CN106315624A - Manganese potassium ferricyanide crystal synthesis - Google Patents
Manganese potassium ferricyanide crystal synthesis Download PDFInfo
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Abstract
The invention relates to a synthesis method for crystal with a molecular formula of KMn[Fe(CN)6].2H2O and the crystal with the molecular formula of Mn2[Fe(CN)6].0.5H2O by taking potassium ferrocyanide as a raw material as well as a mixing crystal synthetic method, and the crystal obtained by the synthesis method and the mixing crystal can be used for preparing a T1 MR imaging contrast agent and a T2 MR imaging contrast agent.
Description
Technical field
The present invention relates to a kind of with potassium ferrocyanide for Material synthesis one molecular formula as KMn [Fe (CN)6]·2H2O crystallization, molecule
Formula is Mn2[Fe(CN)6]·0.5H2The crystallization of O and the synthetic method of mixed crystallization thereof, the crystallization of this method synthesis, hybrid junctions
Crystalline substance can be used for preparing T1 mri contrast agent and T2 mri contrast agent.
Background technology
The present invention relates to a kind of with potassium ferrocyanide for Material synthesis one molecular formula as KMn [Fe (CN)6]·2H2O and molecular formula are
Mn2[Fe(CN)6]·0.5H2The synthetic method of the crystalline mixture of O, the crystalline mixture of this method synthesis can be used for preparing T1
Mri contrast agent and T2 mri contrast agent.By usual method, after ferricyanate mixes with manganous salt, it is only capable of
It is Mn to molecular formula3[Fe(CN)6]2·13H2The crystallization of O, it is difficult to obtaining molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate
Potassium crystallizes；By the method for the present invention, can definitely obtain molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystallizes；Also
Available molecular formula is Mn2[Fe(CN)6]·0.5H2The crystallization of O；Also can get molecular formula is KMn [Fe (CN)6]·2H2O and point
Minor is Mn2[Fe(CN)6]·0.5H2The mixed crystallization of O, and ratio can adjust, with prepare different proportion molecular formula as KMn
[Fe(CN)6]·2H2O and molecular formula are Mn2[Fe(CN)6]·0.5H2The mixed crystallization of O is that precursor prepares the T1 nuclear-magnetism of its nanometer altogether
The T2 mri contrast agent of contrast agent and the nanometer of shaking.
Summary of the invention
The present invention relates to a kind of with potassium ferrocyanide for Material synthesis molecular formula as KMn [Fe (CN)6]·2H2O and molecular formula are
Mn2[Fe(CN)6]·0.5H2The synthetic method of the crystalline mixture of O, the crystalline mixture of this method synthesis can be used for preparing T1
Mri contrast agent and T2 mri contrast agent.By usual method, after ferricyanate mixes with manganous salt, it is only capable of
It is Mn to molecular formula3[Fe(CN)6]2·13H2The crystallization of O, it is difficult to obtaining molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate
Potassium crystallizes；By the method for the present invention, can definitely obtain molecular formula is KMn [Fe (CN)6]2H2O Manganese hexacyanoferrate potassium crystallizes；Also may be used
Obtaining molecular formula is KMn [Fe (CN)6]·2H2O and molecular formula are Mn2[Fe(CN)6]·0.5H2The mixed crystallization of O, and ratio can
With adjust, with prepare different proportion molecular formula as KMn [Fe (CN)6]2H2O and molecular formula are Mn2[Fe(CN)6]·0.5H2O's
Mixed crystallization is that precursor prepares the T1 mri contrast agent of its nanometer and the T2 mri contrast agent of nanometer.
1. the present invention relates to a kind of with potassium ferrocyanide for Material synthesis molecular formula as KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium
The synthetic method of crystallization, mainly comprises the steps that
With dissolve in the ferrocyanic acid salt of lactic acid aqueous solution and dissolve in lactic acid aqueous solution manganous salt by hybrid reaction, obtain
Molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystallizes.
Wherein the concentration of lactic acid aqueous solution is 0%-30% (weight), and solubility manganous salt is at the lactic acid of 0%-30% (weight)
Mole in aqueous solution with solubility ferrocyanic acid salt mole ratio in the lactic acid aqueous solution of 0%-30% (weight) is
≥2∶1。
Molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystallizes, and its x-ray diffractogram of powder is Fig. 1, and its crystallization is big
Little see Fig. 4.
