target molecules can be highly polarized by triplet DNP. In addition, a sufficient longitudinal relaxation time can be realized.

[0010] (2) In the above (1), the supramolecular synthon can include an acid-acid, acid-amide, or amide-amide supramolecular synthon. Thereby, a polarization source such as pentacene can be easily incorporated into the crystal structure, and the nuclear spins of the target molecules can be efficiently highly polarized by triplet DNP.

[0011] (3) In the above (1) or (2), the target molecule may be benzoic acid, salicylic acid, 3-nitrobenzoic acid, pentafluorobenzoic acid, nicotinamide, isonicotinamide, 4-methylbenzamide, salicylamide, benzamide, picolinamide, aspirin or ethenzamide. Thereby, the nuclear spins of these molecules can be highly polarized by triplet DNP.

[0012] (4) In the above (3), the supramolecular synthon may be a supramolecular synthon of acid-amide, and the combination of the first molecule and the second molecule may be any of salicylic acid and benzamide, salicylic acid and picolinamide, or 3-nitrobenzoic acid and benzamide. Thereby, by performing triplet DNP on the high polarization target, the nuclear spins of each molecule can be highly polarized. For example, a high polarization rate of 0.015% to 0.146% can be achieved.

[0013] (5) In the above (3), the combination of the first molecule and the second molecule may be salicylic acid and salicylamide. Thereby, by performing triplet DNP on the high polarization target, the nuclear spins of each molecule can be highly polarized. For example, a high polarization rate of 0.349% can be achieved.

[0014] (6) In the above (3), the combination of the first molecule and the second molecule may be a combination of benzoic acid and 4-methylbenzamide, salicylamide, or pentafluorobenzoic acid. Thereby, by performing triplet DNP on the high polarization target, the nuclear spins of each molecule can be highly polarized.

[0015] (7) In the above (3), the target molecule may be aspirin and the coformer molecule may be pentafluorobenzoic acid, or the target molecule may be ethenzamide and the coformer molecule may be pentafluorobenzoic acid, 3-nitrobenzoic acid, or salicylic acid. Thereby, by performing triplet DNP on the high polarization target, the nuclear spins of aspirin or ethenzamide can be highly polarized.

[0016] (8) The highly polarizable object according to the second aspect of the present invention includes a first coformer molecule, a second coformer molecule, a target molecule that is a target for highly polarizing nuclear spins by triplet DNP, and a polarization source. The first coformer molecule and the second coformer molecule constitute a crystal structure of a co-crystal including a supramolecular synthon having a hexagonal structure. The target molecule is bonded to the first coformer molecule and the second coformer molecule, or the first coformer molecule, by intermolecular forces, and the polarization source is disposed at a position substituting a part of the crystal structure. Thereby, the polarization source can be incorporated into the crystal structure. Therefore, the nuclear spins of the target molecule can be highly polarized by triplet DNP. Also, a sufficient longitudinal relaxation time can be realized.

[0017] (9) In the above (8), the supramolecular synthon can include an acid-acid, acid-amide, or amide-amide supramolecular synthon. Thereby, the polarization source can be easily incorporated into the crystal structure, and the nuclear spins of the target molecule can be efficiently highly polarized by triplet DNP.

[0018] (10) In the above (8) or (9), the target molecule may be picolinic acid, acetic acid, succinic acid, sebacic acid, dodecanedioic acid, pyruvic acid, formic acid, urea, nicotinamide, or isonicotinamide. Thereby, the nuclear spins of these molecules can be highly polarized by triplet DNP.

[0019] (11) In the above (10), the supramolecular synthon is an amide-amide supramolecular synthon, the first coformer molecule and the second coformer molecule are isonicotinamide, and the target molecule may be benzoic acid, salicylic acid, or picolinic acid. Thereby, by performing triplet DNP on the highly polarizable object, the nuclear spins of the target molecule can be highly polarized.

[0020] (12) In the above (10), the supramolecular synthon may be an amide-amide supramolecular synthon, the first coformational molecule and the second coformational molecule may be nicotinamide, and the target molecule may be succinic acid, sebacic acid or dodecanedioic acid. Thus, by performing triplet DNP on the high-polarization target, the nuclear spins of these molecules can be highly polarized by triplet DNP. For example, a high polarization rate of 0.0079% can be achieved for succinic acid and nicotinamide, and 0.00405% for sebacic acid and nicotinamide.

[0021] (13) In the above (10), the supramolecular synthon may be an amide-amide supramolecular synthon, the first coformational molecule and the second coformational molecule may be isonicotinamide, and the target molecule may be sebacic acid, dodecanedioic acid or acetic acid. Thus, the nuclear spins of sebacic acid, dodecanedioic acid or acetic acid can be highly polarized by triplet DNP. For example, a high polarization rate of 0.00685% can be achieved for dodecanedioic acid.

[0022] (14) In the above (10), the supramolecular synthon may be an amide-amide supramolecular synthon, the first coformational molecule and the second coformational molecule may be nicotinamide, and the target molecule may be urea. Thus, by performing triplet DNP on the high-polarization target, a high polarization rate of 0.0135% can be achieved for urea.

[0023] (15) In the above (1) or (2), the first molecule is a conformer molecule, the second molecule is a target molecule, an acid-amide supramolecular synthon is formed by the first molecule and the second molecule, and a (acid-amide)-(acid-amide) supramolecular synthon is further formed by two first molecules and two second molecules. The polarization source may be arranged at a position that replaces two first molecules that form a part of a plurality of (acid-amide)-(acid-amide) supramolecular synthons in the co-crystal. Thereby, the polarization source can be incorporated into the crystal structure. Therefore, the nuclear spin of the target molecule can be highly polarized by triplet DNP. Also, a sufficient longitudinal relaxation time can be realized.

[0024] (16) In the above (15), the conformer molecule may be picolinamide or 4-methylbenzamide, and the target molecule may be pyruvic acid. Thereby, the nuclear spin of pyruvic acid can be highly polarized by performing triplet DNP on the highly polarized object.

[0025] (17) In the above (15), the conformer molecule may be picolinamide, and the target molecule may be mandelic acid. Thereby, the nuclear spin of mandelic acid can be highly polarized by performing triplet DNP on the highly polarized object.

[0026] (18) In the above (1) or (2), further comprising a third molecule, the first molecule and the third molecule are conformer molecules, the second molecule is a target molecule, the first molecule and the second molecule form an acid-amide supramolecular synthon, the first molecule and the third molecule form an acid-amide supramolecular synthon, two first molecules, one second molecule and one molecule further form an (acid-amide)-(acid-amide) supramolecular synthon, and the polarization source may be arranged at a position substituting the first molecule and the third molecule that form a part of the acid-amide supramolecular synthons among a plurality of (acid-amide)-(acid-amide) supramolecular synthons in the co-crystal. Thereby, the polarization source can be incorporated into the crystal structure. Therefore, the nuclear spin of the target molecule can be highly polarized by triplet DNP. Also, a sufficient longitudinal relaxation time can be realized.

[0027] (19) In the above (18), the first molecule is picolinamide, the third molecule is salicylic acid, and the target molecule may be pyruvic acid, acetic acid or formic acid. Thereby, by performing triplet DNP on the high-polarization target, the nuclear spin of pyruvic acid, acetic acid or formic acid can be highly polarized.

[0028] (20) In the above (18), the first molecule is picolinamide, the third molecule is 4-chlorosalicylic acid, and the target molecule may be pyruvic acid. Thereby, by performing triplet DNP on the high-polarization target, the nuclear spin of pyruvic acid can be highly polarized.

[0029] (21) In the above (18), the first molecule is 4-methylbenzamide, the third molecule is benzoic acid, and the target molecule may be pyruvic acid. Thereby, by performing triplet DNP on the high-polarization target, the nuclear spin of pyruvic acid can be highly polarized.

[0030] (22) The method for manufacturing a highly polarized object according to the third aspect of the present invention includes a step of generating a molten mixture containing a first molecule, a second molecule, and a polarization source by heating, and a cooling step of cooling the molten mixture. At least one of the first molecule and the second molecule is a target molecule that is a target for highly polarizing nuclear spins by triplet DNP. Among the first molecule and the second molecule, the molecule that is not the target molecule is a co-former molecule. By the cooling step, the first molecule and the second molecule constitute a crystal structure of a co-crystal containing a supramolecular synthon having a hexagonal structure, and the polarization source is arranged at a position substituting a part of the crystal structure. Thereby, the polarization source can be incorporated into the crystal structure. Therefore, the nuclear spins of the target molecules can be highly polarized by triplet DNP. Also, a sufficient longitudinal relaxation time can be realized.

