CN112542306A - Strong paramagnetic material based on monovalent metal ions, preparation method and application thereof - Google Patents

Strong paramagnetic material based on monovalent metal ions, preparation method and application thereof Download PDF

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CN112542306A
CN112542306A CN202011502961.4A CN202011502961A CN112542306A CN 112542306 A CN112542306 A CN 112542306A CN 202011502961 A CN202011502961 A CN 202011502961A CN 112542306 A CN112542306 A CN 112542306A
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monovalent metal
aromatic ring
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metal ions
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CN112542306B (en
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方海平
杨海军
张欣
张峰
盛世奇
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Wenzhou Research Institute Of Chinese Academy Of Sciences Wenzhou Institute Of Biomaterials And Engineering
East China University of Science and Technology
Shanghai Advanced Research Institute of CAS
Hefei Institutes of Physical Science of CAS
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Wenzhou Research Institute Of Chinese Academy Of Sciences Wenzhou Institute Of Biomaterials And Engineering
East China University of Science and Technology
Shanghai Advanced Research Institute of CAS
Hefei Institutes of Physical Science of CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0018Diamagnetic or paramagnetic materials, i.e. materials with low susceptibility and no hysteresis

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Abstract

The invention provides a preparation method of a strong paramagnetic material based on monovalent metal ions, which comprises the following steps: and mixing the substance containing aromatic rings with the solution containing monovalent metal ions to obtain the strongly paramagnetic material. Compared with the prior art, the invention forms variable charges on the compound based on the ion-pi interaction between the aromatic ring and the univalent metal cation, and the variable charges can stably exist at normal temperature, thereby obtaining the strong paramagnetic material with super-strong paramagnetism at normal temperature; the preparation method has wide raw material sources, a molecular structure can be designed, a self-assembly structure can be regulated, the use of ferromagnetic substances is effectively avoided, the retention of inorganic magnetic particles in vivo and toxicity risks caused by the retention are avoided, and the biocompatibility is good; meanwhile, the magnetic material has super-strong paramagnetism in monovalent ion solution with physiological concentration, and can be widely applied to the fields of magnetic targeting drugs, nuclear magnetic resonance imaging, magnetic transfection and the like.

Description

Strong paramagnetic material based on monovalent metal ions, preparation method and application thereof
Technical Field
The invention belongs to the technical field of magnetic materials, and particularly relates to a strong paramagnetic material based on monovalent metal ions, and a preparation method and application thereof.
Background
Magnetic materials are widely used in scientific technology of production, life and national defense. The conventional magnetic materials are mainly inorganic substances (such as ferrite) or composite magnetic materials mainly made of inorganic substances, and contain a large amount of ferromagnetic substances (iron, cobalt and nickel), and the magnetic materials are difficult to degrade in vivo or degradation/oxidation products have toxicity, so that research on novel magnetic materials is more and more.
Chinese patent publication No. CN111662450A discloses an organic magnetic polymer material and a preparation method thereof, the material is a polymer network structure using thiazole [5, 4-d ] thiazole as a bridge, wherein 1, 3, 5-s-triphenyl phenol is partially or completely dehydrogenated to generate free radicals, the free radicals alone form local polarization to generate magnetic moments, but have magnetic characteristics only at low temperature (<100 k).
Chinese patent with publication number CN110627835A discloses a water-soluble paramagnetic fullerene-metal nano complex and a preparation method and application thereof, wherein a multi-arm side chain short straight carbon chain contains N, O or branched chains, the tail ends of the multi-arm side chain short straight carbon chain contain hydrophilic groups, and a water-soluble fullerene nitrene derivative capable of providing multi-tooth coordination points can be directly chelated with paramagnetic metal ions, so that the complex has a remarkable MRI image enhancement effect when used as a carbon-based MRI nanoprobe for radiography, has an important application prospect in the technical field of nano diagnosis and treatment, but the normal-temperature paramagnetism of the complex still needs to be enhanced.