2. the present invention relates to one with potassium ferrocyanide for Material synthesis molecular formula as Mn2[Fe(CN)6]·0.5H2O manganous ferrocyanide
The synthetic method of crystallization, mainly comprises the steps that
With dissolve in the ferrocyanic acid salt of lactic acid aqueous solution and dissolve in lactic acid aqueous solution manganous salt by hybrid reaction, obtain
Molecular formula is Mn2[Fe(CN)6]·0.5H2O manganous ferrocyanide crystallizes.
Wherein the concentration of lactic acid aqueous solution is 0%-30% (weight), and solubility manganous salt is at the lactic acid of 0%-30% (weight)
Mole in aqueous solution with solubility ferrocyanic acid salt mole ratio in the lactic acid aqueous solution of 0%-30% (weight) is
1: >=2, its x-ray diffractogram of powder is Fig. 2.
3. the present invention relates to a kind of with potassium ferrocyanide for Material synthesis molecular formula as KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium
It is Mn with molecular formula2[Fe(CN)6]·0.5H2The synthetic method of O ferrocyanide mixed crystalline manganese, mainly comprises the steps that
With dissolve in the ferrocyanic acid salt of lactic acid aqueous solution and dissolve in lactic acid aqueous solution manganous salt by hybrid reaction, obtain
Molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium and molecular formula are Mn2[Fe(CN)6]·0.5H2O manganous ferrocyanide mixes
Crystallization.
Wherein the concentration of lactic acid aqueous solution is 0%-30% (weight), and solubility manganous salt is at the lactic acid of 0%-30% (weight)
Mole in aqueous solution with solubility ferrocyanic acid salt mole ratio in the lactic acid aqueous solution of 0%-30% (weight) is
1: ＜ 4, its x-ray diffractogram of powder is Fig. 3.
Can be according to solubility manganous salt mole in the lactic acid aqueous solution of 0%-30% (weight) and solubility ferrous iron cyanogen
It is KMn that the adjustment of hydrochlorate mole ratio in the lactic acid aqueous solution of 0%-30% (weight) obtains the molecular formula of different proportion
[Fe(CN)6]·2H2O Manganese hexacyanoferrate potassium and molecular formula are Mn2[Fe(CN)6]·0.5H2The mixed crystallization of O manganous ferrocyanide.
4. molecular formula is KMn [Fe (CN)6]·2H2The preparation of O Manganese hexacyanoferrate potassium crystalline nanoparticles mainly comprises the steps that
It is KMn [Fe (CN) by molecular formula6]·2H2The crystallization corrosion of O Manganese hexacyanoferrate potassium is mannitol, meglumine, polyethylene at formula
Ketopyrrolidine, nicotinic acid, disodium edetate, cysteine aqueous solution in；Or corrosion is mannitol, meglumine at formula, gathers
Vinylpyrrolidone, nicotinic acid, disodium edetate aqueous solution in；Or corrosion is mannitol, meglumine, polyethylene pyrrole at formula
Pyrrolidone, nicotinic acid, cysteine aqueous solution in；Or corrosion formula be mannitol, meglumine, polyvinylpyrrolidone,
Disodium edetate, cysteine aqueous solution in；Or corrosion is mannitol, meglumine, polyvinylpyrrolidone, cigarette at formula
In aqueous acid；Or corrosion is in the aqueous solution that formula is mannitol, meglumine, polyvinylpyrrolidone, disodium edetate；
Or corrosion is in the aqueous solution that formula is mannitol, meglumine, polyvinylpyrrolidone, cysteine；Or corrosion at formula is
Mannitol, meglumine, polyvinylpyrrolidone aqueous solution in；Or corrosion is mannitol, meglumine, nicotinic acid at formula, depends on
Ground acid disodium, cysteine aqueous solution in, stir to solution transparent after, add and continue stirring extremely after polyvinylpyrrolidone
Solution is transparent；Or corrosion formula be mannitol, meglumine, nicotinic acid, disodium edetate, aqueous solution in, stirring to solution
After transparent, continue stirring after adding polyvinylpyrrolidone transparent to solution；Or corrosion formula be mannitol, meglumine,
Nicotinic acid, cysteine aqueous solution in, stir to solution transparent after, add and continue stirring after polyvinylpyrrolidone to solution
Transparent；Or corrosion is in the aqueous solution that formula is mannitol, meglumine, disodium edetate, cysteine, stir saturating to solution
After bright, continue stirring after adding polyvinylpyrrolidone transparent to solution；Or corrosion is mannitol, meglumine, cigarette at formula