[0031] (23) The method for manufacturing a highly polarized object according to the fourth aspect of the present invention includes a step of generating a molten mixture containing a first co-former molecule, a second co-former molecule, a target molecule that is a target for highly polarizing nuclear spins by triplet DNP, and a polarization source, and a cooling step of cooling the molten mixture. By the cooling step, the first co-former molecule and the second co-former molecule constitute a crystal structure of a co-crystal containing a supramolecular synthon having a hexagonal structure, and the target molecule is bonded to the first co-former molecule and the second co-former molecule, or the first co-former molecule by intermolecular forces, and the polarization source is arranged at a position substituting a part of the crystal structure. Thereby, the polarization source can be incorporated into the crystal structure. Therefore, the nuclear spins of the target molecules can be highly polarized by triplet DNP. Also, a sufficient longitudinal relaxation time can be realized.

[0032] (24) The method for highly polarizing nuclear spins according to the fifth aspect of the present invention includes an optical irradiation step of irradiating a sample disposed in a space where a uniform static magnetic field is formed with light, and a microwave irradiation step of irradiating the sample with microwaves while applying a sweeping magnetic field to the sample following the optical irradiation step. The sample includes any one of the above (1), (2), (8), and (9) highly polarizable objects, and after repeating the optical irradiation step and the microwave irradiation step, further includes a dissolution step of dissolving target molecules in the sample to generate a solution. Thereby, a solution of target molecules with highly polarized nuclear spins can be generated.

[0033] (25) The apparatus for highly polarizing nuclear spins according to the sixth aspect of the present invention is an apparatus for highly polarizing nuclear spins in a sample by triplet DNP, and includes a magnetic field forming unit for forming a static magnetic field, an optical irradiation unit for irradiating a sample disposed in a region where the static magnetic field is formed with light, a microwave irradiation unit for irradiating the sample disposed in the region where the static magnetic field is formed with microwave pulses, and a control unit for controlling the optical irradiation unit and the microwave irradiation unit. The sample includes any one of the above (1), (2), (8), and (9) highly polarizable objects, and the control unit controls the optical irradiation unit and the microwave irradiation unit to highly polarize the nuclear spins in the highly polarizable object by triplet DNP. Thereby, the nuclear spins of target molecules can be highly polarized.

Advantages of the Invention

[0034] According to the present invention, it is possible to provide a highly polarizable object including a molecule that is a target for high polarization by triplet DNP, a method for producing the same, a method for high polarization, and an apparatus for high polarization, which can add a polarization source and achieve a sufficient longitudinal relaxation time. That is, it is possible to realize target molecules with highly polarized nuclear spins in a room temperature environment without cooling a sample containing the target molecules. For example, as the target molecule, a molecule used for a drug substance, a ligand, or a metabolite molecule probe can be used. By using an aqueous solution containing target molecules with highly polarized nuclear spins in an NMR spectrometer or an MRI apparatus, ultra-high sensitivity chemical analysis or ultra-high sensitivity metabolic imaging becomes possible.

[0035] In addition, it is possible to realize a small and low-cost nuclear spin hyperpolarization device that can highly polarize nuclear spins at room temperature and is applicable to chemical analysis or medical applications. By attaching this hyperpolarization device to a commercially available NMR spectrometer or MRI device, ultra-high-sensitivity chemical analysis or ultra-high-sensitivity metabolic imaging becomes possible.

Brief Description of the Drawings

[0036]

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DETAILED DESCRIPTION OF THE INVENTION

[0037] In the following embodiments, the same parts are denoted by the same reference numerals. Their names and functions are also the same. Therefore, detailed descriptions thereof will not be repeated.

[0038] (First Embodiment) Referring to FIG. 1, the highly polarizable object 100 according to the first embodiment of the present invention includes a first molecule 102, a second molecule 104, and a polarization source 108. The first molecule 102 and the second molecule 104 are bonded to form a bonding portion 106, constituting a cocrystal. At least one of the first molecule 102 and the second molecule 104 is a molecule (hereinafter referred to as a target molecule) that is the target of high polarization of nuclear spins by triplet DNP. Among the first molecule 102 and the second molecule 104, the molecule that is not a target molecule is a molecule (hereinafter referred to as a coformer molecule) that constitutes a cocrystal together with the target molecule. One component constituting the cocrystal is formed by one first molecule 102 and one second molecule 104. Both the cocrystal and the eutectic are composed of a plurality of types of non-ionized molecules. While the eutectic maintains the crystal phases of the respective types of molecules, the cocrystal is composed of a plurality of types of molecules present in the same crystal lattice.

[0039] The polarization source 108 is dispersed and arranged at a position that replaces a part (i.e., a component) of the cocrystal in the crystal structure of the cocrystal formed by the first molecule 102 and the second molecule 104. The polarization source 108 is a molecule having electrons in the photoexcited triplet state and is the first molecule to be highly polarized in triplet DNP. By transferring the high polarization of the nuclear spin of the polarization source 108 to the first molecule 102 and the second molecule 104, high polarization of the nuclear spin of the target molecule is realized.

[0040] To form a co-crystal of the first molecule 102 and the second molecule 104, for example, the powdered first molecule 102 and the second molecule 104 are mixed, melted by heating or the like, and then cooled. As a result, referring to FIG. 2, the group 112 of the first molecule 102 and the group 114 of the second molecule 104 are bonded to form a bonding portion 106, and a co-crystal component 110 is formed. The groups 112 and 114 are groups (specifically, functional groups) in organic chemistry. The bonding portion 106 is formed by a bond other than a covalent bond such as a hydrogen bond, and the co-crystal component 110 is a supramolecule. A part of a plurality of co-crystal components 110 that is substituted by the polarization source 108 is the highly polarized object 100. In FIG. 2, the polygons (i.e., hexagons) included in the first molecule 102 and the second molecule 104 mean aromatic rings such as benzene rings. The white circles shown in FIG. 2 represent atoms or atomic groups (such as nitrogen atoms, hydroxyl groups, carboxylic acids, etc.) that form non-covalent bonds such as hydrogen bonds. The dashed lines between the white circles represent non-covalent bonds such as hydrogen bonds.

[0041] The bonding portion 106 is the basic skeleton of a non-covalent bond such as a hydrogen bond formed in a supramolecule (co-crystal component 110), and is a supramolecular synthon. Each of the groups 112 and 114 is, for example, a carboxyl group (-COOH) or an amide group (-CO-NH 2 )). For example, when both the groups 112 and 114 are carboxyl groups, an acid-acid supramolecular synthon (homo-dimer) shown in FIG. 3 is formed as the bonding portion 106. In FIG. 3, the dashed lines represent non-covalent bonds (the same applies hereinafter). When both the groups 112 and 114 are amide groups, an amide-amide supramolecular synthon (homo-dimer) is formed as the bonding portion 106 with reference to FIG. 4. When one of the groups 112 and 114 is a carboxyl group and the other is an amide group, an acid-amide supramolecular synthon (hetero-dimer) shown in FIG. 5 is formed as the bonding portion 106. The shapes that form the basis of these supramolecular synthons are all hexagons.

[0042] For the polarization source 108, pentacene shown in FIG. 6 or a pentacene derivative can be used. The pentacene derivative means a molecule represented by the chemical formula shown in FIG. 7. In the chemical formula shown in FIG. 7, each R independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a hydrogen atom (H), a deuterium atom (D), or an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, and at least one of the Rs is a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. Further, in the chemical formula shown in FIG. 7, those in which a part of the aromatic ring is substituted by a nitrogen atom or the like (for example, 6,13-diazapentacene, etc.) are also included in the derivatives. Note that the polarization source 108 is not limited to pentacene derivatives, and acene-based molecules can be used. Acene means a hydrocarbon having a structure in which a plurality of benzene rings are linearly condensed. The acene-based molecule means naphthalene (molecular formula C 10 H 8 ), anthracene (molecular formula C 14 H 10 ), tetracene (molecular formula C 18 H 12 ), pentacene (molecular formula C 22 H 14 ), hexacene (molecular formula C 26 H 16 ), and heptacene (molecular formula C 30 H 18 ), and derivatives thereof.

[0043] Hereinafter, combinations of the first molecule 102 and the second molecule 104 will be specifically exemplified. For example, as a combination of the first molecule 102 and the second molecule 104, benzoic acid (molecular formula C 7 H 6 O 2 ) shown in FIG. 8 and 4-methylbenzamide (molecular formula C 8 H 9 NO) shown in FIG. 9 can be used. As the benzoic acid, as shown in FIG. 10, deuteration (that is, substitution of a hydrogen atom ( 1 H) with a deuterium atom ( 2 H)) gives d 5- Benzoic acid (molecular formula C 7 D 5 O 2 H) may also be used. In FIG. 10, D represents a deuterium atom. The combination of the first molecule 102 and the second molecule 104 may be benzoic acid (see FIGS. 8 and 10) and salicylamide (molecular formula C 7 H 7 NO 2 ) shown in FIG. 11.