In the current normal-temperature paramagnetic organic materials, paramagnetic divalent or polyvalent metal ions are basically contained, wherein most heavy metal ions can have adverse effects on the environment and human health.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a paramagnetic material based on monovalent metal ions, which has super paramagnetism at room temperature, and a preparation method and an application thereof.
The invention provides a preparation method of a strong paramagnetic material based on monovalent metal ions, which comprises the following steps:
and mixing the substance containing aromatic rings with the solution containing monovalent metal ions to obtain the strongly paramagnetic material.
Preferably, the aromatic ring in the aromatic ring-containing substance comprises one or more of benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrimidine, pyrrole, furan, thiophene, imidazole, indole, purine and derivative structures of the substances; the ratio of the aromatic ring-containing substance to the monovalent metal ion is (0.1 to 10) mg: (0.01 to 4000) mmol.
Preferably, the aromatic ring-containing substance is one or more of organic small molecules, organic macromolecules and biomolecules; the biological molecules are one or more of amino acids, polypeptides, proteins, DNA and RNA; the monovalent metal ion is preferably Li+、Na+、K+、Rb+、Cs+With Ag+One or more of (a).
Preferably, the aromatic ring-containing material is selected from one or more of tyrosine, phenylalanine, tyrosine and/or phenylalanine-containing polypeptides, pyrrole, indole, pyridine, bipyridine and imidazole.
Preferably, the method comprises the following steps:
mixing the substance containing aromatic rings with a solvent to obtain a solution of the substance containing aromatic rings;
and mixing the solution of the substance containing the aromatic ring with a solution containing monovalent metal ions to obtain the strongly paramagnetic material.
Preferably, the solution of the aromatic ring-containing substance is left to stand for self-assembly and then mixed with the solution containing monovalent metal ions; the standing temperature is 5-90 ℃; the standing time is 3-10 days.
Preferably, the solvent is one or more of water, ethanol, dimethyl sulfoxide and N-methyl pyrrolidone;
the ratio of the aromatic ring-containing substance to the solvent is (1-10) mg: 10 ml.
Preferably, the concentration of the monovalent metal ions in the solution containing the monovalent metal ions is 100-1000 mM; the volume ratio of the solution of the self-assembled structured matter to the solution containing the monovalent metal ion is 1: (0.5-2).
The invention also provides a strong paramagnetic material based on the monovalent metal ions, which is prepared by the preparation method.
The invention also provides application of the strong paramagnetic material based on the monovalent metal ions prepared by the preparation method in preparation of magnetic targeting therapeutic drugs, micro-control medical instruments and surgical robots.
The invention provides a preparation method of a strong paramagnetic material based on monovalent metal ions, which comprises the following steps: and mixing the substance containing aromatic rings with the solution containing monovalent metal ions to obtain the strongly paramagnetic material. Compared with the prior art, the invention forms variable charges on the compound based on the ion-pi interaction between the aromatic ring and the univalent metal cation, and the variable charges can stably exist at normal temperature, thereby obtaining the strong paramagnetic material with super-strong paramagnetism at normal temperature; the preparation method has wide raw material sources, a molecular structure can be designed, a self-assembly structure can be regulated, the use of ferromagnetic substances is effectively avoided, the retention of inorganic magnetic particles in vivo and toxicity risks caused by the retention are avoided, and the biocompatibility is good; meanwhile, the magnetic material has super-strong paramagnetism in monovalent ion solution with physiological concentration, and can be widely applied to the fields of magnetic targeting drugs, nuclear magnetic resonance imaging, magnetic transfection and the like.