In aqueous acid, after stirring to solution is transparent, continue stirring after adding polyvinylpyrrolidone transparent to solution；Or corrosion
In the aqueous solution that formula is mannitol, meglumine, disodium edetate, after stirring to solution is transparent, add polyvinyl pyrrole
Stirring is continued transparent to solution after alkanone；Or corrosion is in the aqueous solution that formula is mannitol, meglumine, cysteine, stirring
To solution transparent after, add that to continue stirring after polyvinylpyrrolidone transparent to solution；In said process, polyvinylpyrrolidine
Ketone can substitute with chitosan, or available dextran substitutes, or available carboxyl dextran substitutes, or available glucosan substitutes,
Or available Sensor Chip CM 5 substitutes, or available Polyethylene Glycol substitutes, each Ingredient Amount be mannitol be 2-20% (weight), Portugal
Methylamine is 2%-20% (weight), and nicotinic acid is 0.01-5.0% (weight), and disodium edetate is 0.01-5.0% (weight), half Guang
Propylhomoserin is 0.01%-5.0% (weight), and polyvinylpyrrolidone is 2%-20% (weight), and chitosan is 1.0%-15% (weight),
Dextran is 1.0%-15% (weight), and carboxyl dextran is 1.0%-15% (weight), and glucosan is 1.0%-15% (weight
Amount), Sensor Chip CM 5 is 1.0%-15% (weight), and Polyethylene Glycol is 1.0%-20% (weight), in said process, respectively becomes
Dividing and all dissolve or continue stirring 0.5-36 hour after corrosion, the molecular formula forming stable transparent is KMn [Fe (CN)6]·2H2O ferrum
Cyaniding manganese potassium crystalline nanoparticles and nano-particle solution thereof.Wherein:
Nanoparticle Size is between 20nm-30nm, and its transmission electricity Electronic Speculum nanoparticle image is shown in Fig. 5；Its transmission electron microscope nanometer
The particle spectrum ratio containing potassium ferromanganese is about 1: 1: 1, sees Fig. 6；
Nano-particle solution Fe content is between 0.1-400mM；
Nanoparticle is stablized between 3.5-12.6 at PH；
Free divalent manganesetion concentration is less than 5ppm.
Molecular formula is Mn2[Fe(CN)6]·0.5H2The crystallization of O manganous ferrocyanide, molecular formula are KMn [Fe (CN)6]·2H2O ferrum cyaniding
Manganese potassium and molecular formula are Mn2[Fe(CN)6]·0.5H2The preparation method of O ferrocyanide mixed crystalline manganese nanoparticle with molecular formula is
KMn[Fe(CN)6]·2H2Preparing of O Manganese hexacyanoferrate potassium crystalline nanoparticles is identical.
5. molecular formula is KMn [Fe (CN)6]·2H2Preparing of O Manganese hexacyanoferrate potassium crystalline nanoparticles mri contrast agent is main
Comprise the following steps:
Molecular formula is KMn [Fe (CN)6]·2H2It is dense that O Manganese hexacyanoferrate potassium crystalline nanoparticles solution is configured to containing manganese 2-50mM
Degree, through 0.22 μm microporous filter membrane aseptic filtration, aseptic subpackaged in cillin bottle, i.e. prepare six cyanogen metal complexs of liquid manganese
Nano-NMR contrast agent, can use by injection for intravenous；
It is KMn [Fe (CN) by prepared molecular formula6]·2H2O Manganese hexacyanoferrate potassium crystalline nanoparticles solution is configured to containing manganese
The concentration of 2-50mM, through 0.22 μm microporous filter membrane aseptic filtration, gained filtrate is by the vacuum drying of aseptic spray chilling or vacuum
Freeze-drying method processes, and obtains dry powder, and aseptic subpackaged in cillin bottle, i.e. preparing molecular formula is KMn [Fe (CN)6]·2H2O
Manganese hexacyanoferrate potassium crystallization nano freeze-dried powder mri contrast agent, its x-ray diffractogram of powder is shown in Fig. 7, it was demonstrated that nanoparticle
Molecular structure is KMn [Fe (CN)6]·2H2O；Use front water for injection or injection normal saline dilution, be made into containing manganese
The concentration of 2-50mM, can use by injection for intravenous.
Molecular formula is Mn2[Fe(CN)6]·0.5H2The crystallization of O manganous ferrocyanide, molecular formula are KMn [Fe (CN)6]·2H2O ferrum cyaniding
Manganese potassium and molecular formula are Mn2[Fe(CN)6]·0.5H2The preparation method of O ferrocyanide mixed crystalline manganese nanoparticle with molecular formula is
KMn[Fe(CN)6]·2H2Preparing of O Manganese hexacyanoferrate potassium crystalline nanoparticles mri contrast agent is identical.
6. molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystalline nanoparticles mri contrast agent is used for rat
Liver magnetic resonance imaging test result indicate that:
T1 contrastographic picture is obviously enhanced, and signal enhancement value strengthens more than 220% relatively than unenhanced signal value, sees Fig. 8, Fig. 9；Make
Rat after shadow experiment is raised 2 weeks, its outward appearance of period and behavior no abnormality seen.
T2 contrastographic picture is obviously reduced, and signal enhancement value, than blank signal value relative reduction more than 65%, is shown in Figure 10, Figure 11；
Rat after radiography experiment is raised 2 weeks, its outward appearance of period and behavior no abnormality seen.
Molecular formula is Mn2[Fe(CN)6]·0.5H2The crystallization of O manganous ferrocyanide, molecular formula are KMn [Fe (CN)6]·2H2O ferrum cyaniding
Manganese potassium and molecular formula are Mn2[Fe(CN)6]·0.5H2The preparation method of O ferrocyanide mixed crystalline manganese nanoparticle with molecular formula is
KMn[Fe(CN)6]·2H2O Manganese hexacyanoferrate potassium crystalline nanoparticles mri contrast agent is used for rat liver magnetic resonance imaging
Experimental result is similar to.
Accompanying drawing explanation
Fig. 1 be the molecular formula prepared by the embodiment of the present invention 1 be KMn [Fe (CN)6]·2H2The powder X-ray of O Manganese hexacyanoferrate potassium crystallization
X ray diffration pattern x.
Fig. 2 be the molecular formula prepared by the embodiment of the present invention 2 be Mn2[Fe(CN)6]·0.5H2The powder X-ray of O manganous ferrocyanide crystallization
X ray diffration pattern x.
Fig. 3 be the molecular formula prepared by the embodiment of the present invention 3 be KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium and molecular formula are
Mn2[Fe(CN)6]·0.5H2The x-ray diffractogram of powder of O manganous ferrocyanide crystalline mixture.
Fig. 4 be the molecular formula prepared by the embodiment of the present invention 1 be KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystallizes, 1000
Crystallographic image under times optical microscope.
Fig. 5 be the molecular formula prepared by the embodiment of the present invention 4 be KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystalline particle solution
Transmission electron microscope picture, nano particle diameter is between 20-30nm.
Fig. 6 be the molecular formula prepared by the embodiment of the present invention 4 be KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystalline particle solution
Transmission electron microscope elementary analysis energy spectrogram, records potassium: manganese: the ratio of ferrum is about 1: 1: 1.
Fig. 7 be the embodiment of the present invention 6 Middle molecule formula be KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystalline particle solution is by cold
The lyophilized powder x-ray diffractogram of powder prepared after freezing vacuum drying.
Fig. 8 be the embodiment of the present invention 7 molecular formula be KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystalline nanoparticles nuclear magnetic resonance, NMR
Contrast agent is in rat liver magnetic resonance imaging is tested, by the dosage of 1ml/300g by tail vein injection to rat body
Before Nei, do magnetic resonance imaging, obtain magnetic resonance imaging T1 image and the signal value of the rat liver before injection.
Fig. 9 be the embodiment of the present invention 7 Middle molecule formula be KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystalline nanoparticles nuclear-magnetism is altogether
Shake contrast agent for rat liver magnetic resonance imaging test in, by the dosage of 1ml/300g by tail vein injection to rat
Internal, do magnetic resonance imaging, the magnetic resonance imaging T1 image of rat liver and signal value when must inject latter 20 minutes.
Figure 10 be the embodiment of the present invention 8 molecular formula be KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystalline nanoparticles nuclear magnetic resonance, NMR
Contrast agent is in rat liver magnetic resonance imaging is tested, by the dosage of 1ml/300g by tail vein injection to rat body
Before Nei, do magnetic resonance imaging, obtain magnetic resonance imaging T2 image and the signal value of the rat liver before injection.
Figure 11 be the embodiment of the present invention 8 Middle molecule formula be KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystalline nanoparticles nuclear-magnetism is altogether
Shake contrast agent for rat liver magnetic resonance imaging test in, by the dosage of 1ml/300g by tail vein injection to rat
Internal, do magnetic resonance imaging, the magnetic resonance imaging T2 image of rat liver and signal value when must inject latter 20 minutes.
