CN114804152A - KMn 3+ [Fe 2+ （CN） 6 ]Preparation method of (1) - Google Patents
KMn 3+ [Fe 2+ （CN） 6 ]Preparation method of (1) Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000013078 crystal Substances 0.000 claims abstract description 59
- 239000002105 nanoparticle Substances 0.000 claims abstract description 38
- GOCOEGCLSONNRM-UHFFFAOYSA-N [Mn+3].[K+] Chemical compound [Mn+3].[K+] GOCOEGCLSONNRM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000002405 nuclear magnetic resonance imaging agent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 14
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 5
- 150000002696 manganese Chemical class 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 66
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 38
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 36
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 36
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 36
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 33
- 229930195725 Mannitol Natural products 0.000 claims description 33
- MBBZMMPHUWSWHV-BDVNFPICSA-N N-methylglucamine Chemical compound CNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO MBBZMMPHUWSWHV-BDVNFPICSA-N 0.000 claims description 33
- 239000000594 mannitol Substances 0.000 claims description 33
- 229960001855 mannitol Drugs 0.000 claims description 33
- 235000010355 mannitol Nutrition 0.000 claims description 33
- 229960003194 meglumine Drugs 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 19
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 19
- 235000018417 cysteine Nutrition 0.000 claims description 19
- 229940124274 edetate disodium Drugs 0.000 claims description 19
- 229960003512 nicotinic acid Drugs 0.000 claims description 19
- 235000001968 nicotinic acid Nutrition 0.000 claims description 19
- 239000011664 nicotinic acid Substances 0.000 claims description 19
- 229920002307 Dextran Polymers 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229960002433 cysteine Drugs 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Chemical group 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Chemical group 0.000 claims description 4
- 239000011572 manganese Substances 0.000 abstract description 39
- 238000005481 NMR spectroscopy Methods 0.000 abstract description 15
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 102
- -1 potassium ferricyanide Chemical compound 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 9
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 229960003351 prussian blue Drugs 0.000 description 6
- 239000013225 prussian blue Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- BVYFGGZPLVYOQU-UHFFFAOYSA-N [K].N#C[Fe]C#N Chemical compound [K].N#C[Fe]C#N BVYFGGZPLVYOQU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
- A61K49/08—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by the carrier
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
- A61K49/18—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes
- A61K49/1818—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention relates to a molecular formula KMn 3+ [Fe 2+ (CN) 6 ]The prepared light blue crystal nano particle can be used for preparing T1 nuclear magnetic resonance contrast agent material and T2 nuclear magnetic resonance contrast agent material. According to the usual method, [ Fe (CN) ] 6 ] 4‑ K of + After the salt is mixed with the trivalent manganese salt, only the molecular formula K can be obtained 2 Mn 2+ [Fe 2+ (CN) 6 ]White crystals of (2) and the expected molecular formula KMn cannot be obtained 3+ [Fe 2+ (CN) 6 ]The light blue crystals of (4); the molecular structure KMn obtained by the method 3+ [Fe 2+ (CN) 6 ]Light blue ofPotassium manganese (III) ferrocyanide crystals. Molecular formula is KMn 3+ [Fe 2+ (CN) 6 ]The potassium manganese (III) ferrocyanide light blue crystal is used as a precursor for preparing the nano particle material, and the molecular formula of the nano particle material is KMn 3+ [Fe 2+ (CN) 6 ]A T1 or T2 or T1 and T2 bifunctional nuclear magnetic resonance contrast agent material of a potassium manganese (III) ferrocyanide light blue crystallized nano solution.
