CN104512911A - Preparation methods of bismuth ferricyanide crystal and nano particle thereof - Google Patents

Preparation methods of bismuth ferricyanide crystal and nano particle thereof Download PDF

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CN104512911A
CN104512911A CN201310461542.4A CN201310461542A CN104512911A CN 104512911 A CN104512911 A CN 104512911A CN 201310461542 A CN201310461542 A CN 201310461542A CN 104512911 A CN104512911 A CN 104512911A
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吴学文
吴界
陈虹
黄颂平
姚国胜
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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
    • C01C3/11—Complex cyanides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Iron (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)

Abstract

The invention relates to preparation methods of a compound crystal and a nano particle thereof, wherein the compound is represented as the molecular formula of A<x>Bi<y>[M(CN)6]<z>.nH2O, wherein A is lithium, sodium, potassium, ammonium or thallium; M is chromium, manganese, iron, cobalt or ruthenium; x=0-2, y=1-4, z=1-4; and n=0,1-20. The crystal and the nano particle thereof can be used for preparing a CT contrast medium.

Description

The preparation method of a kind of iron cyaniding bismuth crystallization and nanoparticle thereof
Technical field
The present invention relates to a kind of molecular formula is AxBiy [M (CN) 6] znH2O, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the compound crystal of n=0,1-20 and the preparation method of nanoparticle thereof, this crystallization and nanoparticle thereof can be used for the preparation of CT contrast medium.
Background technology
Molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the compound crystal of n=0,1-20 and the preparation method of nanoparticle thereof, this crystallization and nanoparticle thereof can be used for the preparation of CT contrast medium.
Summary of the invention
The invention provides a kind of molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the compound crystal of n=0,1-20 and the preparation method of nanoparticle thereof, this crystallization and nanoparticle thereof can be used for the preparation of CT contrast medium.
1, molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And n=0, the preparation of the compound crystal of 1-20 mainly comprises the following steps:
With six cyanogen metal complex ion [M (CN) 6] n-(M=Cr, Mn, Fe, Co or Ru +, n=2-3) and trivalent bismuth ion Bi 3+by hybrid reaction, obtaining molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the crystallization of n=0,1-20 compound.
Wherein six cyanogen metal complex ion [M (CN) 6] n-m=Cr, Mn, Fe, Co or Ru +, n=2-3), the aqueous citric acid solution being dissolved in 5%-20% (weight) is called A1, is dissolved in 5%-20% (weight) aqueous tartaric acid solution and is called A2, be dissolved in lactic acid: the lactic acid aqueous solution of the volume ratio 1:5-20 of water is called A3;
Wherein trivalent bismuth ion Bi 3+, the aqueous citric acid solution being dissolved in 5%-20% (weight) is called B1, is dissolved in 5%-20% (weight) aqueous tartaric acid solution and is called B2, be dissolved in lactic acid: the lactic acid aqueous solution of the volume ratio 1:5-20 of water is called B3;
A1 to be poured in B1 to obtain into C1, or A1 to be poured in B2 to obtain into C2, or A1 to be poured in B3 to obtain into C3;
A2 to be poured in B1 to obtain into D1, or A2 to be poured in B2 to obtain into D2, or A2 to be poured in B3 to obtain into D3;
A3 to be poured in B1 to obtain into E1, or A3 to be poured in B2 to obtain into E1, or A3 to be poured in B3 to obtain into E3;
Crystallization CI, C2, C3, D1, D2, D3, E1, E2, E3 that above-mentioned hybrid mode obtains, its molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the crystallization of the compound of n=0,1-20, wherein Bi [Fe (CN) 6] 4H 2the x-ray diffractogram of powder of O compound crystal is Fig. 1, and crystalline particle particle diameter is between 0.5-120 micron.
2, molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And n=0, the nanoparticle preparation of the compound crystal of 1-20 mainly comprises the following steps:
Be AxBiy [M (CN) by molecular formula 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; With the compound crystal of n=0,1-20 is dissolved in the aqueous solution of formula for meglumine, Sunmorl N 60S, Zonon D, polyvinylpyrrolidone; Or be dissolved in the aqueous solution of formula for meglumine, Sunmorl N 60S, Zonon D, after solution is transparent, then add polyvinylpyrrolidone; Or be dissolved in the aqueous solution of formula for meglumine, Sunmorl N 60S, after solution is transparent, add polyvinylpyrrolidone, after solution is transparent, then add Zonon D; Wherein polyvinylpyrrolidone can substitute with chitosan or available carboxyl dextran, wherein each Ingredient Amount is meglumine 5%-20% (weight), Sunmorl N 60S 5%-20% (weight), Zonon D 0.5-3.0% (weight), polyvinyl pyrrolidone content is 5%-15% (weight), chitosan content is 2.5%-15% (weight), carboxyl dextran content is 2.5%-15% (weight), after each composition all adds, continue to stir 6-36 hour, the molecular formula forming stable transparent is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the nano-particle solution of the compound crystal of n=0,1-20, its PH scope is between 1.5-11.5, and trivalent bismuth ion content is between 0.001-600mM, and nano particle diameter is between 1-800nm.
3, molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the nano-particle solution of the compound crystal of n=0,1-20, wherein Bi [Fe (CN) 6] 4H 2the nano-particle solution CT pH-value determination pH of O crystallization as a result, when bismuth is identical with iodine volumetric molar concentration, Bi [Fe (CN) 6] 4H 2the nano-particle solution CT value of O crystallization is 1.30-1.80 times of iodo CT contrast medium CT value, can be used as the preparation of CT contrast medium.
(1) Bi [Fe (CN) 6] the nano-particle solution CT value of 4H2O crystallization and the relation of bismuth-containing amount
(2) relation of iodo CT contrast medium CT value and amount of iodine
Accompanying drawing explanation
Fig. 1 is the AxBiy [M (CN) prepared by the embodiment of the present invention 1 6] znH 2o crystallization, wherein Bi [Fe (CN) 6] 4H 2the powder x-ray diffraction figure of O crystallization.
Fig. 2 is the AxBiy [M (CN) prepared by the embodiment of the present invention 2 6] znH 2the nano-particle solution of O crystallization, wherein Bi [Fe (CN) 6] 4H 2the nano-particle solution transmission electron microscope picture of O crystallization, nano particle diameter is between 1-50nm.
Fig. 3 is the AxBiy [M (CN) prepared by the embodiment of the present invention 2 6] znH 2the nano-particle solution of O crystallization, wherein Bi [Fe (CN) 6] 4H 2the nano-particle solution sample transmission electron microscope X-ray energy spectrum figure of O crystallization, the element ratio recording bismuth and iron is 1:1.
Embodiment
Embodiment 1:
Molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And Bi [Fe (CN) in the compound crystal of n=0,1-20 6] 4H 2the preparation of O crystallization:
Take 989 milligrams of K 3[Fe (CN) 6] put into 100 ml beakers, add lactic acid: the lactic acid aqueous solution 25ml of the volume ratio 1:10 of water dissolves completely, be called for short sample A; Take 1455 milligrams of Bi (NO 3) 35H 2o puts into 100 ml beakers, adds lactic acid: the lactic acid aqueous solution 25ml of the volume ratio 1:10 of water dissolves completely, is called for short sample B; Poured into by sample A in the beaker of sample B, seal beaker mouth with sealing compound, under lucifuge, room temperature obtains iron cyaniding bismuth Bi [Fe (CN) after leaving standstill 0-12 hour 6] 4H 2o crystallization, crystalline particle particle diameter is between 0.5-120 micron, and its x-ray diffractogram of powder is Fig. 1.
Embodiment 2:
Molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And Bi [Fe (CN) in the compound crystal of n=0,1-20 6] 4H 2the preparation of the nanoparticle of O crystallization:
Take meglumine 10.00g, Sunmorl N 60S 10g, Zonon D 0.40g, in 100ml beaker, adds water to 40ml, magnetic agitation, to dissolving completely, is called for short sample A.
Take polyvinylpyrrolidone 10g gradation again to add in sample A, constantly stir, and be progressively heated to 60 DEG C, maintain 60 DEG C and dissolve completely to polyvinylpyrrolidone, solution is that micro-Huang is transparent, and then is cooled to room temperature, is called for short sample B.
Take iron cyaniding bismuth Bi [Fe (CN) 6] 4H 2o crystallization 6.86g joins in sample B, constantly stirs, to iron cyaniding bismuth Bi [Fe (CN) 6] 4H 2o crystallization is dissolved completely, and solution is amber transparent, continues stirring 12 hours, obtains iron cyaniding bismuth Bi [Fe (CN) 6] 4H 2o crystalline nanoparticles solution, is called for short sample C.The pH value recording sample C is 8.5; Transmission electron microscope observation is to sample C nano particle equiblibrium mass distribution in the solution, and particle diameter, at 1-50nm, is shown in Fig. 2; The element ratio that transmission electron microscope X-ray energy spectrum records sample C bismuth and iron is 1:1, sees Fig. 3;
Embodiment 3:
Molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And Bi [Fe (CN) in the compound crystal nano-particle solution of n=0,1-20 6] 4H 2o crystalline nanoparticles solution C T pH-value determination pH result:
(1) Bi [Fe (CN) 6] 4H 2the nano-particle solution CT value of O crystallization and the relation of bismuth-containing amount
(2) relation of iodo CT contrast medium CT value and amount of iodine
When bismuth is identical with the volumetric molar concentration of iodine, Bi [Fe (CN) 6] 4H 2the nano-particle solution CT value of O crystallization is 1.30-1.80 times of iodo CT contrast medium CT value, can be used as the preparation of CT contrast medium.

