CN106084246A - A kind of both sexes carboxylic acid metal's coordination polymer based on gadolinium and preparation method thereof - Google Patents

A kind of both sexes carboxylic acid metal's coordination polymer based on gadolinium and preparation method thereof Download PDF

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CN106084246A
CN106084246A CN201610403497.0A CN201610403497A CN106084246A CN 106084246 A CN106084246 A CN 106084246A CN 201610403497 A CN201610403497 A CN 201610403497A CN 106084246 A CN106084246 A CN 106084246A
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gadolinium
carboxylic acid
acid metal
coordination polymer
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CN106084246B (en
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陈金香
覃亮
陈文华
刘叔文
庞建新
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Southern Medical University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • A61K49/10—Organic compounds
    • A61K49/101—Organic compounds the carrier being a complex-forming compound able to form MRI-active complexes with paramagnetic metals
    • A61K49/106—Organic compounds the carrier being a complex-forming compound able to form MRI-active complexes with paramagnetic metals the complex-forming compound being cyclic, e.g. DOTA
    • 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
    • A61K49/10—Organic compounds
    • A61K49/12—Macromolecular compounds
    • A61K49/122—Macromolecular compounds dimers of complexes or complex-forming compounds

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Abstract

The present invention relates to a kind of both sexes carboxylic acid metal's coordination polymer based on gadolinium, these both sexes carboxylic acid metal's coordination polymer be repetitive be [Gd (Cmdcp) (H2O)3](NO3)·3H2The gadolinium metal coordinating polymer of O, described chemical formula [Gd (Cmdcp) (H2O)3](NO3)·3H2Cmdcp in O is N carboxymethyl (3,5 dicarboxyl) pyridinium bromide；The good water solubility of both sexes carboxylic acid metal's coordination polymer of the present invention, metal payload rate is high, has good contrast activity.