Detailed description of the invention
Embodiment 1:
Molecular formula is KMn [Fe (CN)6]·2H2The preparation of O Manganese hexacyanoferrate potassium crystallization
Weigh 12.6732 grams of K4[Fe(CN)6]·3H2O puts in 250 milliliters of beakers, adds 10% lactic acid aqueous solution 100ml complete
CL, is called for short sample A；Weigh 11.8752 grams of MnCl2·4H2O puts in 250 milliliters of flasks, adds 10% lactic acid aqueous solution
100ml is completely dissolved, and is called for short sample B；A sample is poured in the beaker of B sample, seal beaker mouth with sealing compound, room under lucifuge
Gentle and quiet put 12 hours after to obtain molecular formula be KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystallizes, and washes through repeatedly taking out with high purity water
Crystallization, after gained crystallization is drained, through vacuum lyophilization, obtains the crystallization being dried, and its x-ray diffractogram of powder is shown in Fig. 1.
Embodiment 2:
Molecular formula is Mn2[Fe(CN)6]·0.5H2The preparation of O manganous ferrocyanide crystallization
Weigh 12.6732 grams of K4[Fe(CN)6]·3H2O puts in 250 milliliters of beakers, adds 10% lactic acid aqueous solution 100ml complete
CL, is called for short sample A；Weigh 2.9688 grams of MnCl2·4H2O puts in 250 milliliters of flasks, adds 10% lactic acid aqueous solution
100ml is completely dissolved, and is called for short sample B；A sample is poured in the beaker of B sample, seal beaker mouth with sealing compound, room under lucifuge
Gentle and quiet put 12 hours after to obtain molecular formula be Mn2[Fe(CN)6]·0.5H2O manganous ferrocyanide crystallizes, and washes through repeatedly taking out with high purity water
Crystallization, after gained crystallization is drained, through vacuum lyophilization, obtains the crystallization being dried, and its x-ray diffractogram of powder is shown in Fig. 2.
Embodiment 3:
Molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium and molecular formula are Mn2[Fe(CN)6]·0.5H2O manganous ferrocyanide
The preparation of mixed crystallization
Weigh 6.3366 grams of K4[Fe(CN)6]·3H2O puts in 250 milliliters of beakers, adds 10% lactic acid aqueous solution 100ml complete
Dissolve, be called for short sample A；Weigh 2.9688 grams of MnCl2·4H2O puts in 250 milliliters of flasks, adds 10% lactic acid aqueous solution 100ml
It is completely dissolved, is called for short sample B；Being poured into by A sample in the beaker of B sample, seal beaker mouth with sealing compound, under lucifuge, room temperature stands
Obtaining minor after 12 hours is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium and molecular formula are Mn2[Fe(CN)6]·0.5H2O is ferrous
Cyaniding mixed crystalline manganese, washes crystallization through repeatedly taking out with high purity water, after gained crystallization is drained, through vacuum lyophilization, is dried
Crystallization, its x-ray diffractogram of powder is shown in Fig. 3.
Embodiment 4:
Molecular formula is KMn [Fe (CN)6]·2H2The preparation of O Manganese hexacyanoferrate potassium crystalline nanoparticles
Weigh 8.00g mannitol, meglumine 4.00g, nicotinic acid 0.0311g, disodium edetate 0.0411g, cysteine 0.0511g
In 100ml beaker, add water to 70ml, magnetic agitation, to being completely dissolved, be called for short sample A.
Weigh polyvinylpyrrolidone 8.5g again to add in sample A, be stirred continuously, be completely dissolved to polyvinylpyrrolidone, solution
Transparent in micro-Huang, then it is cooled to room temperature, is called for short sample B.
Weighing molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystallization 0.2736g joins in sample B, is stirred continuously,
To the complete corrosion of this crystallization, continuing stirring 12 hours, obtaining molecular formula is KMn [Fe (CN)6]·2H2The crystallization of O Manganese hexacyanoferrate potassium is received
Rice corpuscles solution, is called for short sample C.The pH value recording sample C is 8.5；Transmission electron microscope observation to sample C nano particle molten
Equiblibrium mass distribution in liquid, particle diameter, at 20-30nm, is shown in Fig. 5；Transmission electron microscope elementary analysis power spectrum records sample C potassium: manganese:
The ratio of ferrum is 1: 1: 1, sees Fig. 6；With manganese ion free in reverse osmosis unit separation sample C, measure with atomic absorption method and divide
The free manganese ion concentration separated out, calculates that in sample C, free manganese ion concentration is 3.3ppm.
Embodiment 5:
By KMn [Fe (CN) prepared in embodiment 26]·2H2O Manganese hexacyanoferrate potassium crystalline nanoparticles solution sample C is configured to
Containing the concentration of manganese 10mM, through 0.22 μm microporous filter membrane aseptic filtration, aseptic subpackaged in cillin bottle, i.e. prepare liquid
Molecular formula KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystalline nanoparticles solution nuclear magnetic resonance contrast agent, is called for short sample D, is available for
Intravenous injection uses.