Claims (12)

1. a molecular formula is: A xbi y[M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the preparation method of the compound crystal of n=0,1-20.
2. compound according to claim 1, is characterized in that, with six cyanogen metal complex ion [M (CN) 6] n-(M=Cr, Mn, Fe, Co or Ru, n=2-3) and trivalent bismuth ion Bi 3+by hybrid reaction, obtaining molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the crystallization of n=0,1-20.
3. six cyanogen metal complex ion [M (CN) according to claim 2 6] n-(M=Cr, Mn, Fe, Co or Ru +, n=2-3), it is characterized in that, be dissolved in the aqueous citric acid solution of 5%-20% (weight), 5%-20% (weight) aqueous tartaric acid solution, lactic acid: in the lactic acid aqueous solution of the volume ratio 1:5-20 of water.
4. trivalent bismuth ion Bi according to claim 2 3+, it is characterized in that, be dissolved in the aqueous citric acid solution of 5%-20% (weight), 5%-20% (weight) aqueous tartaric acid solution, lactic acid: in the lactic acid aqueous solution of the volume ratio 1:5-20 of water.
5. AxBiy [M (CN) according to claim 2 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the crystallization of n=0,1-20, wherein Bi [Fe (CN) 6] 4H 2the x-ray diffractogram of powder of O compound crystal is Fig. 1.
6. AxBiy [M (CN) according to claim 2 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the crystallization of n=0,1-20, crystalline particle particle diameter is between 0.5-120 micron.
7., according to claim 2, described crystallization is dissolved respectively by following 3 kinds of modes:
Be dissolved in the aqueous solution of formula for meglumine, Sunmorl N 60S, Zonon D, polyvinylpyrrolidone;
Or be dissolved in the aqueous solution of formula for meglumine, Sunmorl N 60S, Zonon D, stir 0.5-6 hour, after forming steady clear solution, then gradation adds polyvinylpyrrolidone;
Or be dissolved in the aqueous solution of formula for meglumine, Sunmorl N 60S, stir 0.5-6 hour, after forming stable transparent solution, gradation adds polyvinylpyrrolidone, is stirred to after forming clear solution, then adds Zonon D;
Continue to stir 6-36 hour; Formation molecular formula is AxBiy [M (CN) 6] znH 2o, wherein A=Li, Na, K, NH 4, or Tl; M=Cr, Mn, Fe, Co or Ru; X=0-2; Y=1-4; Z=1-4; And the nano-particle solution of the stable transparent of n=0,1-20 compound crystal;
In said process, polyvinylpyrrolidone can substitute with chitosan or available carboxyl dextran; In said process, various Ingredient Amount is: meglumine 5%-20% (weight), Sunmorl N 60S 5%-20% (weight), Zonon D 0.5-3.0% (weight), polyvinyl pyrrolidone content is 5%-15% (weight), chitosan content is 2.5%-15% (weight), and carboxyl dextran content is 2.5%-15% (weight).
8. nano-particle solution according to claim 7, is characterized in that wherein trivalent bismuth ion content is between 0.001-600mM.
9. nano-particle solution according to claim 7, it is characterized in that, its PH is between 1.5-11.5.
10. nano-particle solution according to claim 7, it is characterized in that, described nano particle diameter is between 1nm-800nm.
11. nano-particle solution according to claim 7, is characterized in that, when bismuth is identical with the volumetric molar concentration of iodine, described nano-particle solution CT value be the 1.30-1.80 of iodo CT contrast medium CT value doubly.
12. nano-particle solution according to claim 7, is characterized in that the preparation being used as CT contrast medium.
CN201310461542.4A 2013-10-08 2013-10-08 Preparation methods of bismuth ferricyanide crystal and nano particle thereof Pending CN104512911A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LIANG-DONG FENG ET AL.: "Electrochemical Controllable Synthesis of Bismuth Hexacyanoferrate(II) Nanoplates and Its Application in Electrocatalysis", 《JOURNAL OF PHYSICAL CHEMISTRY C》 *
VINDYA S. PERERA ET AL.: "Nanoparticles of the Novel Coordination Polymer KBi(H2O)2[Fe(CN)6] nH2O As a Potential Contrast Agent for Computed", 《INORGANIC CHEMISTRY》 *
W. PETTER ET AL.: "The Crystal Structure of BiFe(CN)·4H20 and BiCo(CN)6·4H20", 《INORGANICA CHIMICA ACTA》 *

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Application publication date: 20150415