Description
Technical Field
The invention relates to a molecular structural formula of KMn (III) [ Fe (II) (CN) 6 ](for the sake of clarity, KMn is used below 3+ [Fe 2+ (CN) 6 ]Stands for KMn (III) [ Fe (II) (CN) 6 ]To be described) of a novel compound potassium manganese (III) ferrocyanide. The molecular structural formula is KMn 3+ [Fe 2+ (CN) 6 ]The XRD and molecular structure of the potassium manganese (III) ferrocyanide crystal is KMn 2+ [Fe 3+ (CN) 6 ]The potassium ferricyanide has a different XRD from that of potassium ferricyanide, and has a molecular structure of K 2 Mn 2+ [Fe 2+ (CN) 6 ]The ferrous manganese cyanide dipotassium has different XRD from the molecular structure KFe 3+ [Fe 2+ (CN) 6 ]XRD similarity for potassium ferricyanide (prussian blue); the molecular structural formula is KMn 3+ [Fe 2+ (CN) 6 ]The potassium manganese (III) ferrocyanide crystal can be prepared into nanoparticles, and the nanoparticles can be used for preparing T1 nuclear magnetic resonance contrast agent materials and T2 nuclear magnetic resonance contrast agent materials, or preparing bifunctional nuclear magnetic resonance contrast agent materials with T1 and T2.
Background
The invention relates to a molecular structure KMn 3+ [Fe 2+ (CN) 6 ]The crystal synthesized by the method can be prepared into nano particles, and can be used for preparing T1 nuclear magnetic resonance contrast agent materials and T2 nuclear magnetic resonance contrast agent materials or preparing T1 and T2 bifunctional nuclear magnetic resonance contrast agent materials.
According to the usual method, [ Fe ] 3+ (CN) 6 ] 3- K of + Aqueous salt solution with Mn 2+ Simply mixing the aqueous salt solution to obtain Mn as molecular formula 2+ 3 [Fe 3+ (CN) 6 ] 2 ·13H 2 Brown ferricyanide crystals with O as the main component; if the above process is carried out under conditions of 100 deg.C distillation for 72 hr, KMn can be obtained 2+ [Fe 3+ (CN) 6 ]·2H 2 Brown crystals of potassium manganese ferricyanide of O; if in the above reaction, [ Fe ] 3+ (CN) 6 ] 3- K of + Saline solution changed to [ Fe 2+ (CN) 6 ] 4- K of + The salt solution, the reaction product has a molecular structure of K 2 Mn 2+ [Fe 2+ (CN) 6 ]The main white crystal of manganese hexacyanoferrate dipotassium, the XRD pattern and the molecular structure of which are KMn 2+ [Fe 3+ (CN) 6 ]·2H 2 The XRD patterns of brown crystals of potassium manganese ferricyanide of O are similar, namely the XRD patterns cannot distinguish that the molecular structure is KMn 2+ [Fe 3+ (CN) 6 ]·2H 2 The brown crystal of potassium manganese ferricyanide of O and the molecular structure are K 2 Mn 2+ [Fe 2+ (CN) 6 ]·nH 2 White crystals of O, but their color and Fe 2p The XPS spectra are different and can be distinguished; notably, in the above reaction, [ Fe ] 3+ (CN) 6 ] 3- K of + Saline solution changed to [ Fe 2+ (CN) 6 ] 4- K of + Brine solution of Mn 2+ Change of salt to stable Mn 3+ Salt, the XRD pattern and the molecular structure of the reaction product are K 2 Mn 2+ [Fe 2+ (CN) 6 ]The same, the product element analysis shows that the element ratio of the reaction product Fe to Mn to K is 1: 2 or less, and the Fe of the reaction product 2p XPS spectra of (A) demonstrate that Fe remains as Fe 2+ The molecular structure of the reaction product is still mainly K 2 Mn 2+ [Fe 2+ (CN) 6 ]The predicted molecular structure is not obtained as KFe 3+ [Fe 2+ (CN) 6 ]The element ratio of Fe to Mn to K is 1: 1. The method of the invention can be used for preparing KMn with molecular structural formula 3+ [Fe 2+ (CN) 6 ]The potassium manganese (III) ferrocyanide crystal has light blue color and a molecular structure of KMn 2+ [Fe 3+ (CN) 6 ]·2H 2 O has different XRD pattern and color, and has a molecular structure KFe similar to that of potassium ferricyanide (Prussian blue) 3+ [Fe 2+ (CN) 6 ]The XRD of the method is similar to that of the conventional method, and the element analysis shows that the element ratio of Fe to Mn to K is 1: 1, and Fe 2p XPS spectra of (A) demonstrate that Fe is Fe 2+ Mn is Mn according to the principle that the valence of the molecule is zero 3+ With Mn 3+ 2p The XPS test results are consistent, and the molecular structure of the obtained product is proved to be KMn 3+ [Fe 2+ (CN) 6 ]Molecular Structure KFe with Potassium iron Cyanide (Prussian blue) 3+ [Fe 2+ (CN) 6 ]In contrast, Mn 3+ Substituted for Fe 3+ And the rest are unchanged, and the two have the same XRD according to the XRD testing principle.