[0044] As the combination of the first molecule 102 and the second molecule 104, salicylic acid (molecular formula C 7 H 6 O 3 ) shown in FIG. 12 and benzamide (molecular formula C 7 H 7 NO) shown in FIG. 13 can be used. The combination of the first molecule 102 and the second molecule 104 may be salicylic acid (see FIG. 12) and picolinamide (molecular formula C 6 H 6 N 2 O) shown in FIG. 14. The combination of the first molecule 102 and the second molecule 104 may be 3-nitrobenzoic acid (molecular formula C 7 H 5 NO 4 ) shown in FIG. 15 and benzamide (see FIG. 13). In these cases, an acid - amide supramolecular synthon is formed as the bonding part 106.

[0045] As the combination of the first molecule 102 and the second molecule 104, salicylic acid (see FIG. 12) and salicylamide (see FIG. 11) can be used.

[0046] The combination of the first molecule 102 and the second molecule 104 may be benzoic acid (see FIGS. 8 and 10) and pentafluorobenzoic acid (molecular formula C 7 F 5 O 2 H) shown in FIG. 16.

[0047] As the combination of the first molecule 102 and the second molecule 104, aspirin (i.e., acetylsalicylic acid) (molecular formula C 9 H 8O 4 ) and pentafluorobenzoic acid (see Fig. 16) can be used. Also, as the combination of the first molecule 102 and the second molecule 104, ethenzamide (molecular formula C 9 H 11 NO 2 ) and pentafluorobenzoic acid (see Fig. 16) can be used. The combination of the first molecule 102 and the second molecule 104 may be ethenzamide (see Fig. 17) and 3-nitrobenzoic acid (see Fig. 15). The combination of the first molecule 102 and the second molecule 104 may be ethenzamide (see Fig. 17) and salicylic acid (see Fig. 12). Aspirin and ethenzamide are used as drugs or ligands and are target molecules of triplet DNP.

[0048] (Method for producing highly polarized object) With reference to Fig. 19, the method for producing the highly polarized object 100 will be specifically described. In step 200, the first molecule and the second molecule are mixed. For example, the first molecule and the second molecule (molar ratio is, for example, 1:1) are put into a mortar and mechanically ground into a powder and mixed. Note that the ratio of mixing the first molecule and the second molecule is not limited to a molar ratio of 1:1, and an appropriate molar ratio can be determined.

[0049] In step 202, the mixture generated in step 200 is heated and melted. For example, the mixture is heated to a temperature in the range of 150°C to 200°C.

[0050] In step 204, a polarization source (see Figs. 6 and 7) is added to the melted mixture. For example, a trace amount (for example, about 0.1 mol% or less with respect to the whole mixture) of a powder polarization source is put into the melted mixture and stirred.

[0051] In step 206, the melted mixture added with the polarization source is rapidly cooled using a cooling material such as liquid nitrogen or ice water. For example, the container containing the melted mixture added with the polarization source is brought into contact with (e.g., immersed in) liquid nitrogen or ice water. Thereby, as shown in FIG. 1, in the eutectic formed by the first molecule 102 and the second molecule 104, a highly polarized object 100 having a structure in which some components are replaced by the polarization source 108 is formed. During melting, the bonds between molecules (such as hydrogen bonds or π-π interactions) are broken, and the component molecules are moving in the liquid. During cooling, while the bonds are being formed and broken, it converges to a stable crystal structure. In this process, the polarization source can easily enter the position where the components of the eutectic are originally arranged. Note that the cooling material may be a refrigerant (such as dry ice and methanol, or ice and salt), or may be liquid water.

[0052] After mixing and melting the first molecule and the second molecule of the above-described combination, by adding a pentacene derivative (see FIGS. 6 and 7) and rapidly cooling, as shown in FIG. 1, a highly polarized object 100 in which a part of the eutectic is replaced by the polarization source 108 can be generated. Both the first molecule and the second molecule contain an aromatic ring, and the supramolecular synthon formed by the groups of the first molecule and the second molecule has a hexagonal shape. The pentacene (see FIG. 6) or the pentacene derivative (see FIG. 7) used as the polarization source has five benzene rings. Therefore, a part of the components of the eutectic by the first molecule 102 and the second molecule 104 can be easily replaced by the pentacene (see FIG. 6) or the pentacene derivative (see FIG. 7) which is the polarization source. That is, during the process of forming the eutectic, the polarization source can easily enter the position where the components of the eutectic are originally arranged. As a result, as described later, the nuclear spin of the highly polarized object 100 (i.e., either the first molecule or the second molecule) can be highly polarized by triplet DNP.

[0053] In the above description, the case where a polarization source is added in a state where the mixture of the first molecule and the second molecule is heated and melted has been described, but the present invention is not limited thereto. The mixture obtained by adding a polarization source to the first molecule and the second molecule may be heated and melted. In any case, a molten mixture containing the first molecule, the second molecule, and the polarization source may be generated, and the molten mixture may be rapidly cooled.

[0054] The fact that the highly polarized object 100 is a co-crystal can be confirmed by, for example, powder X-ray diffraction, solid NMR, etc. For example, by comparing the XRD (X-Ray Diffraction) pattern obtained by X-ray diffracting the synthesized highly polarized object 100 with a known XRD pattern, it can be confirmed that a co-crystal is formed.

[0055] (High polarization device) In order to highly polarize the nuclear spin of the highly polarized object 100 shown in FIG. 1, triplet DNP is performed using a high polarization device. Referring to FIG. 20, the high polarization device 300 includes a main magnetic field forming unit 302, a cavity 304, a laser light source 308, a microwave source 310, and an amplification unit 312. The cavity 304 is disposed between the magnetic poles of the main magnetic field forming unit 302. The laser light source 308 generates laser light that irradiates a sample 306 disposed in the cavity 304. The microwave source 310 generates microwaves. The amplification unit 312 amplifies the microwaves output from the microwave source 310 and irradiates the sample 306.

[0056] Furthermore, the high polarization device 300 for nuclear spins includes a sweeping magnetic field forming unit 314, a power supply unit 316, an NMR signal detection unit 318, an NMR analysis unit 320, and a control unit 322. The sweeping magnetic field forming unit 314 is disposed in the cavity 304. The power supply unit 316 supplies current to the sweeping magnetic field forming unit 314. Thereby, the sweeping magnetic field forming unit 314 forms a sweeping magnetic field that irradiates the sample 306, as will be described later. The NMR signal detection unit 318 detects an NMR signal. The NMR analysis unit 320 analyzes the NMR signal detected by the NMR signal detection unit 318. The control unit 322 controls these units.

[0057] An example of the configuration of the cavity 304 and its surroundings is shown in FIG. 21. In FIG. 21, the cavity 304 and the waveguide 334 are shown broken.

[0058] Referring to FIG. 20, the main magnetic field forming unit 302 is an electromagnet to which a current is supplied from a power source (not shown), and forms a static magnetic field with uniform direction and intensity in the region where the sample 306 is disposed. The sample 306 is the highly polarizable object 100 shown in FIG. 1. In FIG. 20, two main magnetic field forming units 302 are arranged, which are electromagnets having two opposing magnetic poles (for example, opposing Helmholtz coils). Since the polarization rate of the optically excited triplet electron spin is not proportional to the temperature and the magnetic field strength, it is not necessary to use a magnet that generates a high magnetic field such as a superconducting magnet for the main magnetic field forming unit 302. Therefore, a relatively inexpensive air-core solenoid coil electromagnet can be used as the main magnetic field forming unit 302.

[0059] The main magnetic field forming unit 302 may be an electromagnet having no opposing magnetic poles, for example, an electromagnet using an air-core solenoid coil. When a solenoid coil is used, the cavity 304 is disposed inside the solenoid coil. The main magnetic field forming unit 302 may be a permanent magnet.

[0060] The cavity 304 functions as a resonator for microwaves supplied from the microwave source 310 via the amplifier unit 312 and the waveguide 334 (see FIG. 21). The cavity 304 is formed of an electrical conductor that is not a magnetic material. The cavity 304 is formed such that its resonance frequency is equal to the frequency of the microwaves output from the microwave source 310. The junction between the cavity 304 and the waveguide 334 is preferably coupled by a known iris in order to suppress reflection of the supplied microwaves.

[0061] The laser light source 308 shown in FIG. 20 is controlled by the control unit 322 to output laser light of a predetermined wavelength for a predetermined period at a predetermined timing. The output laser light is transmitted to the cavity 304 via the optical transmission unit 330 (see FIG. 21). A condensing unit 332 is provided in the cavity 304 to condense the laser light emitted from the optical transmission unit 330 and irradiate the sample 306. For the laser light source 308, for example, a flash lamp-excited dye laser can be used. The optical transmission unit 330 is, for example, an optical fiber, and the condensing unit 332 is, for example, a lens.