Description

A kind of both sexes carboxylic acid metal's coordination polymer based on gadolinium and preparation method thereof
Technical field
The present invention relates to chemical field, be specifically related to metal coordinating polymer.
Background technology
Nuclear magnetic resonance (MRI) is a nuclear magnetic resonance technique important application in biomedicine, and property that it is radiationless is damaged Wound, the advantage such as high-resolution and faster image taking speed, can effectively detect tissue necrosis, ischemia and various malignant change ((such as tumor).Although the development time of nmr imaging technique is the longest, but have become as now in medical imaging technology least One of technology that can or lack, and greatly promoted developing rapidly of medical science, neuro physiology and cognitive neuroscience.
When clinical implementation MRI scan, owing to normal structure and pathological tissues only show the least signal difference, about The clinical MRI scanning having 35% needs the contrast using magnetic resonance contrast agent (MRI contrast agents) to strengthen image. Contrast agent, also known as contrast medium (Contrast Agent/Contrast Media), is to inject for strengthening or affect observing effect Or take the chemicals of tissue or organ.MRI contrast agent can make the SI of local signal intensity (SI) and other position Compare observable change, reach preferably to expose the purpose of pathological tissues.The most clinical the most frequently used contrast agent is containing Gd3+ Paramagnetic metal coordination compound, wherein diethyl pentetic acid close gadolinium (Gd-DTPA) most.But apply at present Little molecule-type contrast agent there is more problem, as relaxivity is low, consumption is big, and toxicity is high, and circulation time is short etc. in blood, makes Shadow effect is the most inconspicuous.Along with the development of contrast agent enhanced MRI imaging technique is with universal, its imaging advantage obtains more and more Certainly, in addition at the application potential in molecular imaging field, the research work of contrast agent performance improvement is also subject to increasing Pay close attention to.
Metal coordinating polymer (Metal-organic Frameworks, MOFs) is a class by metal center and organic joins Body by the way of self assembly, a kind of porous crystalline material of formation, have that synthetic method is simple, with low cost, physical chemistry The feature of unique properties.Therefore, this material gas absorption with separate, organic reaction catalysis, bio-imaging, magnetic material, The field such as Small-molecule probe and medicine carrying is respectively provided with certain application prospect.But the research that MOFs is in terms of MRI contrast agent is always Fail to be goed deep into.
2008, Lin seminar of the U.S. first will be based on p-phthalic acid and Gd3+The MOFs constructed is applied to MRI radiography In, although this material shows higher transverse relaxation rate and more obvious T1 weighted imaging effect in vitro, but owing to changing Therefore the toxicity of compound is higher cannot be carried out in-depth study.Although it is relatively low that this seminar have selected toxicity in research subsequently Mn2+The MOFs constructed with p-phthalic acid is as MRI contrast agent, but the not enough defect of water solublity makes this research not obtain yet more Further break through.Therefore, design synthesis has preferable water miscible MOFs material, to further investigation MOFs further at MRI Research in terms of mri contrast agent is significant.
Root is according to the literature[1-3], quaternary ammonium salt functional group is because of its bigger polarity so that this compounds has preferable water Dissolubility.Quaternary ammonium salt functional group is incorporated in MOFs the water solublity that can significantly strengthen this compounds.Quaternary carboxylic acid Part the most not only plays the stronger coordination ability of carboxylic acid and the advantage of various coordination mode, and effectively overcomes carboxylic acids The defect that MOFs dissolubility is poor.Gd3+Because having substantial amounts of unpaired electron, there is bigger magnetic moment, susceptibility and longer The Study of Electron Spin Relaxation Time time, in the tissue relaxivity of proton can be greatly improved.At present, joining containing carboxylic acid and quaternary ammonium salt group Body research is less, and reports as the most rarely seen document of research of MRI contrast agent about this type of MOFs.
List of references:
[1]Okware SI,Omaswa F,Talisuna A,et al.Managing Ebola from rural to urban slum settings:experiences from Uganda.Afr Health Sci,2015,15(1),312- 321.
[2]Schuler-Faccini L,Ribeiro EM,Feitosa IM,et al.Possible association between zika virus infection and microcephaly-brazil,2015.MMWR Morb Mortal Wkly Rep,2016,65(3),59-62.
[3]Kurosaki Y,Magassouba N,Oloniniyi OK,et al.Development and evaluation of reverse transcription-loop-mediated isothermal amplification (RT-LAMP)assay coupled with a portable device for rapid diagnosis of ebola virus disease in Guinea.Plos Negl Trop Dis,2016,10(2),2-8
Summary of the invention
The technical problem to be solved is to provide a kind of both sexes carboxylic acid metal's coordination polymer based on gadolinium, and these are two years old Property carboxylic acid metal's coordination polymer good water solubility, metal payload rate is high, has good contrast activity.
The present invention solves the technical scheme of the problems referred to above:
A kind of both sexes carboxylic acid metal's coordination polymer based on gadolinium, these both sexes carboxylic acid metal's coordination polymer is that repetitive is [Gd(Cmdcp)(H2O)3](NO3)·3H2The gadolinium metal coordinating polymer of O, chemical formula [Gd (the Cmdcp) (H of described repetitive2O)3] (NO3)·3H2Cmdcp in O is N-carboxymethyl-(3,5-dicarboxyl) pyridinium bromide；Described gadolinium metal coordinating polymer has three-dimensional Network, its space group is P21/ n, cell parameter is respectivelyα =90 °, β=102.2020 (10) °, γ=90 °, ir data (KBr) is: 3410 (s), 1647 (s), 1610 (s), 1390(s),1238(m),1175(w),1114(w),935(m),770(m),728(m),630(m),520(m)cm-1。
Above-mentioned both sexes copper carboxylate metal coordinating polymer is colourless bulk crystals at normal temperatures, and its constitutional repeating unit contains One [Gd (Cmdcp) (H2O)3]+Cation, a NO3 -Anion and three dissociating water molecules.Each Gd3+With from 5 In Cmdcp part, four carboxyls are coordinated in monodentate mode, while a carboxyl is coordinated in chelating mode, also with 3 hydrones It is coordinated, forms the anti-prism structure in single cap four directions.Cmdcp part and Gd3+Connect node simultaneously as five, form three dimensional network Lattice structure.