The molecular structure synthesized by the method is KMn 3+ [Fe 2+ (CN) 6 ]The nano particles prepared from the potassium manganese (III) ferrocyanide light blue crystal have good chemical stability and morphological stability, and the relaxation rate test of the nano particle solution shows that the molecular structure is KMn 3+ [Fe 2+ (CN) 6 ]The potassium manganese (III) ferrocyanide light blue crystallized nanoparticle solution can be used as a T1 or T2 single-function nuclear magnetic resonance contrast agent material, and can also be used as a T1 and T2 double-function nuclear magnetic resonance contrast agent material; according to the analysis of the existing research data, the molecular structure is KMn 3+ [Fe 2+ (CN) 6 ]The potassium manganese (III) ferrocyanide crystal or the nano-particle thereof can also be used as potential Mn 3+ Catalyst materials and high performance chemical battery materials.
Disclosure of Invention
The invention relates to a molecular formula KMn 3+ [Fe 2+ (CN) 6 ]The prepared light blue crystal nano particle can be used for preparing T1 nuclear magnetic resonance contrast agent material and T2 nuclear magnetic resonance contrast agent material. According to the usual method, ferrocyanide ([ Fe (CN)) 6 ] 4- K of + Salt) with a trivalent manganese salt, only the molecular formula K is obtained 2 Mn 2+ [Fe 2+ (CN) 6 ]White crystals of (2) and the expected molecular formula KMn cannot be obtained 3+ [Fe 2+ (CN) 6 ]The light blue crystals of (4); the molecular structure KMn can be obtained exactly by the method of the invention 3+ [Fe 2+ (CN) 6 ]The pale blue potassium manganese (III) ferrocyanide crystals. The molecular formula synthesized by the method is KMn 3+ [Fe 2+ (CN) 6 ]The potassium manganese (III) ferrocyanide light blue crystal has the morphological characteristics of difficult dissociation and stability in water, thereby being beneficial to the KMn molecular formula 3+ [Fe 2+ (CN) 6 ]The potassium ferricyanide manganese (III) is used as a precursor to prepare the nano particle material, and the nano particle material can be used for preparing KMn with the molecular formula 3+ [Fe 2+ (CN) 6 ]Nanometer solution T1 nuclear magnetic resonance contrast agent material of potassium ferricyanide (III) potassium light blue crystal and molecular formula KMn 3+ [Fe 2+ (CN) 6 ]Nanometer solution T2 magnetic resonance contrast agent material of potassium manganese (III) ferricyanide light blue crystal, or KMn 3+ [Fe 2+ (CN) 6 ]The nanometer solution of potassium manganese (III) ferricyanide light blue crystal is T1 and T2 difunctional nuclear magnetic resonance contrast agent material.
1. The invention relates to a molecular formula KMn 3+ [Fe 2+ (CN) 6 ]The preparation method of the potassium manganese (III) ferricyanide light blue crystal mainly comprises the following steps:
with a molecular structure (NH) soluble in aqueous solution 4 ) 4 [Fe 2+ (CN) 6 ]Adding 1-2 times equimolar KCl into the ammonium ferrocyanide, and mixing and reacting with equimolar trivalent manganese salt soluble in concentrated phosphoric acid to obtain the compound with the molecular formula of KMn 3+ [Fe 2+ (CN) 6 ]Potassium manganese (III) ferrocyanide crystals that are pale blue.