[0062] The microwave source 310 is controlled by the control unit 322 to generate and output microwaves of a predetermined frequency for a predetermined period at a predetermined timing. A microwave generator can be used for the microwave source 310. In DNP, in order to supply microwave pulses to the sample, a pulse wave is generated from the microwaves continuously output from the microwave source 310 by a switch (not shown).

[0063] The power supply unit 316 receives control by the control unit 322 and supplies current to the sweep magnetic field forming unit 314. The sweep magnetic field is used to excite a set of spins with a width in the resonance frequency, and by changing the current value flowing through the sweep magnetic field forming unit 314 over time, the magnetic field strength is changed, that is, the magnetic field is swept. The intensity of the sweep magnetic field is sufficiently smaller than the intensity of the main magnetic field. The direction of the sweep magnetic field is the same as or opposite to the direction of the main magnetic field. FIG. 21 shows the case where a saddle coil is used as the sweep magnetic field forming unit 314. FIG. 21 shows two of the four parallel straight portions that constitute the sweep magnetic field forming unit 314 (i.e., the saddle coil). In FIG. 21, since the main magnetic field direction is vertically upward perpendicular to the paper surface, if currents in opposite directions are supplied to the two straight portions (similarly for the remaining two straight portions not shown), a sweep magnetic field in the same direction as or opposite to the main magnetic field can be formed in the region where the sample 306 is placed.

[0064] The NMR signal detection unit 318 is a coil for detecting an NMR signal (e.g., FID (Free Induction Decay) signal) generated by spins precessing around the main magnetic field. The coil constituting the NMR signal detection unit 318 can detect a magnetic field change in a direction orthogonal to the main magnetic field. The NMR analysis unit 320 measures an NMR signal using the NMR signal detection unit 318 under the control of the control unit 322 and performs NMR analysis. Note that the resonance frequency of the NMR signal detection unit 318 is adjusted by adjustment components (not shown) such as a capacitor to be equal to the NMR frequency corresponding to the intensity of the main magnetic field.

[0065] Referring to FIG. 21, the sample container 336 holds the sample 306. The sample container 336 is formed of a material that transmits the supplied laser light and microwaves, and is, for example, a glass tube. The sample container 336 and the NMR signal detection unit 318 are preferably held so as to be displaceable with respect to the cavity 304. That is, it is preferable to have a mechanism that allows the sample container 336 to be moved outside the cavity 304, enables the sample 306 to be introduced into the sample container 336, and can place the sample container 336 containing the sample 306 at a predetermined position inside the cavity 304. Similarly, it is preferable to have a mechanism that allows the NMR signal detection unit 318 to be moved outside the cavity 304 and can place the NMR signal detection unit 318 at a predetermined position (around the sample 306) inside the cavity 304.

[0066] The solvent supply unit 338 holds a solvent (solution) 350 for dissolving the solid sample 306. In FIG. 21, a dropper is shown as an example of the solvent supply unit 338. The solvent 350 held by the solvent supply unit 338 is dropped onto the sample 306 to generate a solution containing the sample 306.

[0067] (High polarization of nuclear spins) Hereinafter, with reference to FIG. 22, a method for highly polarizing the nuclear spins of the sample 306 (i.e., the high-polarization target 100 shown in FIG. 1) using the high-polarization device 300 shown in FIG. 20 will be described.

[0068] In step 400, sample 306 is prepared as the high polarization object. Specifically, the high polarization object 100 shown in FIG. 1 is generated by the manufacturing method shown in FIG. 19. The NMR signal detector 318 is set in the sample container 336 into which the sample 306 is introduced, and the sample container 336 is arranged in the cavity 304 so that the sample 306 is located at the center of the cavity 304. Here, it is assumed that the polarization source included in the high polarization object 100 is pentacene (see FIG. 6).

[0069] The amount of the sample 306 (i.e., the high polarization object 100) can be determined according to the ability (output power) of the laser light source used. If a laser light source capable of outputting strong laser light is used, a larger amount of the sample 306 can be highly polarized.

[0070] In step 402, in a state where the main magnetic field forming unit 302 is energized to form a static magnetic field, the control unit 322 controls the laser light source 308, the microwave source 310, and the sweeping magnetic field forming unit 314 to perform triplet DNP on the sample 306. Specifically, referring to FIG. 23, while the sweeping magnetic field forming unit 314 sweeps the magnetic field, the sample 306 is irradiated with laser light by the laser light source 308 during the period T1, and then the sample 306 is irradiated with microwaves by the microwave source 310 during the subsequent period T2. Note that during the period T1, the sweeping of the magnetic field is optional.

[0071] In step 404, the control unit 322 determines whether to end the triplet DNP. If it is determined to end, the control proceeds to step 406. Otherwise, after the period T3 has elapsed, the control returns to step 402. As a result, the sequence shown in FIG. 23 is repeated with the period T3 as one cycle.

[0072] The determination of the end of the triplet DNP is made, for example, by previously setting the number of executions N and determining whether the laser light irradiation and the microwave irradiation have been executed N times. Alternatively, the end of the triplet DNP may be determined by previously setting the execution time ΔT and determining whether the time ΔT has elapsed since the laser light irradiation and the microwave irradiation were first performed.

[0073] The high polarization target object 100, which is the sample 306, contains pentacene (see FIG. 6) as a polarization source. When pentacene is irradiated with laser light, the electrons of pentacene are excited by the laser light and transition from the ground state S 0 of the energy level to the excited singlet state S 1 . Thereafter, mainly, it emits light such as spontaneous emission and transitions to the ground state, but in addition, it transitions to the excited triplet state (T 3 ) due to spin-orbit interaction (intersystem crossing (ISC)). According to the selection rule in this quantum process, the electron spin distribution is largely biased by about 70%. The excited triplet state decays (transitions) to the ground state S 0 after about 100 microseconds, but microwave irradiation is performed during that time to perform pulsed DNP. If pentacene is in a magnetic field, the levels of the excited triplet state are separated into three levels (denoted as |+1>, |0>, and |-1> in descending order of energy level). Therefore, when microwave irradiation with a frequency corresponding to the energy difference between the |-1> level and the |0> level, or the energy difference between the |0> level and the |+1> level is performed, the high polarization of the electron spin is transferred to the hydrogen nucleus ( 1 H) spin (hereinafter also referred to as hydrogen nuclear spin) by a mechanism such as cross polarization. The time for microwave irradiation is preferably 1 μs or more. At this time, the hydrogen nuclear spin of pentacene is highly polarized, and the high polarization is further transferred to the hydrogen nuclear spins of the first molecule 102 and the second molecule 104 constituting the high polarization target object 100. Therefore, as described above, by repeating step 402, the hydrogen nuclear spins of the entire sample 306 can be highly polarized.

[0074] When it is determined that the triplet DNP is terminated, in step 406, the control unit 322 stops the laser light source 308, the microwave source 310, and the power supply unit 316.

[0075] In step 408, the solvent 350 held by the solvent supply unit 338 is dropped onto the sample 306 to dissolve the first molecule 102 in the sample 306. As a result, an aqueous solution in which the first molecule 102 in the sample is dissolved is generated. By using a solvent that does not dissolve pentacene, the pentacene remaining without being dissolved can be easily removed by a filter or the like. As the solvent, for example, an aqueous solution containing an aqueous sodium carbonate solution, an alcohol containing methanol, a solvent containing chloroform, or the like can be used.

[0076] As described above, an aqueous solution containing a target molecule (either the first molecule 102 or the second molecule 104) with highly polarized hydrogen nuclei can be generated. By using this aqueous solution in an NMR spectrometer and an MRI apparatus, ultra-high sensitivity NMR spectroscopy and ultra-high sensitivity MRI can be realized. If a target molecule that is harmless to the human body and is metabolized in the body is used, an aqueous solution containing the target molecule and not containing pentacene, which is harmful to the human body, can be safely used in an MRI examination or the like targeting the human body.

[0077] In the above description, the case where the end of the triplet DNP is determined using the preset number of repetitions N or the preset execution time ΔT has been described, but it is not limited to this. For example, while repeatedly executing the triplet DNP, when an NMR signal is observed by the NMR signal detection unit 318 and an NMR signal of a predetermined intensity is observed, it may be determined that the triplet DNP is terminated.

[0078] In the above description, the case where the liquid for dissolving the target molecule is dropped onto the high polarization target 100 has been described, but it is not limited to this. For example, the liquid for dissolving the target molecule may be sprayed onto the high polarization target 100 using a spray or the like. Further, the high polarization target 100 may be put into the liquid for dissolving the target molecule contained in the container.

[0079] In the above description, the case of adding pentacene as the polarization source has been described, but it is not limited thereto. Pentacene derivatives other than pentacene (see Fig. 7) may be used.

[0080] (Second Embodiment) In the above description, the case where the target molecule to be highly polarized constitutes a supramolecular synthon has been described, but it is not limited thereto. In the second embodiment, a supramolecular synthon is formed by molecules other than the target molecule.