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FIG. 1 is a photograph of AYFF in example 1 of the present invention just after mixing with a 300mM NaCl solution;
FIG. 2 is a photograph of AYFFF mixed with 300mM NaCl solution for 2 minutes and applied with 0.5T magnetic field in example 1 of the present invention;
FIG. 3 is a photograph of AYFFF and 300mM NaCl solution placed under a 0.5T magnetic field for 10 minutes in example 1 of the present invention;
FIG. 4 is a photograph of AYFFF and 300mM NaCl solution placed under a 0.5T magnetic field for 30 minutes in example 1 of the present invention;
FIG. 5 is a photograph of AYFFF of comparative example 4 of the present invention just after mixing with an equal volume of water;
FIG. 6 is a photograph of AYFFF mixed with water in equal volume for 2 minutes in comparative example 4 of the present invention, and a 0.5T magnetic field was applied;
FIG. 7 is a photograph of AYFFF mixed with water in equal volume in comparative example 4 of the present invention, which was left under a 0.5T magnetic field for 10 minutes;
FIG. 8 is a photograph of AYFFF of comparative example 4 of the present invention, which was mixed with water in equal volume and then left under a 0.5T magnetic field for 30 minutes.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a strong paramagnetic material based on monovalent metal ions, which comprises the following steps: and mixing the substance containing aromatic rings with the solution containing monovalent metal ions to obtain the strongly paramagnetic material.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
Mixing an aromatic ring-containing substance with a solution containing monovalent metal ions; the aromatic ring of the aromatic ring-containing substance preferably includes benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrimidine, pyrrole, furan, thiophene, imidazole, indole, purine and the likeOne or more of a derivative structure; the aromatic ring-containing substance is preferably one or more of organic small molecules, organic macromolecules and biomolecules; the biomolecule is preferably one or more of amino acid, polypeptide, protein, DNA and RNA; in the present invention, the aromatic ring-containing substance is most preferably one or more of tyrosine, phenylalanine, tyrosine and/or phenylalanine-containing polypeptides, pyrrole, indole, pyridine, bipyridine and imidazole; the polypeptide containing tyrosine and/or phenylalanine is preferably one or more of two-octapeptide, more preferably the polypeptide shown in formula (I) and/or the polypeptide shown in formula (II); the monovalent metal ion is preferably Li+、Na+、K+、Rb+、Cs+With Ag+One or more of; the solution of monovalent metal ions is preferably obtained by dissolving a salt of monovalent metal ions in water; the salt of the monovalent metal ion is preferably one or more of a halide salt, a nitrate salt, a phosphate salt and a sulfate salt; the ratio of the aromatic ring-containing substance to the monovalent metal ion is preferably (0.1 to 2) mg: (0.01 to 4000) mmol, more preferably (0.1 to 2) mg: (0.01 to 400) mmol, and preferably (0.1 to 2) mg: (0.01 to 40) mmol, and preferably (0.1 to 2) mg: (0.1 to 10) mmol, most preferably (0.1 to 2) mg: (0.15-1) mmol; in some embodiments provided herein, the ratio of aromatic ring-containing material to monovalent metal ion is preferably 0.5 mg: 0.3 mmol; in some embodiments provided herein, the ratio of aromatic ring-containing material to monovalent metal ion is preferably 0.5 mg: 0.6 mmol; in some embodiments provided herein, the ratio of aromatic ring-containing material to monovalent metal ion is preferably 0.5 mg: 0.24 mmol; in some embodiments provided herein, the ratio of aromatic ring-containing material to monovalent metal ion is preferably 0.3 mg: 0.5 mmol; in some embodiments provided herein, the ratio of aromatic ring-containing material to monovalent metal ion is preferably 2 mg: 0.15 mmol; in some embodiments provided herein, the ratio of aromatic ring-containing material to monovalent metal ion is preferably 0.2 mg: 1mmol of the active component; in other embodiments of the inventionThe ratio of the aromatic ring-containing substance to the monovalent metal ion is preferably 0.1 mg: 0.3 mmol.