Molecular formula is KMn 3+ [Fe 2+ (CN) 6 ]Potassium manganese (III) ferrocyanide light blue crystal, the XRD pattern of which is shown in figure 1, and the molecular structure KFe of prussian blue 3+ [Fe 2+ (CN) 6 ]The XRD patterns of the compounds are similar.
Molecular formula is KMn 3+ [Fe 2+ (CN) 6 ]Potassium manganese (III) ferrocyanide in pale blue crystals, Fe in XPS test 2p The spectrum of (A) is shown in figure 2, the absorption peak is 708.5eV, the peak is single peak, the left side has no shoulder peak, and the Fe is proved to be positive divalent, namely the Fe in the structure is Fe 2+ 。
Molecular formula is KMn 3+ [Fe 2+ (CN) 6 ]Potassium manganese (III) ferrocyanide in pale blue crystals, Mn in XPS test 2p The spectrum of (A) is shown in FIG. 3, the absorption peak is 641.24eV, and the Mn is proved to be positive trivalent (the absorption peak of divalent manganese is generally 640.80eV), namely, the manganese in the structure is Mn 3+ 。
Molecular formula is KMn 3+ [Fe 2+ (CN) 6 ]The potassium manganese (III) ferrocyanide is light blue crystal, and the element ratio of K, Mn and Fe in XPS test is about 1: 1.
The molecular structure is KMn 3+ [Fe 2+ (CN) 6 ]Potassium manganese (III) ferrocyanide in pale blue crystals with a ratio of Fe to Mn to K of 1: 1 in the ICP test, taking into account that the valence of Fe is Fe 2+ The valence of K is K + With reference to FIG. 1, the molecular structure KFe of Prussian blue is associated with the XRD pattern 3+ [Fe 2+ (CN) 6 ]The XRD pattern of (A) is similar to that of the Prussian blue molecular structure KFe 3+ [Fe 2+ (CN) 6 ]Middle Fe 3+ Quilt Mn 3+ The principle that the valence of each element of the compound is zero proves that the molecular structure of the prepared product is KMn [ Fe ] 2+ (CN) 6 ]The medium Mn is Mn 3+ The molecular structure of the prepared product is KMn 3+ [Fe 2+ (CN) 6 ]Known as potassium manganese (III) ferrocyanide.
2. Molecular formula is KMn 3+ [Fe 2+ (CN) 6 ]The preparation of the potassium manganese (III) ferrocyanide light blue crystalline nanoparticles and the solution thereof mainly comprises the following steps:
molecular formula is KMn 3+ [Fe 2+ (CN) 6 ]The potassium manganese (III) ferrocyanide is dissolved in the aqueous solution of mannitol, meglumine, polyvinylpyrrolidone, nicotinic acid, edetate disodium and cysteine; or dissolved in water solution containing mannitol, meglumine, polyvinylpyrrolidone, nicotinic acid, and edetate disodium; or dissolved in water solution of mannitol, meglumine, polyvinylpyrrolidone, nicotinic acid, and cysteine; or dissolved in water solution containing mannitol, meglumine, polyvinylpyrrolidone, edetate disodium, and cysteine; or dissolved in water solution of mannitol, meglumine, polyvinylpyrrolidone and nicotinic acid; or dissolved in water solution containing mannitol, meglumine, polyvinylpyrrolidone and edetate disodium; or dissolved in water solution of mannitol, meglumine, polyvinylpyrrolidone and cysteine; or dissolved in mannitol, meglumine, and polyethylenePyrrolidone in an aqueous solution; or dissolving in aqueous solution of mannitol, meglumine, nicotinic acid, edetate disodium, and cysteine, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; or dissolving in aqueous solution of mannitol, meglumine, nicotinic acid, and edetate disodium, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; or dissolving