[0081] The highly polarized object according to the second embodiment of the present invention is a co-crystal similar to the highly polarized object 100 shown in Fig. 1, and a part of its components is replaced by a polarization source. Referring to Fig. 24, the co-crystal component 120, which is a component of the highly polarized object according to the second embodiment, is composed of a first molecule 122, a second molecule 124, and third molecules 136 and 138. At least one of the third molecules 136 and 138 is a target molecule that is the object of high polarization of nuclear spins by triplet DNP. The molecules other than the target molecule are co-former molecules that form a co-crystal together with the target molecule. The first molecule 122 has a group 132, and the second molecule 124 has a group 134. The groups 132 and 134 are groups (specifically, functional groups) in organic chemistry. The groups 132 and 134 are bonded to form a bonding part 126. The white circles shown in Fig. 24 represent atoms or atomic groups (such as nitrogen atoms, hydroxyl groups, carboxylic acids, etc.) that form non-covalent bonds (see the dashed lines) such as hydrogen bonds.

[0082] The bonding part 126 is a supramolecular synthon similar to the bonding part 106 (see Fig. 2). Each of the groups 132 and 134 is, for example, a carboxyl group or an amide group, similar to the first molecule 102 and the second molecule 104 (see Fig. 2). Therefore, as the bonding part 126, an acid-acid supramolecular synthon (see Fig. 3), an amide-amide supramolecular synthon (see Fig. 4), or an acid-amide supramolecular synthon (see Fig. 5) is formed.

[0083] The third molecules 136 and 138 are bonded to the first molecule 122 and the second molecule 124, respectively, by non-covalent bonds such as hydrogen bonds. In FIG. 24, the polygons (i.e., hexagons) contained in the first molecule 122 and the second molecule 124 mean aromatic rings such as benzene rings. Each of the third molecules 136 and 138 may or may not contain an aromatic ring.

[0084] In FIG. 24, a state is shown in which the third molecule 136 is non-covalently bonded to the aromatic ring portion of the first molecule 122, and the third molecule 138 is non-covalently bonded to the aromatic ring portion of the second molecule 124. The third molecule 136 may be non-covalently bonded to the group 132 instead of the aromatic ring portion of the first molecule 122, and the third molecule 138 may be non-covalently bonded to the group 134 instead of the aromatic ring portion of the second molecule 124. Each of the third molecules 136 and 138 may be non-covalently bonded to the first molecule 122 and the second molecule 124. The third molecules 136 and 138 may be molecules with the same name or molecules with different names. Also, one of the third molecules 136 and 138 may not be present. In FIG. 24, the third molecules 136 and 138 are shown separately, but the third molecules 136 and 138 may be bonded by non-covalent bonds, and the third molecules 136 and 138 may form a supramolecular synthon. Also, a molecule that is not a target molecule among the third molecules 136 and 138 may be a molecule with the same name as the first molecule 122 or the second molecule 124.

[0085] The polarization source is, for example, pentacene (see FIG. 6) or a pentacene derivative (see FIG. 7). The polarization source is dispersed and arranged at a position substituting a part of the components of the co-crystal, that is, the first molecules 122 and 124, in the crystal structure of the co-crystal which is a high polarization object.

[0086] Hereinafter, combinations of the first molecule 122, the second molecule 124, the third molecules 136 and 138 will be specifically exemplified. For example, the first molecule 122 and the second molecule 124 are isonicotinamide (molecular formula C 6 H 6 N 2O), and the third molecules 136 and 138 can be benzoic acid (see FIGS. 8 and 10). The first molecule 122 and the second molecule 124 can be isonicotinamide (see FIG. 25), and the third molecules 136 and 138 may be salicylic acid (see FIG. 12). The first molecule 122 and the second molecule 124 are isonicotinamide (see FIG. 25), and the third molecules 136 and 138 are picolinic acid (molecular formula C 6 H 5 NO 2 ) shown in FIG. 26 may also be used. In these cases, an amide - amide supramolecular synthon is formed as the bonding part 126.

[0087] The first molecule 122 and the second molecule 124 are nicotinamide (molecular formula C 6 H 6 N 2 O) shown in FIG. 27, and the third molecules 136 and 138 can be succinic acid (molecular formula C 4 H 6 O 4 ) shown in FIG. 28. The first molecule 122 and the second molecule 124 are nicotinamide (see FIG. 27), and the third molecules 136 and 138 may be sebacic acid (molecular formula C 10 H 18 O 4 ) shown in FIG. 29. Also, the first molecule 122 and the second molecule 124 are nicotinamide (see FIG. 27), and the third molecules 136 and 138 may be dodecanedioic acid (molecular formula C 12 H 22 O 4 ) shown in FIG. 30. In these cases, an amide - amide supramolecular synthon is formed as the bonding part 126 by the first molecule 122 and the second molecule 124.

[0088] The first molecule 122 and the second molecule 124 can be isonicotinamide (see FIG. 25), and the third molecules 136 and 138 can be sebacic acid (see FIG. 29). The first molecule 122 and the second molecule 124 can be isonicotinamide (see FIG. 25), and the third molecules 136 and 138 may be dodecanedioic acid (see FIG. 30). Further, the first molecule 122 and the second molecule 124 can be isonicotinamide (see FIG. 25), and the third molecules 136 and 138 may be acetic acid (molecular formula C 2 H 4 O 2 ) shown in FIG. 31. In these cases, an amide - amide supramolecular synthon is formed as the bonding part 126 by the first molecule 122 and the second molecule 124.

[0089] The first molecule 122 and the second molecule 124 can be nicotinamide (see FIG. 27), and the third molecules 136 and 138 can be urea (molecular formula CH 4 N 2 O) shown in FIG. 32. An amide - amide supramolecular synthon is formed as the bonding part 126 by the first molecule 122 and the second molecule 124. The target molecule urea is used as a probe for MRI.

[0090] The highly polarized object according to the second embodiment can be manufactured in the same manner as the highly polarized object 100 (see FIG. 1). That is, a mixture of the first molecule, the second molecule, and the third molecule is heated and melted, a polarization source (see FIGS. 6 and 7) is added to the melted mixture and stirred, and then rapidly cooled. Alternatively, a polarization source (see FIGS. 6 and 7) may be added to a mixture of the first molecule, the second molecule, and the third molecule, and the mixture may be heated and melted and then rapidly cooled. Thereby, similar to the highly polarized object 100, a highly polarized object in which a part of the co - crystal is replaced by a polarization source can be generated. To highly polarize the nuclear spins of the highly polarized object according to the second embodiment, triplet DNP may be performed using the above - described highly polarizing apparatus (see FIG. 20) (see FIG. 23).

[0091] Both the first molecule 122 and the second molecule 124 contain aromatic rings, and the supramolecular synthon formed by the groups of the first molecule 122 and the second molecule 124 is hexagonal. Pentacene (see Fig. 6) or a pentacene derivative (see Fig. 7) used as a polarization source has five benzene rings. Therefore, a part of the components constituting the co-crystal (i.e., the first molecule 122 and the second molecule 124) can be easily replaced by pentacene (see Fig. 6) or a pentacene derivative (see Fig. 7) which is a polarization source. That is, in the process of forming the co-crystal, the polarization source can easily enter the position where the components of the co-crystal are originally arranged. As a result, the nuclear spin of the target molecule which is the object of high polarization by triplet DNP can be highly polarized.

[0092] (Third Embodiment) In the second embodiment, the case where the polarization source is dispersed at the position where two conformer molecules (i.e., the first molecule 122 and the second molecule 124 in Fig. 24) forming the supramolecular synthon are substituted in the co-crystal has been described, but it is not limited thereto. In the third embodiment, in the co-crystal composed of a component containing a supramolecular synthon formed by four molecules including a target molecule and a conformer molecule, the polarization source is dispersed at the position where two conformer molecules are substituted.

[0093] The highly polarizable object according to the third embodiment is a co-crystal, similar to the highly polarizable object 100 shown in FIG. 1, and a part of its components is replaced by a polarization source. Referring to FIG. 33, the co-crystal component 150 of the highly polarizable object according to the third embodiment is composed of first molecules 152a and 152b and second molecules 154a and 154b. The second molecules 154a and 154b are target molecules that are the objects of high polarization of nuclear spins by triplet DNP. The first molecules 152a and 152b are co-former molecules that form a co-crystal together with the target molecules. The first molecules 152a and 152b each have groups 162a and 162b. The second molecules 154a and 154b each have groups 164a and 164b. For a plurality of elements (molecules and groups) with the same name, different alphabets are attached to the end of the symbol to distinguish each element, and the plurality of elements are collectively represented without attaching an alphabet. The groups 162a, 162b, 164a, and 164b are groups (specifically, functional groups) in organic chemistry. The groups 162a, 162b, 164a, and 164b are bonded to form a bonding portion 156. The white circles shown in FIG. 33 represent atoms or atomic groups (nitrogen atoms, hydroxyl groups, carboxylic acids, etc.) that form non-covalent bonds (see dashed lines) such as hydrogen bonds.