Figure BDA0002844143500000051
In the present invention, it is preferable that the aromatic ring-containing substance is mixed with a solvent to obtain a solution of the aromatic ring-containing substance, and then the solution of the aromatic ring-containing substance is mixed with a solution containing a monovalent metal ion; the solvent is a solvent for partially dissolving the aromatic ring-containing substances, and the aromatic ring-containing substances and the monovalent metal ions can be better compounded when the solvent is dissolved in the solvent; the solvent can be water or an organic solvent, and in the invention, one or more of water, ethanol, dimethyl sulfoxide and N-methylpyrrolidone are preferred; the ratio of the aromatic ring-containing substance to the solvent is preferably (1 to 10) mg: 10 ml; in some embodiments provided herein, the ratio of aromatic ring-containing material to solvent is preferably 5 mg: 10 ml; in some embodiments provided herein, the ratio of aromatic ring-containing material to solvent is preferably 10 mg: 10 ml; in some embodiments provided herein, the ratio of aromatic ring-containing material to solvent is preferably 2 mg: 10 ml; in some embodiments provided herein, the ratio of aromatic ring-containing material to solvent is preferably 3 mg: 10 ml; in other embodiments provided herein, the ratio of aromatic ring-containing material to solvent is preferably 1 mg: 10 ml; the concentration of the monovalent metal ions in the solution containing the monovalent metal ions is preferably 100 to 1000mM, more preferably 200 to 800mM, and still more preferably 240 to 600 mM; the volume ratio of the solution of the substance having a self-assembled structure to the solution containing the monovalent metal ion is preferably 1: (0.5 to 2), more preferably 1: (0.8 to 1.5), and more preferably 1: 1; the mixing is preferably by shaking, mixing and blending.
According to the invention, the aromatic ring-containing substance is preferably self-assembled and then mixed with a solution containing monovalent metal ions. The self-assembly step is preferably as follows: mixing the substance containing aromatic rings with a solvent to obtain a solution of the substance containing aromatic rings; the solution of the aromatic ring-containing substance is allowed to stand and then mixed with a solution containing monovalent metal ions. The solution of the aromatic ring-containing substance is the same as described above and is not described in detail herein; the temperature of the standing is preferably 5-90 ℃; in some embodiments provided herein, the temperature of the resting is preferably 5 ℃; in some embodiments provided herein, the temperature of the resting is preferably 20 ℃; in some embodiments provided herein, the temperature of the resting is preferably 30 ℃; in some embodiments provided herein, the temperature of the resting is preferably 45 ℃; in some embodiments provided herein, the temperature of the resting is preferably 60 ℃; in some embodiments provided herein, the temperature of the resting is preferably 90 ℃; the standing time is preferably 3-10 days, and more preferably 3-5 days.
After mixing, the obtained material is clarified liquid, suspension or supernatant and precipitate according to different raw materials.
After mixing, preferably, the method also comprises post-treatment and purification to obtain a strong paramagnetic material; the post-treatment step preferably comprises one or more of standing, filtering, centrifuging and freeze-drying; the standing time is preferably 5 min-5 h.
The invention is based on the ion-pi interaction between aromatic ring and univalent metal cation, so that variable charges are formed on the compound, and the variable charges can stably exist at normal temperature, thereby obtaining the strong paramagnetic material with super-strong paramagnetism at normal temperature; the preparation method has wide raw material sources, a molecular structure can be designed, a self-assembly structure can be regulated, the use of ferromagnetic substances is effectively avoided, the retention of inorganic magnetic particles in vivo and toxicity risks caused by the retention are avoided, and the biocompatibility is good; meanwhile, the magnetic material has super-strong paramagnetism in monovalent ion solution with physiological concentration, and can be widely applied to the fields of magnetic targeting drugs, nuclear magnetic resonance imaging, magnetic transfection and the like.
The invention also provides a strong paramagnetic material based on the monovalent metal ions, which is prepared by the preparation method.
The mass magnetic susceptibility of the strongly paramagnetic material is preferably 5 × 10 or more-6More preferably not less than 5.17X 10-6
The invention also provides application of the univalent metal ion-based strong paramagnetic material prepared by the preparation method in preparation of magnetic targeting therapeutic drugs, micro-control medical instruments and surgical robots.