in aqueous solution of mannitol, meglumine, nicotinic acid, and cysteine, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; or dissolving in aqueous solution of mannitol, meglumine, edetate disodium, and cysteine, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; or dissolving in aqueous solution of mannitol, meglumine and nicotinic acid, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; or dissolving in water solution of mannitol, meglumine, and edetate disodium, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; or dissolving in aqueous solution of mannitol, meglumine and cysteine, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; in the above process, the polyvinylpyrrolidone may be replaced with chitosan, or dextran may be replaced with dextran, or carboxyl dextran may be replaced with dextran, or dextran may be replaced with carboxymethyl dextran, or polyethylene glycol may be replaced, the amounts of the components are 2-20 wt% mannitol, 2-20 wt% meglumine, 0.01-5.0 wt% nicotinic acid, 0.01-5.0 wt% edetate disodium, 0.01-5.0 wt% cysteine, 2-20 wt% polyvinylpyrrolidone, 1.0-15 wt% chitosan, 1.0-15 wt% dextran, 1.0-15 wt% carboxyl dextran, 1.0-15 wt% carboxymethyl dextran, polyethylene glycol 1.0-20 wt%, and in the above process, all the components are completely dissolved or eroded, and then continuously stirred for 0.5-36 hr to form stable molecular formulaIs KMn 3+ [Fe 2+ (CN) 6 ]·nH 2 Potassium manganese (III) ferrocyanide crystal nanoparticles and nanoparticle solutions thereof. Wherein:
the size of the nano-particles is between 10nm and 300nm, and the transmission electron microscope nano-particle image is shown in figure 4; the ratio of K, Mn and Fe is about 1: 1 as determined by the energy spectrum of the nano particles of the transmission electron microscope, and the figure is 5;
the manganese content of the nano particle solution is between 0.1 and 40 mM;
the nanoparticles are stable at a pH of between 3.5 and 12.5;
relaxation rate test value r of nano particle solution under 0.5T magnetic field 1 ＝1.47mmol -1 s -1 ，r 2 ＝1.79mmol - 1 s -1 The nano particle solution can be used as a T1 or T2 magnetic resonance contrast agent material or a T1 and T2 bifunctional magnetic resonance contrast agent material.
Drawings
FIG. 1 shows KMn prepared in example 1 of the present invention 3+ [Fe 2+ (CN) 6 ]Powder X-ray diffraction pattern of potassium manganese (III) ferrocyanide pale blue crystals.
FIG. 2 shows KMn prepared in example 1 of the present invention 3+ [Fe 2+ (CN) 6 ]Powdery Fe of bluish crystals of potassium manganese (III) ferrocyanide 2+ 2p XPS spectra of (a).
FIG. 3 shows KMn prepared in example 1 of the present invention 3+ [Fe 2+ (CN) 6 ]Powdery Mn of bluish crystals of potassium manganese (III) ferrocyanide 3+ 2p XPS spectra of (a).
FIG. 4 shows KMn prepared in example 2 of the present invention 3+ [Fe 2+ (CN) 6 ]The transmission electron microscope picture of the potassium manganese (III) ferrocyanide light blue crystal particle solution shows that the particle size of the nano particles is between 10 and 300 nm.
FIG. 5 shows KMn prepared in example 2 of the present invention 3+ [Fe 2+ (CN) 6 ]The elemental analysis energy spectrogram of the potassium manganese (III) ferrocyanide light blue crystal particle solution by a transmission electron microscope is used for measuring K toThe ratio of Mn to Fe is about 1: 1.