Embodiment 6:
By KMn [Fe (CN) prepared in embodiment 26]·2H2O Manganese hexacyanoferrate potassium crystalline nanoparticles solution sample C is configured to
Containing the concentration of manganese 10mM, through 0.22 μm microporous filter membrane aseptic filtration, sterile cryo is vacuum dried, aseptic subpackaged to XiLin
In Ping, the molecular formula i.e. preparing solid is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystalline nanoparticles lyophilized powder nuclear magnetic resonance, NMR
Contrast agent, is called for short sample E, can use by injection for intravenous；Take lyophilized powder and do powder X-ray diffraction test, it was demonstrated that lyophilized powder is received
Rice corpuscles molecular structure is KMn [Fe (CN)6]·2H2O, is shown in Fig. 7.
Embodiment 7:
Sample D obtained by embodiment 3 press the dosage of 1ml/300g by tail vein injection to rat body, do nuclear-magnetism common
The radiography that shakes is tested, and records magnetic resonance imaging T1 image and the signal value of rat liver, see Fig. 8 before injection sample D；Injection sample
The magnetic resonance imaging T1 image of rat liver and signal value when 20 minutes after D, be shown in Fig. 9.
Rat liver magnetic resonance imaging T1 image after injection sample D is obviously enhanced, and signal value increases relatively than before injection sample D
Strong by more than 220%；Rat after injection sample D is raised 2 weeks, and period rat outward appearance and behavior are no abnormal.
Embodiment 8:
Sample E obtained in embodiment 6 is injected and is configured to 10mM solution with water, quiet by tail by the dosage of 1ml/300g
Arteries and veins is expelled in rat body, does magnetic resonance imaging experiment, records the magnetic resonance imaging T2 of rat liver before injection sample E
Image and signal value, be shown in Figure 10；The magnetic resonance imaging T2 image of rat liver and signal value when 20 minutes after injection sample E,
See Figure 11.
Rat liver magnetic resonance imaging T2 image after injection sample E is the most dimmed, and signal value drops relatively than before injection sample E
Low by more than 65%；Rat after injection sample E is raised 2 weeks, and period rat outward appearance and behavior are no abnormal.
Claims (13)
1. a molecular formula is KMn [Fe (CN)6]·2H2The crystallization of O Manganese hexacyanoferrate potassium, a kind of molecular formula are Mn2
[Fe(CN)6]·0.5H2The crystallization of O manganous ferrocyanide, a kind of molecular formula are KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium and molecular formula
For Mn2[Fe(CN)6]·0.5H2O ferrocyanide mixed crystalline manganese and synthetic method thereof.
The most according to claim 1, molecular formula is KMn [Fe (CN)6]·2H2The crystallization of O Manganese hexacyanoferrate potassium and synthetic method thereof,
It is that the ferrocyanic acid salt dissolving in lactic acid aqueous solution is passed through hybrid reaction with the manganous salt dissolving in lactic acid aqueous solution, is divided
Minor is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium crystallizes, and its x-ray diffractogram of powder is shown in Fig. 1.
The most according to claim 1, molecular formula is Mn2[Fe(CN)6]·0.5H2The crystallization of O manganous ferrocyanide and synthetic method thereof,
It is that the ferrocyanic acid salt dissolving in lactic acid aqueous solution is passed through hybrid reaction with the manganous salt dissolving in lactic acid aqueous solution, is divided
Minor is Mn2[Fe(CN)6]·0.5H2O manganous ferrocyanide crystallizes, and its x-ray diffractogram of powder is shown in Fig. 2.
The most according to claim 1, molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium and molecular formula are Mn2
[Fe(CN)6]·0.5H2O ferrocyanide mixed crystalline manganese and synthetic method thereof, be by dissolve in the ferrocyanic acid salt of lactic acid aqueous solution with
The manganous salt dissolving in lactic acid aqueous solution passes through hybrid reaction, and obtaining molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate
Potassium and molecular formula are Mn2 [Fe (CN)6]·0.5H2O ferrocyanide mixed crystalline manganese, its x-ray diffractogram of powder is shown in Fig. 3.
The most according to claim 2, molecular formula is KMn [Fe (CN)6]·2H2The crystallization of O Manganese hexacyanoferrate potassium and synthetic method thereof,
It is characterized in that, the concentration of dlactic acid aqueous solution is 0%-30% (weight).