[0094] The bonding portion 156 is a supramolecular synthon. Each of the groups 162a, 162b, 164a, and 164b is a carboxyl group or an amide group. For example, the groups 162a and 164a form a supramolecular synthon of acid-amide (see FIG. 5), and the groups 162b and 164b form the same supramolecular synthon as the groups 162a and 164a. Furthermore, a supramolecular synthon of (acid-amide)-(acid-amide) is formed as the bonding portion 156. FIG. 34 shows the chemical formula of the supramolecular synthon of (acid-amide)-(acid-amide).

[0095] The polarization source is, for example, pentacene (see Fig. 6) or a pentacene derivative (see Fig. 7). The polarization source is dispersedly arranged at a position in the co-crystal that replaces an addable site 166 (i.e., the first molecules 152a and 152b) that is part of the co-crystal component 150.

[0096] For example, the first molecule 152 is picolinamide (see Fig. 14), and the second molecule 154 can be pyruvic acid (molecular formula C 3 H 4 O 3 ) shown in Fig. 35. The first molecule 152 may be 4-methylbenzamide (see Fig. 9), and the second molecule 154 may be pyruvic acid (see Fig. 35). The target molecule, pyruvic acid, is utilized as a probe for MRI.

[0097] Also, the first molecule 152 may be mandelic acid (molecular formula C 8 H 8 O 3 ) shown in Fig. 36, and the second molecule 154 may be picolinamide (see Fig. 14).

[0098] (Variant example) In the above, the case where the four molecules constituting the co-crystal component contain two types of molecules has been described, but it is not limited to this. The four molecules constituting the co-crystal component may contain three types of molecules.

[0099] The highly polarizable object according to the modified example is a co-crystal, similar to the highly polarizable object 100 shown in FIG. 1, and a part of its components is replaced by a polarization source. Referring to FIG. 37, the co-crystal component 170 of the highly polarizable object according to the modified example is composed of a first molecule 172a and 172b, a second molecule 174, and a third molecule 176. The second molecule 174 is a target molecule that is the target of the hyperpolarization of the nuclear spin by triplet DNP. The first molecules 172a and 172b and the third molecule 176 are co-former molecules that form a co-crystal together with the target molecule. The first molecules 172a and 172b each have a group 182a and 182b, respectively. The second molecule 174 and the third molecule 176 each have a group 184 and 186, respectively. The groups 182a, 182b, 184, and 186 are groups (specifically, functional groups) in organic chemistry. The groups 182a, 182b, 184, and 186 are bonded to form a bonding part 178. The white circles shown in FIG. 37 represent atoms or atomic groups (such as nitrogen atoms, hydroxyl groups, carboxylic acids, etc.) that form non-covalent bonds (see the dashed lines) such as hydrogen bonds.

[0100] The bonding part 178 is a supramolecular synthon. Each of the groups 182a, 182b, 184, and 186 is a carboxyl group or an amide group. For example, a supramolecular synthon of acid - amide (see FIG. 5) is formed by the groups 182a and 186, and a supramolecular synthon of acid - amide is also formed by the groups 184 and 182b. Furthermore, a supramolecular synthon of (acid - amide)-(acid - amide) (see FIG. 34) is formed as the bonding part 178 by them.

[0101] The polarization source is, for example, pentacene (see FIG. 6) or a pentacene derivative (see FIG. 7). The polarization source is dispersed and arranged at a position in the co-crystal that replaces an addable site 188 (that is, the first molecule 172a and the third molecule 176), which is a part of the co-crystal component 170.

[0102] For example, the first molecule 172 is picolinamide (see FIG. 14), the third molecule 176 is salicylic acid (see FIG. 12), and the second molecule 174 (target molecule) is pyruvic acid (see FIG. 35). The first molecule 172 may be picolinamide, the third molecule 176 may be 4-chlorosalicylic acid shown in FIG. 38, and the second molecule 174 (target molecule) may be pyruvic acid. Further, the first molecule 172 may be 4-methylbenzamide (see FIG. 9), the third molecule 176 may be benzoic acid (see FIGS. 8 and 10), and the second molecule 174 (target molecule) may be pyruvic acid. Pyruvic acid, which is the target molecule, is used as a probe for MRI.

[0103] When the first molecule 172 is picolinamide (see FIG. 14) and the third molecule 176 is salicylic acid (see FIG. 12), the second molecule 174 (target molecule) may be acetic acid (see FIG. 31) or formic acid (molecular formula CH 2 O 2 ) shown in FIG. 39. Acetic acid, which is the target molecule, is used as a probe for MRI.

[0104] The highly polarized object according to the third embodiment and its modified example can also be manufactured in the same manner as the highly polarized object 100 (see FIG. 1). That is, the first molecule and the second molecule, or a mixture of the first molecule to the third molecule is heated and melted, a polarization source (see FIGS. 6 and 7) is added to the melted mixture and stirred, and then rapidly cooled. Alternatively, a polarization source (see FIGS. 6 and 7) may be added to the mixture of the first molecule and the second molecule, or the mixture of the first molecule to the third molecule, and the mixture may be heated and melted and then rapidly cooled. Thereby, similar to the highly polarized object 100, a highly polarized object in which a part of the co-crystal is replaced by a polarization source can be generated. To highly polarize the nuclear spin of the highly polarized object according to the third embodiment and its modified example, triplet DNP may be performed using the above-described highly polarizing device (see FIG. 20) (see FIG. 23).

[0105] A part of the components constituting the co-crystal, that is, the first molecules 152a and 152b in the third embodiment and the first molecule 172a and the third molecule 176 in the modification example, can be easily replaced by pentacene (see FIG. 6) or a pentacene derivative (see FIG. 7) which is a polarization source. That is, in the process of forming the co-crystal, the polarization source can easily enter the position where the components of the co-crystal are originally arranged. As a result, the nuclear spin of the target molecule which is a highly polarized object by triplet DNP can be highly polarized.

Example

[0106] The experimental results are shown below to demonstrate the effectiveness of the present invention. As described above, a highly polarized object was generated, and triplet DNP was performed using the highly polarized device shown in FIG. 20.

[0107] (Highly polarized object 1) As described above in the first embodiment, a highly polarized object of a co-crystal in which benzoic acid (see FIG. 8) and 4-methylbenzamide (see FIG. 9) have a molar ratio of 1:1 and pentacene is added at 0.06 mol% with respect to the whole was synthesized. The synthesized highly polarized object was highly polarized by triplet DNP, and the observed NMR signal (the signal obtained by Fourier-transforming the FID signal) is shown in FIG. 40. With the repetition frequency of the sequence of laser light irradiation, microwave irradiation, and sweeping magnetic field application shown in FIG. 23 being 50 Hz, triplet DNP was performed for 90 seconds. In FIG. 40, the signal indicated by reference sign A shows the NMR signal observed after performing triplet DNP, and the signal indicated by reference sign B shows the NMR signal observed without performing triplet DNP. Comparing these, it can be seen that the synthesized highly polarized object was highly polarized by performing triplet DNP. A polarization rate P of 0.041% was achieved. The amplification factor with respect to the thermal equilibrium state (see reference sign B) was 310 times. The longitudinal relaxation time was 140 seconds, and a sufficiently long time was realized.

[0108] (Highly polarized object 2) As described above in the first embodiment, a highly polarized object of a co-crystal in which salicylic acid (see Fig. 12) and benzamide (see Fig. 13) have a molar ratio of 1:1 and pentacene is added at 0.06 mol% with respect to the whole was synthesized. The synthesized highly polarized object was highly polarized by triplet DNP, and the observed NMR signal (the signal obtained by Fourier-transforming the FID signal) is shown in Fig. 41. In the same manner as above, the repetition frequency of the sequence was set to 50 Hz, and triplet DNP was performed for 420 seconds. In Fig. 41, the meanings of reference signs A and B are the same as those in Fig. 40. By comparing these, it can be seen that the synthesized highly polarized object was highly polarized by performing triplet DNP. A polarization rate P of 0.146% was achieved. The amplification factor with respect to the thermal equilibrium state (see reference sign B) was 1095 times. The longitudinal relaxation time was 411.6 seconds, and a sufficiently long time was realized.

[0109] (Highly polarized object 3) As described above in the first embodiment, a highly polarized object of a co-crystal in which salicylic acid (see Fig. 12) and picolinamide (see Fig. 14) have a molar ratio of 1:1 and pentacene is added at 0.06 mol% with respect to the whole was synthesized. The synthesized highly polarized object was highly polarized by triplet DNP, and the observed NMR signal (the signal obtained by Fourier-transforming the FID signal) is shown in Fig. 42. In the same manner as above, the repetition frequency of the sequence was set to 50 Hz, and triplet DNP was performed for 420 seconds. In Fig. 42, the meanings of reference signs A and B are the same as those in Fig. 40. By comparing these, it can be seen that the synthesized highly polarized object was highly polarized by performing triplet DNP. A polarization rate P of 0.093% was achieved. The amplification factor with respect to the thermal equilibrium state was 700 times. The longitudinal relaxation time was 180 seconds, and a sufficiently long time was realized.