Detailed Description
Example 1:
molecular formula is KMn 3+ [Fe 2+ (CN) 6 ]·nH 2 Preparation of potassium manganese (III) O ferrocyanide light blue crystals 1
Weigh 5.68 g (NH) 4 ) 4 [Fe(CN) 6 ]And 1.70g of KCl are put into a 100ml beaker, and 40ml of water is added to be completely dissolved, which is called sample A for short; weighing 7.040 g of manganese (III) triacetoacetonate, putting the weighed materials into a 250 ml flask, adding 100ml of concentrated phosphoric acid, and stirring until the concentrated phosphoric acid is completely dissolved, wherein the solution is transparent and is called sample B for short; slowly dripping the sample A into a beaker of the sample B under stirring, sealing the opening of the beaker with sealing glue, standing for 6 hours at room temperature in a dark place to obtain a molecular formula KMn 3+ [Fe 2+ (CN) 6 ]The potassium manganese (III) ferrocyanide is a light blue crystal, and the crystal is repeatedly pumped and washed by high-purity water; vacuum drying the obtained crystals at 34 deg.C for 24 hr to obtain dried crystals, wherein XRD pattern of crystal powder is shown in FIG. 1; in the XPS spectrum of the crystalline powder, the XPS spectrum of the iron is Fe 2+ 2P The spectrum is shown in FIG. 2, and XPS spectrum of manganese is Mn 3+ 2P The spectrum of the XPS is shown in FIG. 3, and the element ratio K, Mn and Fe is about 1: 1; the ICP measurement of the crystal powder sample was carried out with the element ratio K, Mn and Fe being 1: 1. The above data prove that the molecular structure of the compound obtained by the above reaction is KMn 3+ [Fe 2+ (CN) 6 ]Known as potassium manganese (III) ferrocyanide compound, the crystal color is light blue. Considering the ubiquitous water of crystallization in the structure of the Prussian blue analogue and the closest water of crystallization of the analogue compound structure, the molecular structure of the compound is estimated to be KMn 3+ [Fe 2+ (CN) 6 ]·nH 2 O, wherein n is 0, 1, 1.5, 2.
Example 2:
molecular formula is KMn 3+ [Fe 2+ (CN) 6 ]Preparation of potassium ferricyanide (III) light blue crystal nano-particles
Weighing 8.00g of mannitol, 4.00g of meglumine, 0.0311g of nicotinic acid, 0.0411g of edetate disodium and 0.0511g of cysteine in a 100ml beaker, adding water to 70ml, and stirring by magnetic force until the mixture is completely dissolved, namely sample A.
And weighing 8.5g of polyvinylpyrrolidone, adding the polyvinylpyrrolidone into the sample A, continuously stirring until the polyvinylpyrrolidone is completely dissolved, and cooling to room temperature, namely sample B for short.
Weighing KMn 3+ [Fe 2+ (CN) 6 ]0.4769g of potassium manganese (III) ferrocyanide bluish crystals are added into the sample B, the mixture is continuously stirred until the crystals are completely corroded, the stirring is continued for 12 hours, and the molecular formula is KMn 3+ [Fe 2+ (CN) 6 ]Regulating the pH value of a bluish crystal nano particle solution of potassium manganese (III) ferrocyanide to 8.5 sample C by using a 10% hydrochloric acid solution; the particle size of the nanoparticles of the sample C in the solution is 10-300nm as observed by a transmission electron microscope, and is shown in figure 4; the ratio of K to Mn to Fe of the nanoparticles in sample C was about 1: 1 as determined by elemental analysis spectroscopy with a transmission electron microscope, see FIG. 5.
Example 3:
the molecular formula KMn prepared in example 2 3+ [Fe 2+ (CN) 6 ]Potassium manganese (III) ferrocyanide bluish crystalline nanoparticle solution sample C tested T1 and T2 relaxivity, and the results were tested in a 0.5T magnetic field: r is 1 ＝1.47mmol -1 s -1 ，r 2 ＝1.79mmol -1 s -1 The molecular formula is KMn 3+ [Fe 2+ (CN) 6 ]The potassium manganese (III) ferrocyanide light blue crystal nanoparticle solution can be used as a T1 or T2 magnetic resonance contrast agent material, and can also be used as a T1 and T2 dual-function magnetic resonance contrast agent material.
Claims (6)
1. A molecular formula of KMn (III) [ Fe (II) (CN) 6 ]Potassium manganese (III) ferrocyanide in light blue crystals.
2. The compound of claim 1, having the formula KMn (III) [ Fe (II) (CN) 6 ]The preparation method of the potassium manganese (III) ferrocyanide light blue crystal comprises the following steps: will be soluble in aqueous solution (NH) 4 ) 4 [Fe 2+ (CN) 6 ]Adding equimolar to twice equimolar KCl solutionMixing and reacting with equimolar trivalent manganese salt which can be dissolved in concentrated phosphoric acid to obtain the molecular formula KMn 3+ [Fe 2+ (CN) 6 ]Potassium manganese (III) ferrocyanide crystals that are pale blue.