The invention prepares the strong paramagnetic material by compounding monovalent metal ions existing in human bodies and substances containing aromatic rings, particularly biomolecules containing aromatic rings, can be used as a carrier of magnetic targeting therapeutic drugs, has good biocompatibility, is easy to degrade and metabolize in vivo, avoids the use of ferromagnetic particles, avoids the toxicity risk caused by the retention of inorganic magnetic particles in vivo, and simultaneously has easy design of molecular structure, thereby playing more important role in basic research and clinical practice.
In order to further illustrate the present invention, the following describes a strongly paramagnetic material based on monovalent metal ions and a method for preparing the same in detail with reference to the following examples.
Test procedure for mass magnetic susceptibility in examples:
the magnetic susceptibility was measured using a quantity Design MPMS3-SQUID magnetometer. About 160 microliters of a sample to be tested was placed in a liquid sample holder (C130D, Quantum Design), sealed firmly without leakage (the tightness was tested well before the experiment), the magnetic field was scanned between-3T and 3T, there was a measurement point every 0.25T, all signals were corrected by directly subtracting the voltage signals (normalized by weight ratio) of the sample holder and the solvent (water or saline solution), and finally the magnetization (M) versus magnetic field (H) curve was obtained. According to the expression, the mass magnetic susceptibility (chi) of a sample to be measured is obtained through fitting, namely the slope of an M and H curve, wherein a is the magnetic moment measured by a SQUID magnetometer, M is the solid content of the sample to be measured (when the sample to be measured is suspension, the sample is uniformly mixed and then tested, the material mass is equal to the sample concentration multiplied by the volume, and when the sample to be measured is supernatant, the concentration of the material in the sample can be measured by an ultra-micro ultraviolet spectrometer). The mass magnetic susceptibility units in the invention are all made of cgs units.
Example 1
Dispersing 5mg of AYFFF (the structure is shown as formula (I)) into 10ml of water to obtain a supersaturated solution with the concentration of 0.5 mg/ml; then standing the supersaturated solution at 20 ℃ for 3 days to enable the AYFFF to be self-assembled into a certain structure; finally adding an equal volume of 300mM NaCl solution, and precipitating for 30 minutes; the resulting supernatant contains a large amount of strongly paramagnetic material.
The supernatant obtained in example 1 was tested, and the mass magnetic susceptibility of the obtained material was 2.32X 10-4emu/g, which presents super-strong paramagnetism at normal temperature.
The pictures obtained by mixing example 1AYFFF with NaCl solution and then placing in a 0.5T magnetic field are shown in fig. 1 to 4, where fig. 1 is a picture immediately after mixing, fig. 2 is a picture after mixing and standing for 2min and placing in a 0.5T magnetic field, fig. 3 is a picture after mixing and standing for 10min in a 0.5T magnetic field, and fig. 4 is a picture after mixing and standing for 30min in a 0.5T magnetic field. From fig. 1 to 4, it can be seen that many fibrous materials move toward the magnet, indicating that the applied magnetic field can effectively control the movement of the strongly paramagnetic material.
Example 2
The preparation method is the same as that of example 1, except that: an equal volume of 300mM K was added2SO4After the solution is dissolved, shaking up to obtain a suspension of the strongly paramagnetic material.
The suspension of the strongly paramagnetic material obtained in example 2 was tested to obtain a suspension having a mass magnetic susceptibility of 1.13X 10-5emu/g。
Example 3
The preparation method is the same as that of example 1, except that: an equal volume of 80mM Li was added3PO4Standing the solution for 30min, and finally freeze-drying to obtain the strong paramagnetic material.
The strongly paramagnetic material obtained in example 3 was tested to obtain a material having a mass magnetic susceptibility of up to 5.17X 10- 6emu/g。
Example 4
The preparation method is the same as that of example 1, except that: the used biological molecule is dipeptide FF (the structural formula of which is shown in formula (II)), the added salt solution is CsCl solution, the precipitation time is 5 minutes, and the obtained supernatant contains a large amount of strong paramagnetic materials.