[0110] (Highly polarized object 4) As described above in the first embodiment, a highly polarized object of a co-crystal in which salicylic acid (see Fig. 12) and salicylamide (see Fig. 11) have a molar ratio of 1:1 and pentacene is added at 0.06 mol% with respect to the whole thereof was synthesized. The synthesized highly polarized object was highly polarized by triplet DNP, and the observed NMR signal (a signal obtained by Fourier-transforming the FID signal) is shown in Fig. 43. Similar to the above, with the repetition frequency of the sequence being 50 Hz, triplet DNP was performed for 420 seconds. In Fig. 43, the meanings of reference signs A and B are the same as those in Fig. 40. Comparing these, it can be seen that the synthesized highly polarized object was highly polarized by performing triplet DNP. A polarization rate P of 0.349% was achieved. The amplification factor with respect to the thermal equilibrium state was 2621 times. The longitudinal relaxation time was 303.9 seconds, and a sufficiently long time was realized.

[0111] (Highly polarized object 5) As described above in the first embodiment, a highly polarized object of a co-crystal in which 3-nitrobenzoic acid (see Fig. 15) and benzamide (see Fig. 13) have a molar ratio of 1:1 and pentacene is added at 0.06 mol% with respect to the whole thereof was synthesized. The synthesized highly polarized object was highly polarized by triplet DNP, and the observed NMR signal (a signal obtained by Fourier-transforming the FID signal) is shown in Fig. 44. Similar to the above, with the repetition frequency of the sequence being 50 Hz, triplet DNP was performed for 420 seconds. In Fig. 44, the meanings of reference signs A and B are the same as those in Fig. 40. Comparing these, it can be seen that the synthesized highly polarized object was highly polarized by performing triplet DNP. A polarization rate P of 0.015% was achieved. The amplification factor with respect to the thermal equilibrium state was 115 times. The longitudinal relaxation time was 43.5 seconds, and a sufficiently long time was realized.

[0112] (Highly polarized object 6) As described above in the second embodiment, a highly polarized object of a co-crystal in which nicotinamide (see Fig. 27) and succinic acid (see Fig. 28) have a molar ratio of 2:1 and pentacene is added at 0.06 mol% with respect to the whole was synthesized. The synthesized highly polarized object was highly polarized by triplet DNP, and the observed NMR signal (a signal obtained by Fourier-transforming the FID signal) is shown in Fig. 45. With the repetition frequency of the sequence shown in Fig. 23 being 100 Hz, triplet DNP was performed for 90 seconds. In Fig. 45, the meanings of reference signs A and B are the same as those in Fig. 40. Comparing these, it can be seen that the synthesized highly polarized object was highly polarized by performing triplet DNP. A polarization rate P of 0.0079% was achieved. The amplification factor with respect to the thermal equilibrium state was 60 times.

[0113] (Highly polarized object 7) As described above in the second embodiment, a highly polarized object of a co-crystal in which nicotinamide (see Fig. 29) and sebacic acid (see Fig. 29) have a molar ratio of 2:1 and pentacene is added at 0.06 mol% with respect to the whole was synthesized. The synthesized highly polarized object was highly polarized by triplet DNP, and the observed NMR signal (a signal obtained by Fourier-transforming the FID signal) is shown in Fig. 46. With the repetition frequency of the sequence shown in Fig. 23 being 200 Hz, triplet DNP was performed for 90 seconds. In Fig. 46, the meanings of reference signs A and B are the same as those in Fig. 40. Comparing these, it can be seen that the synthesized highly polarized object was highly polarized by performing triplet DNP. A polarization rate P of 0.00405% was achieved. The amplification factor with respect to the thermal equilibrium state was 30 times.

[0114] (Highly polarized object 8) As described above in the second embodiment, a co-crystal hyperpolarization target was synthesized in which isonicotinamide (see Fig. 16) and dodecanedioic acid (see Fig. 30) had a molar ratio of 2:1, and pentacene was added at 0.06 mol% with respect to the whole. The synthesized hyperpolarization target was hyperpolarized by triplet DNP, and the observed NMR signal (the signal obtained by Fourier-transforming the FID signal) is shown in Fig. 47. With the repetition frequency of the sequence shown in Fig. 23 set to 100 Hz, triplet DNP was performed for 120 seconds. In Fig. 47, the meanings of reference signs A and B are the same as those in Fig. 40. By comparing these, it can be seen that the synthesized hyperpolarization target was hyperpolarized by performing triplet DNP. A polarization rate P of 0.00685% was achieved. The amplification factor with respect to the thermal equilibrium state was 51.4 times. The longitudinal relaxation time was 26.1 seconds, and a sufficiently long time was realized.

[0115] (Hyperpolarization target 9) As described above in the second embodiment, a co-crystal hyperpolarization target was synthesized in which urea (see Fig. 32) and nicotinamide (see Fig. 27) had a molar ratio of 1:2, and pentacene was added at 0.06 mol% with respect to the whole. The synthesized hyperpolarization target was hyperpolarized by triplet DNP, and the observed NMR signal (the signal obtained by Fourier-transforming the FID signal) is shown in Fig. 48. With the repetition frequency of the sequence set to 100 Hz as above, triplet DNP was performed for 120 seconds. In Fig. 48, the meanings of reference signs A and B are the same as those in Fig. 40. By comparing these, it can be seen that the synthesized hyperpolarization target was hyperpolarized by performing triplet DNP. A polarization rate P of 0.0135% was achieved. The amplification factor with respect to the thermal equilibrium state was 101 times. The longitudinal relaxation time was 10 seconds, and a sufficiently long time was realized.

[0116] (Hyperpolarization target 10) As described above in the second embodiment, a co-crystalline highly polarizable object was synthesized in which pyruvic acid (see Fig. 35), salicylic acid (see Fig. 12), and picolinamide (see Fig. 14) were in a molar ratio of 1:1:2, and pentacene was added at 0.06 mol% with respect to the whole. The synthesized highly polarizable object was highly polarized by triplet DNP, and the observed NMR signal (the signal obtained by Fourier-transforming the FID signal) is shown in Fig. 49. With the repetition frequency of the sequence shown in Fig. 23 set to 200 Hz, triplet DNP was performed for 90 seconds. In Fig. 49, the meanings of reference signs A and B are the same as those in Fig. 40. By comparing these, it can be seen that the synthesized highly polarizable object was highly polarized by performing triplet DNP. A polarization rate P of 0.024% was achieved. The amplification factor with respect to the thermal equilibrium state was 200 times. The longitudinal relaxation time was 67.8 seconds, realizing a sufficiently long time.

[0117] (Highly Polarizable Object 11) As described above in the third embodiment, a co-crystalline highly polarizable object was synthesized in which pyruvic acid (see Fig. 35) and picolinamide (see Fig. 14) were in a stoichiometric ratio of 1:1, and pentacene was added at 0.06 mol% with respect to the whole. The synthesized highly polarizable object was highly polarized by triplet DNP, and the observed NMR signal (the signal obtained by Fourier-transforming the FID signal) is shown in Fig. 50. With the repetition frequency of the sequence shown in Fig. 23 set to 50 Hz, triplet DNP was performed for 90 seconds. In Fig. 50, the meanings of reference signs A and B are the same as those in Fig. 40. By comparing these, it can be seen that the synthesized highly polarizable object was highly polarized by performing triplet DNP. A polarization rate P of 0.076% was achieved. The amplification factor with respect to the thermal equilibrium state was 57 times.

[0118] (Highly Polarizable Object 12) As described above in the third embodiment, a highly polarized object of a co-crystal was synthesized in which pyruvic acid (see Fig. 35) and 4-methylbenzamide (see Fig. 9) were in a stoichiometric ratio of 1:1, and pentacene was added at 0.06 mol% with respect to the whole. The synthesized highly polarized object was highly polarized by triplet DNP, and the observed NMR signal (the signal obtained by Fourier-transforming the FID signal) is shown in Fig. 51. With the repetition frequency of the sequence shown in Fig. 23 being 200 Hz, triplet DNP was performed for 90 seconds. In Fig. 51, the meanings of reference signs A and B are the same as those in Fig. 40. Comparing these, it can be seen that the synthesized highly polarized object was highly polarized by performing triplet DNP. A polarization rate P of 0.00487% was achieved. The amplification factor with respect to the thermal equilibrium state was 36.6 times. The longitudinal relaxation time was 30.5 seconds, and a sufficiently long time was realized.