3. The compound of claim 1, having the formula KMn (III) [ Fe (II) (CN) 6 ]The potassium manganese (III) ferrocyanide is a light blue crystal, and is corroded in an aqueous solution of mannitol, meglumine, polyvinylpyrrolidone, nicotinic acid, edetate disodium and cysteine; or dissolved in water solution containing mannitol, meglumine, polyvinylpyrrolidone, nicotinic acid, and edetate disodium; or dissolved in water solution of mannitol, meglumine, polyvinylpyrrolidone, nicotinic acid, and cysteine; or dissolved in water solution containing mannitol, meglumine, polyvinylpyrrolidone, edetate disodium, and cysteine; or dissolved in water solution of mannitol, meglumine, polyvinylpyrrolidone and nicotinic acid; or dissolved in water solution containing mannitol, meglumine, polyvinylpyrrolidone and edetate disodium; or dissolved in water solution of mannitol, meglumine, polyvinylpyrrolidone and cysteine; or dissolved in water solution containing mannitol, meglumine, and polyvinylpyrrolidone; or dissolving in aqueous solution of mannitol, meglumine, nicotinic acid, edetate disodium, and cysteine, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; or dissolving in aqueous solution of mannitol, meglumine, nicotinic acid, and edetate disodium, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; or dissolving in aqueous solution of mannitol, meglumine, nicotinic acid, and cysteine, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; or dissolving in aqueous solution of mannitol, meglumine, edetate disodium, and cysteine, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; or dissolving in aqueous solution of mannitol, meglumine, and nicotinic acid, stirring until the solution is transparent, and adding waterAdding polyvinylpyrrolidone and then continuously stirring until the solution is transparent; or dissolving in water solution of mannitol, meglumine, and edetate disodium, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; or dissolving in aqueous solution of mannitol, meglumine and cysteine, stirring until the solution is transparent, adding polyvinylpyrrolidone, and stirring until the solution is transparent; in the above process, the polyvinylpyrrolidone may be replaced with chitosan, or dextran may be replaced with dextran, or carboxyl dextran may be replaced with dextran, or dextran may be replaced with carboxymethyl dextran, or polyethylene glycol may be replaced, the amounts of the components are 2-20 wt% mannitol, 2-20 wt% meglumine, 0.01-5.0 wt% nicotinic acid, 0.01-5.0 wt% edetate disodium, 0.01-5.0 wt% cysteine, 2-20 wt% polyvinylpyrrolidone, 1.0-15 wt% chitosan, 1.0-15 wt% dextran, 1.0-15 wt% carboxyl dextran, 1.0-15 wt% carboxymethyl dextran, polyethylene glycol 1.0-20 wt%, wherein the components are dissolved or eroded and then stirred for 0.5-36 hr to form stable molecular formula KMn (III) [ Fe (II) (CN) 6 ]The potassium manganese (III) ferrocyanide crystal nano-particles and the nano-particle solution thereof are light blue.
4. The compound of claim 3, having the formula KMn (III) [ Fe (II) (CN) 6 ]The potassium manganese (III) ferrocyanide light blue crystal nano-particles and the nano-particle solution thereof can be used as T1 magnetic resonance contrast agent materials.
5. The compound of claim 3, having the formula KMn (III) [ Fe (II) (CN) 6 ]The potassium manganese (III) ferrocyanide light blue crystal nano-particles and the nano-particle solution thereof can be used as T2 magnetic resonance contrast agent materials.
6. The molecular formula KMn (III) [ Fe (II) (CN) ]according to claim 1 of claim 3 6 ]Ferrocyanide ofThe potassium manganese (III) light blue crystal nano particle and the nano particle solution thereof can be used as a T1 and T2 bifunctional magnetic resonance contrast agent material.
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| PCT/CN2022/094209 WO2022257736A1 (en) | 2021-06-09 | 2022-05-20 | Method for preparing kmn3+[fe2+(cn)6] |
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