Both sexes carboxylic acid gadolinium metal coordinating polymer of the present invention uses preparation method commonly used in the art, e.g., by N- Acetic acid-(3,5-dicarboxylic acids) pyridinium bromide and Gd (NO3)3·6H2O reaction obtains.The method that the present inventor recommends, by following step Rapid composition:
(1) by H3CmdcpBr dissolves and is dispersed in water, and by NaOH solution, pH is adjusted to 6.0～7.0, obtains ligand solution；
(2) it is H by mole3Gd (the NO of CmdcpBr 2/3 times3)2·6H2O is dissolved in the water, and obtains gadolinium saline solution；
(3) ligand solution that step (1) obtains is joined in ligand solution the gadolinium salt that step (2) obtains molten Liquid, and stirring reaction 0.5～1h at a temperature of 90～100 DEG C, filter, collect filtrate；
(4) filtrate that step (3) obtains at room temperature being stood, crystal is collected by filtration, ether is cleaned and is vacuum dried To described both sexes carboxylic acid metal's coordination polymer based on gadolinium.
Described both sexes carboxylic acid metal's coordination polymer based on gadolinium of the present invention has good T1 relaxation rate, Ke Yiying With for paramagnetism mri contrast agent.
Described both sexes carboxylic acid metal's coordination polymer based on gadolinium of the present invention shows more medical paramagnetism in vitro Mri contrast agent Magnevist Solution (Gd-DTPA) higher transverse relaxation rate and more obvious T1 weighted imaging effect.
It also have the advantage that
(1) product raw material sources of the present invention are extensive, are readily available；
(2) reaction condition of Product formation method of the present invention is gentle, and the time is short, can obtain by recrystallization in aqueous, produce Rate is high, and purity is high, nontoxic, has accomplished Green Chemistry, it is not necessary to inert gas shielding；
(3) both sexes carboxylic acid metal coordination polymer shows good external MRI contrast activity.
Accompanying drawing explanation
Fig. 1 is Gd3+Five connecting joint point diagrams.
Fig. 2 is five connecting joint point diagrams of Cmdcp part.
Fig. 3 is the three-dimensional hole structure chart of both sexes carboxylic acid metal's coordination polymer of gadolinium of the present invention.
Fig. 4 is the external contrasting effects figure of both sexes carboxylic acid metal's coordination polymer of gadolinium of the present invention, and in figure, a is chemical combination The relaxation rate figure of thing Gd-MOF and Gd-DTPA, b is the T of compound Gd-MOF and Gd-DTPA1Weighted imaging figure.
Detailed description of the invention
Embodiment 1
1, the preparation of both sexes carboxylic acid metal's coordination polymer based on gadolinium
Preparation method comprises the following steps:
(1) N-(4-carboxybenzyl) of 0.09mmol (28mg)-(3,5-dicarboxyl benzene) pyridinium bromide is dispersed in 5mL water In, molar concentration is that pH is adjusted to 6.0～7.0 by the NaOH solution of 0.1mM (i.e. 0.1mmol/L), obtains ligand solution；
(2) by the Gd (NO of 0.06mmol (27mg)3)2·6H2O is dissolved in 1mL water, obtains gadolinium saline solution；
(3) ligand solution that step (1) obtains is joined the gadolinium saline solution that step (2) obtains, stirring reaction 0.8h, mistake Filter, collects filtrate；
(4) filtrate step 3 obtained at room temperature stands one week, and crystal is collected by filtration, and ether is cleaned and is vacuum dried Obtain 31mg clear crystal (through measuring and calculating productivity: 56%).
2, the qualification of both sexes carboxylic acid metal's coordination polymer based on gadolinium
By following elementary analysis, IR spectrum and X-ray single crystal diffraction Analysis and Identification, colourless obtained by above-mentioned steps 1 Crystal is both sexes carboxylic acid metal's coordination polymer based on gadolinium of the present invention, and the molecular formula of its repetitive is [Gd (Cmdcp)(H2O)3](NO3)·3H2O。
(1) elementary analysis C9H17GdN2O15-2H2O: theoretical value: C, 21.01；H,2.55；N,5.45；Experiment value: C, 20.69；H,2.01；N,5.81.
(2) infrared spectrum (KBr disk, cm-1): 3410 (s), 1647 (s), 1610 (s), 1390 (s), 1238 (m), 1175(w),1114(w),935(m),770(m),728(m),630(m),520(m)。
(3) X-ray single crystal diffraction: crystallographic parameter and part bond distance are as shown in Table 1 and Table 2.X-ray single crystal diffraction is tied Fruit shows, the repetitive in both sexes carboxylic acid metal's coordination polymer based on gadolinium is asymmetric cell, each asymmetric cell In containing [Gd (Cmdcp) (H2O)3]+Cation, a NO3 -Anion and three dissociating water molecules.As it is shown in figure 1, it is every Individual Gd3+[Mn1 marked in Fig. 1] is coordinated in monodentate mode with from four carboxyls in 5 Cmdcp parts, carboxyl with While chelating mode is coordinated, also it is coordinated with 3 hydrones, forms the anti-prism structure in single cap four directions.Cmdcp part (Fig. 2) and Gd3+(Fig. 2) connect node simultaneously as five, form three dimensional network structure (seeing Fig. 3).
Table 1. [Gd (Cmdcp) (H2O)3](NO3)·3H2The crystallographic parameter of O
aR=| | Fo|-|Fc|/|Fo|.bWR={w (Fo 2-Fc 2)2/w(Fo 2)2}1/2.cGOF={w ((Fo 2-Fc 2)2)/(n- p)}1/2
Table 2. [Gd (Cmdcp) (H2O)3](NO3)·3H2Part bond distance's bond angle of O
Utilize the atom that symmetry transformation generates: #1-x+1/2, y-1/2 ,-z+3/2；#2x+1/2,-y+1/2,z+1/2；#3- x+1,-y,-z+2；#4x,y,z+1；#5x-1/2,-y+1/2,z-1/2；#6-x+1/2,y+1/2,-z+3/2；#7x,y,z-1.
Embodiment 2
Both sexes carboxylic acid metal's coordination polymer based on gadolinium that the present embodiment employing embodiment 1 obtains is as MRI contrast agent Carry out performance study.Concrete research method is as described below:
(1) compound concentration of the present invention: under the conditions of 25 DEG C, both sexes carboxylic acid based on gadolinium of the present invention Metal coordinating polymer concentration of aqueous solution is 500 μMs.
(2) external radiography performance test: be 30 DEG C in temperature, in the environment of magnetic field intensity is 0.5T, with Gd-DTPA as sun Property matched group, compares both sexes carboxylic acid metal's coordination polymer based on gadolinium of the present invention and Gd-DTPA under variable concentrations External radiography performance.
(6) experimental result
External visualisation shows (such as Fig. 4), and both sexes carboxylic acid metal's coordination polymer based on gadolinium of the present invention is equal Demonstrate more commercial transverse relaxation rate higher for contrast agent Gd-DTPA and become apparent from T1Weighted imaging effect.