[0119] The present invention has been described by explaining the embodiments above. However, the above-described embodiments are merely examples, and the present invention is not limited only to the above-described embodiments. The scope of the present disclosure is indicated by each claim in the claims, taking into consideration the description in the detailed description of the invention, and includes all modifications within the meaning and scope equivalent to the language described therein.

Explanation of Reference Signs

[0120] 100 Highly polarized object 102, 122, 152a, 152b, 172a, 172b First molecule 104, 124, 154a, 154b, 174 Second molecule 106, 126, 156, 178 Binding part 108 Polarization source 110, 120, 150, 170 Co-crystal component 112, 114, 132, 134, 162a, 162b, 164a, 164b, 182a, 182b, 184, 186 Group 136, 138, 176 Third molecule 166, 188 Addable site 300 Highly polarizing device 302 Main magnetic field forming section 304 Cavity 306 Sample 308 Laser light source 310 Microwave source 312 Amplifying section 314 Sweeping magnetic field forming section 316 Power supply section 318 NMR signal detection section 320 NMR analysis section 322 Control section 330 Optical transmission section 332 Condensing section 334 Waveguide 336 Sample housing section 338 Solvent supply section 350 Solvent

Claims

1. comprising a first molecule, a second molecule, and a polarization source, wherein at least one of the first molecule and the second molecule is a target molecule to be highly polarized in nuclear spin by triplet DNP, among the first molecule and the second molecule, the molecule that is not the target molecule is a co-former molecule, the first molecule and the second molecule constitute a crystal structure of a co-crystal containing a supramolecular synthon having a hexagonal structure, the polarization source is a highly polarized object disposed at a position substituting a part of the crystal structure.

2. The highly polarized object according to claim 1, wherein the supramolecular synthon includes an acid-acid, acid-amide, or amide-amide supramolecular synthon.

3. The highly polarized object according to claim 1 or claim 2, wherein the target molecule is benzoic acid, salicylic acid, 3-nitrobenzoic acid, pentafluorobenzoic acid, isonicotinamide, 4-methylbenzamide, salicylamide, benzamide, picolinamide, aspirin, or ethenzamide.

4. The supramolecular synthon is an acid-amide supramolecular synthon, The highly polarized object according to claim 3, wherein the combination of the first molecule and the second molecule is any one of salicylic acid and benzamide, salicylic acid and picolinamide, or 3-nitrobenzoic acid and benzamide.

5. The highly polarized object according to claim 3, wherein the combination of the first molecule and the second molecule is salicylic acid and salicylamide.

6. The highly polarized object according to claim 3, wherein the combination of the first molecule and the second molecule is a combination of benzoic acid and 4-methylbenzamide, salicylamide, or pentafluorobenzoic acid.

7. the target molecule is aspirin, the co-former molecule is pentafluorobenzoic acid, or the target molecule is ethenzamide, The highly polarized object according to claim 3, wherein the co-former molecule is pentafluorobenzoic acid, 3-nitrobenzoic acid, or salicylic acid.

8. comprising a first co-former molecule, a second co-former molecule, a target molecule to be highly polarized in nuclear spin by triplet DNP, and a polarization source, the first co-former molecule and the second co-former molecule constitute a crystal structure of a co-crystal containing a supramolecular synthon having a hexagonal structure, The target molecule is bound to the first coform molecule and the second coform molecule, or the first coform molecule, by intermolecular forces, The polarization source is a highly polarizable object disposed at a position substituting a part of the crystal structure. **Claim 9** The supramolecular synthon of the highly polarizable object according to claim 8 includes an acid-acid, acid-amide, or amide-amide supramolecular synthon. **Claim 10** The target molecule of the highly polarizable object according to claim 8 or claim 9 is benzoic acid, salicylic acid, picolinic acid, acetic acid, succinic acid, sebacic acid, dodecanedioic acid, pyruvic acid, formic acid, or urea. **Claim 11** The supramolecular synthon is an amide-amide supramolecular synthon, The first coform molecule and the second coform molecule are isonicotinamide, The target molecule of the highly polarizable object according to claim 10 is benzoic acid, salicylic acid, or picolinic acid. **Claim 12** The supramolecular synthon is an amide-amide supramolecular synthon, The first coform molecule and the second coform molecule are nicotinamide, The target molecule of the highly polarizable object according to claim 10 is succinic acid, sebacic acid, or dodecanedioic acid. **Claim 13** The supramolecular synthon is an amide-amide supramolecular synthon, The first coform molecule and the second coform molecule are isonicotinamide, The target molecule of the highly polarizable object according to claim 10 is sebacic acid, dodecanedioic acid, or acetic acid. **Claim 14** The supramolecular synthon is an amide-amide supramolecular synthon, The first coform molecule and the second coform molecule are nicotinamide, The target molecule of the highly polarizable object according to claim 10 is urea. **Claim 15** The first molecule is the coform molecule, The second molecule is the target molecule, An acid-amide supramolecular synthon is formed by the first molecule and the second molecule, A (acid-amide)-(acid-amide) supramolecular synthon is further formed by two of the first molecules and two of the second molecules. The polarization source is arranged at a position in the co-crystal that replaces two of the first molecules that form a part of the supramolecular synthons of a plurality of (acid - amide)-(acid - amide), the highly polarized object according to claim 1 or claim 2.

16. The co-former molecule is picolinamide or 4-methylbenzamide, The target molecule is pyruvic acid, the highly polarized object according to claim 15.

17. The co-former molecule is picolinamide, The target molecule is mandelic acid, the highly polarized object according to claim 15.

18. Further comprising a third molecule, The first molecule and the third molecule are the co-former molecules, The second molecule is the target molecule, An acid - amide supramolecular synthon is formed by the first molecule and the second molecule, An acid - amide supramolecular synthon is formed by the first molecule and the third molecule, A further (acid - amide)-(acid - amide) supramolecular synthon is formed by two of the first molecules, one of the second molecules and one of the third molecules, The polarization source is arranged at a position in the co-crystal that replaces the first molecule and the third molecule that form a part of the supramolecular synthons of a plurality of (acid - amide)-(acid - amide), the highly polarized object according to claim 1 or claim 2.

19. The first molecule is picolinamide, The third molecule is salicylic acid, The target molecule is pyruvic acid, acetic acid or formic acid, the highly polarized object according to claim 18.

20. The first molecule is picolinamide, The third molecule is 4-chlorosalicylic acid, The target molecule is pyruvic acid, the highly polarized object according to claim 18.

21. The first molecule is 4-methylbenzamide, The third molecule is benzoic acid, The target molecule is pyruvic acid, the highly polarized object according to claim 18.

22. A step of generating a molten mixture containing a first molecule, a second molecule and a polarization source by heating, and A cooling step of cooling the molten mixture. At least one of the first molecule and the second molecule is a target molecule to be hyperpolarized in nuclear spin by triplet DNP, Among the first molecule and the second molecule, the molecule that is not the target molecule is a co-former molecule, By the cooling step, The first molecule and the second molecule constitute a crystal structure of a co-crystal containing a supramolecular synthon having a hexagonal structure, The polarization source is arranged at a position substituting a part of the crystal structure, a method for producing a hyperpolarized object.

23. Generating a molten mixture including a first co-former molecule, a second co-former molecule, a target molecule to be hyperpolarized in nuclear spin by triplet DNP, and a polarization source; A cooling step of cooling the molten mixture, By the cooling step, The first co-former molecule and the second co-former molecule constitute a crystal structure of a co-crystal containing a supramolecular synthon having a hexagonal structure, The target molecule is bonded to the first co-former molecule and the second co-former molecule or the first co-former molecule by intermolecular force, The polarization source is arranged at a position substituting a part of the crystal structure, a method for producing a hyperpolarized object.

24. A light irradiation step of irradiating light to a sample arranged in a space where a uniform static magnetic field is formed; Subsequent to the light irradiation step, a microwave irradiation step of irradiating the sample with microwaves while applying a sweeping magnetic field to the sample, The sample includes the hyperpolarized object according to any one of claims 1, 2, 8, and 9, After repeating the light irradiation step and the microwave irradiation step, a dissolution step of dissolving the target molecule in the sample to generate a solution is further included, a method for hyperpolarizing nuclear spin.

25. An apparatus for hyperpolarizing nuclear spin in a sample by triplet DNP, A magnetic field forming unit for forming a static magnetic field; A light irradiation unit for irradiating light to the sample arranged in the region where the static magnetic field is formed; A microwave irradiation unit for irradiating the sample arranged in the region where the static magnetic field is formed with microwave pulses; A control unit for controlling the light irradiation unit and the microwave irradiation unit, The sample includes the hyperpolarized object according to any one of claims 1, 2, 8, and 9, The control unit controls the light irradiation unit and the microwave irradiation unit to highly polarize the nuclear spins in the highly polarizable object by triplet DNP, which is a nuclear spin high polarization device.

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