The most according to claim 2, molecular formula is KMn [Fe (CN)6]·2H2The synthetic method of O Manganese hexacyanoferrate potassium crystallization, its
Feature is, solubility ferrocyanic acid salt is 1: >=2 with the mol ratio of manganous salt.
The most according to claim 3, molecular formula is Mn2[Fe(CN)6]·0.5H2The crystallization of O manganous ferrocyanide and synthetic method thereof,
It is characterized in that, the concentration of dlactic acid aqueous solution is 0%-30% (weight).
The most according to claim 3, molecular formula is Mn2[Fe(CN)6]·0.5H2The crystallization of O manganous ferrocyanide and synthetic method thereof,
It is characterized in that, solubility manganous salt is 1: >=2 with the mol ratio of ferrocyanic acid salt.
The most according to claim 4, molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium and molecular formula are Mn2
[Fe(CN)6]·0.5H2O ferrocyanide mixed crystalline manganese and synthetic method thereof, is characterized in that, the concentration of dlactic acid aqueous solution is
0%-30% (weight).
The most according to claim 4, molecular formula is KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium and molecular formula are Mn2
[Fe(CN)6]·0.5H2O ferrocyanide mixed crystalline manganese and synthetic method thereof, is characterized in that, solubility manganous salt and ferrocyanic acid
The mol ratio of salt is 1: ＜ 4, and the ratio of mixed crystallization can be carried out according to the mol ratio of solubility manganous salt with ferrocyanic acid salt
Adjust.
Molecular formula is KMn [Fe (CN) according to claim 2 by 11.6]·2H2O Manganese hexacyanoferrate potassium crystallizes or according to claim
Molecular formula is Mn by 32[Fe(CN)6]·0.5H2O manganous ferrocyanide crystallization or be KMn by molecular formula according to claim 4
[Fe(CN)6]·2H2O Manganese hexacyanoferrate potassium and molecular formula are Mn2[Fe(CN)6]·0.5H2O ferrocyanide mixed crystalline manganese corrosion is being joined
Side is in the aqueous solution of mannitol, meglumine, polyvinylpyrrolidone, nicotinic acid, disodium edetate, cysteine；Or corrosion
In the aqueous solution that formula is mannitol, meglumine, polyvinylpyrrolidone, nicotinic acid, disodium edetate；Or corrosion is at formula
For mannitol, meglumine, polyvinylpyrrolidone, nicotinic acid, cysteine aqueous solution in；Or corrosion formula be mannitol,
Meglumine, polyvinylpyrrolidone, disodium edetate, cysteine aqueous solution in；Or corrosion is mannitol, Portugal at formula
In methylamine, polyvinylpyrrolidone, cigarette aqueous acid；Or corrosion is mannitol, meglumine, polyvinylpyrrolidine at formula
Ketone, disodium edetate aqueous solution in；Or corrosion is mannitol, meglumine, polyvinylpyrrolidone, cysteine at formula
Aqueous solution in；Or corrosion is in the aqueous solution that formula is mannitol, meglumine, polyvinylpyrrolidone；Or corrosion is at formula
For mannitol, meglumine, nicotinic acid, disodium edetate, cysteine aqueous solution in, stir to solution transparent after, add
Stirring is continued transparent to solution after polyvinylpyrrolidone；Or corrosion is mannitol, meglumine, nicotinic acid, edetic acid two at formula
Sodium, aqueous solution in, stir to solution transparent after, add that to continue stirring after polyvinylpyrrolidone transparent to solution；Or it is molten
Erosion, in the aqueous solution that formula is mannitol, meglumine, nicotinic acid, cysteine, after stirring to solution is transparent, adds poly-second
Stirring is continued transparent to solution after alkene pyrrolidone；Or corrosion is mannitol, meglumine, disodium edetate, half Guang ammonia at formula
In aqueous acid, after stirring to solution is transparent, continue stirring after adding polyvinylpyrrolidone transparent to solution；Or corrosion
In formula is mannitol, meglumine, cigarette aqueous acid, after stirring to solution is transparent, after adding polyvinylpyrrolidone
Continue stirring transparent to solution；Or corrosion is in the aqueous solution that formula is mannitol, meglumine, disodium edetate, stirring is to molten
After liquid is transparent, continue stirring after adding polyvinylpyrrolidone transparent to solution；Or corrosion formula be mannitol, meglumine,
In the aqueous solution of cysteine, after stirring to solution is transparent, continue stirring after adding polyvinylpyrrolidone transparent to solution；
In said process, polyvinylpyrrolidone can substitute with chitosan, or available dextran substitutes, or available carboxyl dextran
Substituting, or available glucosan substitutes, or available Sensor Chip CM 5 substitutes, or available Polyethylene Glycol substitutes, each Ingredient Amount is
Mannitol is 2-20% (weight), and meglumine is 2%-20% (weight), and nicotinic acid is 0.01-5.0% (weight), disodium edetate
For 0.01-5.0% (weight), cysteine is 0.01%-5.0% (weight), and polyvinylpyrrolidone is 2%-20% (weight),
Chitosan is 1.0%-15% (weight), and dextran is 1.0%-15% (weight), and carboxyl dextran is 1.0%-15% (weight
Amount), glucosan is 1.0%-15% (weight), and Sensor Chip CM 5 is 1.0%-15% (weight), and Polyethylene Glycol is 1.0%-20%
(weight), in said process, each composition all dissolves or continues stirring 0.5-36 hour after corrosion, forms the molecule of stable transparent
Formula is KMn [Fe (CN)6]·2H2The nanoparticle of O Manganese hexacyanoferrate potassium crystallization and nano-particle solution thereof.