Claims (2)

1. both sexes carboxylic acid metal's coordination polymer based on gadolinium, these both sexes carboxylic acid metal's coordination polymer be repetitive be [Gd (Cmdcp)(H2O)3](NO3)·3H2The gadolinium metal coordinating polymer of O, chemical formula [Gd (the Cmdcp) (H of described repetitive2O)3](NO3)· 3H2Cmdcp in O is N-carboxymethyl-(3,5-dicarboxyl) pyridinium bromide；Described gadolinium metal coordinating polymer has three dimensional network structure, Its space group is P21/ n, cell parameter is respectivelyα =90 °, β=102.2020 (10) °, γ=90 °, ir data (KBr) is: 3410 (s), 1647 (s), 1610 (s), 1390(s),1238(m),1175(w),1114(w),935(m),770(m),728(m),630(m),520(m)cm-1。
2. the preparation method of the both sexes carboxylic acid metal's coordination polymer based on gadolinium described in claim 1, the method is by following step Rapid composition:
(1) by H3CmdcpBr dissolves and is dispersed in water, and by NaOH solution, pH is adjusted to 6.0～7.0, obtains ligand solution；
(2) it is H by mole3Gd (the NO of CmdcpBr 2/3 times3)2·6H2O is dissolved in the water, and obtains gadolinium saline solution；
(3) ligand solution that step (1) obtains is joined the gadolinium saline solution that step (2) obtains in ligand solution, And stirring reaction 0.5～1h at a temperature of 90～100 DEG C, filter, collect filtrate；
(4) filtrate that step (3) obtains at room temperature being stood, crystal is collected by filtration, ether is cleaned and is vacuum dried and obtains institute The both sexes carboxylic acid metal's coordination polymer based on gadolinium stated.
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CN108373537A (en) * 2017-04-26 2018-08-07 池州学院 A kind of gadolinium coordination polymer and preparation method thereof with adsorpting lead ion
CN112961294A (en) * 2021-02-05 2021-06-15 河南大学 Water-soluble MOF composite polymer material and preparation method and application thereof

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CN108373537B (en) * 2017-04-26 2019-05-24 池州学院 A kind of gadolinium coordination polymer and preparation method thereof with adsorpting lead ion
CN112961294A (en) * 2021-02-05 2021-06-15 河南大学 Water-soluble MOF composite polymer material and preparation method and application thereof

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