The supernatant obtained in example 4 was tested to obtain a magnetic mass susceptibility of 5.93X 10-4emu/g。
Example 5
10mg of biomolecular tyrosine was dispersed in 10ml of water to give a supersaturated solution at a concentration of 1.0mg/ml, at room temperature in a ratio of 2: 1 volume ratio 150mM Ag (NO)3Mixing the solutions, and standing for 1min to obtain mixed solution containing strong paramagnetic material.
The mixed solution obtained in example 5 was tested to obtain a mixed solution having a mass magnetic susceptibility of 6.34X 10-4emu/g。
Example 6
2mg of an organic molecule, indole, was mixed with 10ml of 70% ethanol in water at room temperature in a ratio of 1: adding 1M NaCl solution in the volume ratio of 1, mixing evenly at room temperature, standing for 1 hour, and obtaining a precipitate containing a large amount of strong paramagnetic materials.
The precipitate obtained in example 6 was tested to obtain a mass magnetic susceptibility of 9.39X 10-6emu/g。
Example 7
3mg of the organic molecule pyrrole was dissolved in 10ml of NMP at 60 ℃ in a volume of 1: KCl solution with the concentration of 0.5M is added in a volume ratio of 1, the precipitation time is 20 minutes, and the obtained supernatant contains a large amount of strongly paramagnetic materials.
The supernatant obtained in example 7 was tested to obtain a magnetic mass susceptibility of 3.63X 10-4emu/g。
Example 8
1mg of the organic molecule bipyridine, dissolved in 10ml of DMSO at 90 ℃ in a volume of 1: LiCl solution with the concentration of 300mM is added in 1 volume ratio, the precipitation time is 15 minutes, and the obtained supernatant contains a large amount of strongly paramagnetic materials.
The supernatant obtained in example 8 was tested to obtain a magnetic mass susceptibility of 3.34X 10-5emu/g。
Example 9
The preparation method is the same as that of example 1, except that: the organic molecule used is imidazole, the self-assembly temperature is 45 ℃, and the added salt solution is Na2SO4The precipitation time was 60 minutes and the resulting supernatant contained a large amount of strongly paramagnetic material.
The supernatant obtained in example 9 was tested to obtain a magnetic mass susceptibility of 2.19X 10-3emu/g。
Example 10
Dispersing 5mg of AYFFF into 10ml of water to obtain a supersaturated solution with the concentration of 0.5 mg/ml; then standing the supersaturated solution at 10 ℃ for 3 days to enable the AYFFF to be self-assembled into a certain structure; finally adding an equal volume of 300mM NaCl solution, and precipitating for 30 minutes; the resulting supernatant contains a large amount of strongly paramagnetic material.
The supernatant obtained in example 10 was tested, and the mass magnetic susceptibility of the obtained material was 3.77X 10- 4emu/g, which presents super-strong paramagnetism at normal temperature.
When the supernatant was placed in a 0.5T magnetic field, many fibrous materials were seen to move toward the magnet, indicating that the applied magnetic field was effective in controlling the movement of the strongly paramagnetic material.
Comparative example 1
Dispersing 5mg of biomolecule IIIGK (the structural formula of IIIGK is shown in formula (III), and the molecular structure does not contain any aromatic ring) into 10ml of water to obtain a supersaturated solution with the concentration of 0.5 mg/ml; then standing the supersaturated solution at 20 ℃ for 3 days; finally, an equal volume of 300mM NaCl solution was added and the mixture was allowed to settle for 30 minutes.
Taking the supernatant for testing to obtain the magnetic susceptibility of-1.24 × 10-5emu/g, diamagnetic. This demonstrates the key role of the ion-pi effect in preparing normal temperature super strong paramagnetic material.
Figure BDA0002844143500000101
Comparative example 2
The preparation method is the same as that of comparative example 1, except that: finally, an equal volume of water was added. The mass magnetic susceptibility of the obtained material is-7.5X 10-6emu/g, diamagnetic. This also illustrates the key role of the ion-pi effect in the preparation of normal temperature super-strong paramagnetic materials.