12. is KMn [Fe (CN) according to molecular formula described in claim 116]·2H2The crystallization of O Manganese hexacyanoferrate potassium or molecular formula are
Mn2[Fe(CN)6]·0.5H2The crystallization of O manganous ferrocyanide or molecular formula are KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium and molecule
Formula is Mn2[Fe(CN)6]·0.5H2The nanoparticle of O ferrocyanide mixed crystalline manganese and nano-particle solution thereof, can be used as T1 core
Magnetic resonance contrast agent.
13. is KMn [Fe (CN) according to molecular formula described in claim 116]·2H2The crystallization of O Manganese hexacyanoferrate potassium or molecular formula are
Mn2[Fe(CN)6]·0.5H2The crystallization of O manganous ferrocyanide or molecular formula are KMn [Fe (CN)6]·2H2O Manganese hexacyanoferrate potassium and molecule
Formula is Mn2[Fe(CN)6]·0.5H2The nanoparticle of O ferrocyanide mixed crystalline manganese and nano-particle solution thereof, can be used as T2 core
Magnetic resonance contrast agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017070A (en) * | 2017-12-18 | 2018-05-11 | 吴学文 | The synthesis of Manganese hexacyanoferrate potassium white crystals |
| CN109095477A (en) * | 2017-06-21 | 2018-12-28 | 吴学文 | The synthesis of Manganese hexacyanoferrate potassium crystallization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103251962A (en) * | 2012-02-17 | 2013-08-21 | 苏州迈格锐意医药科技有限公司 | Magnetic resonance contrast material and preparation method thereof, and contrast agent |
| US20130257378A1 (en) * | 2012-03-28 | 2013-10-03 | Yuhao Lu | Transition Metal Hexacyanoferrate Battery Cathode with Single Plateau Charge/Discharge Curve |
| WO2014178170A1 (en) * | 2013-04-29 | 2014-11-06 | Sharp Kabushiki Kaisha | Protected transition metal hexacyanoferrate battery electrode |
| CN104512910A (en) * | 2013-09-30 | 2015-04-15 | 吴学文 | Preparation method of manganese hexacyanoferrate and nanoparticle thereof |
-
2015
- 2015-06-23 CN CN201510346194.5A patent/CN106315624A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103251962A (en) * | 2012-02-17 | 2013-08-21 | 苏州迈格锐意医药科技有限公司 | Magnetic resonance contrast material and preparation method thereof, and contrast agent |
| US20130257378A1 (en) * | 2012-03-28 | 2013-10-03 | Yuhao Lu | Transition Metal Hexacyanoferrate Battery Cathode with Single Plateau Charge/Discharge Curve |
| WO2014178170A1 (en) * | 2013-04-29 | 2014-11-06 | Sharp Kabushiki Kaisha | Protected transition metal hexacyanoferrate battery electrode |
| CN104512910A (en) * | 2013-09-30 | 2015-04-15 | 吴学文 | Preparation method of manganese hexacyanoferrate and nanoparticle thereof |
Non-Patent Citations (1)
| Title |
|---|
| A. GO´MEZ ET AL.，: "The structure of two manganese hexacyanometallates(II):Mn2［Fe(CN)6］•8H2O and Mn2［Os(CN)6］•8H2O", 《POWDER DIFFRACTION》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109095477A (en) * | 2017-06-21 | 2018-12-28 | 吴学文 | The synthesis of Manganese hexacyanoferrate potassium crystallization |
| CN108017070A (en) * | 2017-12-18 | 2018-05-11 | 吴学文 | The synthesis of Manganese hexacyanoferrate potassium white crystals |
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