Comparative example 3
5mg of cellulose (without aromatic ring structure) is dispersed in 10ml of water, and an equal volume of 300mM NaCl solution is added, so that the mass magnetic susceptibility of the obtained material can reach-2.63 multiplied by 10-6emu/g, weak diamagnetism.
When the supernatant is placed in a 0.5T magnetic field, the directional migration of fibrous materials can not be observed, which indicates that the external magnetic field can not effectively control the movement of aromatic ring-free materials.
Comparative example 4
Dispersing 5mg of AYFFF (the structure is shown as formula (I)) into 10ml of water to obtain a supersaturated solution with the concentration of 0.5 mg/ml; then standing the supersaturated solution at 20 ℃ for 3 days to enable the AYFFF to be self-assembled into a certain structure; and finally adding equal volume of water, wherein FIG. 5 is a photograph of just after mixing, FIG. 6 is a photograph of standing for 2min after mixing and placing in a 0.5T magnetic field, FIG. 7 is a photograph of placing for 10min in a 0.5T magnetic field after mixing, and FIG. 8 is a photograph of placing for 30min in a 0.5T magnetic field after mixing.

Claims (10)

1. A preparation method of a strongly paramagnetic material based on monovalent metal ions is characterized in that a substance containing an aromatic ring is mixed with a solution containing monovalent metal ions to obtain the strongly paramagnetic material.
2. The preparation method according to claim 1, wherein the aromatic ring in the aromatic ring-containing substance comprises one or more of benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrimidine, pyrrole, furan, thiophene, imidazole, indole, purine and derivative structures thereof; the concentration range and the proportion of the aromatic ring-containing substance and the monovalent metal ion are (0.1-10) mg: (0.01 to 4000) mmol.
3. The method according to claim 1, wherein the aromatic ring-containing substance is one or more of an organic small molecule, an organic high molecule and a biomolecule; the biological molecules are one or more of amino acids, polypeptides, proteins, DNA and RNA; the monovalent metal ion is preferably Li+、Na+、K+、Rb+、Cs+With Ag+One or more of (a).
4. The method according to claim 1, wherein the aromatic ring-containing substance is selected from one or more of tyrosine, phenylalanine, tyrosine-and/or phenylalanine-containing polypeptides, pyrrole, indole, pyridine, bipyridine and imidazole.
5. The method of claim 1, comprising:
mixing the substance containing aromatic rings with a solvent to obtain a solution of the substance containing aromatic rings;
and mixing the solution of the substance containing the aromatic ring with a solution containing monovalent metal ions to obtain the strongly paramagnetic material.
6. The method according to claim 5, wherein the solution of the aromatic ring-containing substance is left to stand for self-assembly and then mixed with a solution containing monovalent metal ions; the standing temperature is 5-90 ℃; the standing time is 3-10 days.
7. The method according to claim 5, wherein the solvent is one or more of water, ethanol, dimethylsulfoxide and N-methylpyrrolidone;
the ratio of the aromatic ring-containing substance to the solvent is (1-10) mg: 10 ml.
8. The method according to claim 5, wherein the concentration of the monovalent metal ion in the solution containing the monovalent metal ion is 100 to 1000 mM; the volume ratio of the solution of the self-assembled structured matter to the solution containing the monovalent metal ion is 1: (0.5-2).
9. A strongly paramagnetic material based on monovalent metal ions, prepared by the preparation method according to any one of claims 1 to 8.
10. The use of a strongly paramagnetic material based on monovalent metal ions prepared by the preparation method of any one of claims 1 to 8 in the preparation of magnetic targeted therapeutic drugs, micro-controlled medical devices and surgical robots.
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CN115651929A (en) * 2022-11-18 2023-01-31 中国科学院合肥物质科学研究院 Separation method based on DNA magnetic difference

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