CN107286184A - A kind of zinc metal-organic framework materials and preparation method thereof - Google Patents
A kind of zinc metal-organic framework materials and preparation method thereof Download PDFInfo
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- CN107286184A CN107286184A CN201710560258.0A CN201710560258A CN107286184A CN 107286184 A CN107286184 A CN 107286184A CN 201710560258 A CN201710560258 A CN 201710560258A CN 107286184 A CN107286184 A CN 107286184A
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Abstract
There are load slow release function and the stable zinc metal-organic framework materials of low toxicity water resistant to 5 fluorouracil medicine molecules the present invention relates to a kind of.This material has following chemical formula：[(Me2NH2)2Zn3(fdc)4]nDMA, wherein, the dicarboxylates of fdc=furans 2,5, DMA=N, N dimethyl acetamides, (Me2NH2)+=dimethylamine cation.The present invention has synthesized a 3-dimensional metal organic framework material with one-dimensional channels from the dicarboxylic acids of furans 2,5 and zinc (Zn) metal.Zinc metal-organic framework materials of the present invention are the active drug release of a length of 180h and 93% when material after 32.9wt%, and load is sustained in phosphate buffer solution (PBS) to the load factors of 5 fluorouracils in dilute hydrochloric acid solution (pH=5 6).This metal-organic framework materials low toxicity, Stability Analysis of Structures, with very strong water-resistance, is with a wide range of applications in biological encapsulating material field.
Description
Technical field
The invention belongs to technical field of biological material, it is related to a kind of zinc metal-organic framework materials, it is more particularly to a kind of to 5-
Fluorouracil medicine molecule has load-slow-release function and the stable zinc metal-organic framework materials of low toxicity water resistant, and it is that metal has
Machine skeleton class drug loading-sustained release.
Background technology
Metal-organic framework materials (MOFs) are the metal-ligand complexings of a kind of utilization organic ligand and metal ion
Class zeolite (organic zeolite analog) material with supermolecule microporous network structure being self-assembly of, because it has Gao Bibiao
Area and pore volume, synthesis is convenient, skeleton size is variable and can be chemically modified according to target call, structure-rich etc. it is excellent
Point, gets more and more people's extensive concerning in fields such as gas absorption, catalysis, detection, photoelectric material, drug loadings.MOFs materials
The characteristics such as the avtive spot existed in structure controllable, porosity height and the duct of material are that its extensive use provides basis, near several
Year, such material has attracted the high capacity rate and long slowly releasing effect of drug molecule numerous scientific workers to study.Based on metal
In the drug sustained release system of organic porous material, the interaction force of Drug controlled release essentially from Van der Waals force, hydrogen bond, match somebody with somebody
Mutual electrostatic interaction in position key, pi-pi accumulation effect and medicine and material duct between zwitterion.In current anticancer situation
Under, threaten human life and health most serious malignant tumour more than 90% still lack so far efficiently, the medicine of high specificity.It is clinical
Chemotherapy (chemotherapy) is the Main Means for the treatment of cancer, and 5 FU 5 fluorouracil (5-FU) is clinical conventional broad-spectrum anti-cancer drug,
Often it is administered with intravenous injection or drip-feed, in vivo residence time only 5 min, so needing frequent drug administration.Simultaneously as
The medicine poor selectivity, toxic side effect is big, and plasma half-life is extremely short.But by chemical modification or by the way that 5-FU is wrapped in
Particle is prepared in different carrier materials, form a kind of new drug controlled release system to reduce its toxic side effect turns into research
Focus.
The content of the invention
The technical problems to be solved by the invention, which are to provide, relates to a kind of zinc metal-organic framework materials, and the framework material is based on
Furans -2,5 dicarboxylic acids has load-slow-release function to 5 FU 5 fluorouracil drug molecule, has good bear for 5 FU 5 fluorouracil
Load rate and slow releasing function, and low toxicity, water resistant are stable, can be applied to pharmaceutical carrier.
Technical proposal that the invention solves the above-mentioned problems is：
A kind of zinc metal-organic framework materials, its feature as：The material has below formula： [(Me2NH2)2Zn3(fdc)4]nDMA, wherein, fdc is furans -2,5 dicarboxylates, and DMA is N, N- dimethyl acetamides, (Me2NH2)+
For dimethylamine cation；Contain 3 Zn in the asymmetric constitutional repeating unit of the zinc metal organic framework2+Cation, 4
FDC anion and 1 DMA part；Zn2+For four, five, hexa-coordinate structure, Zn1 and Zn3 are six to match somebody with somebody configuration, with from six not
Carboxyl oxygen coordination on same furans -2,5 dicarboxylates, forms an octahedral geometric configuration；Zn2 is pentacoordinate configuration,
Formed by the carboxyl oxygen atom coordination on five different furans -2,5 dicarboxylates, take the trigonal biyramid ball of distortion
Configuration；Zn4 is four-coordination configuration, is matched somebody with somebody by four carboxyl oxygen atoms on four different furans -2,5 dicarboxylates
Position is formed, and is tetrahedral configuration；The connected mode of the fdc parts is to be selected from：μ4Bridging, μ3Bridging and μ3Bridging-chelating；Institute
The porous network structure that material is connected to three-dimensional is stated, wherein including oneMicropore cavity of the size along b direction of principal axis.
According to the further feature of zinc metal-organic framework materials of the present invention, it is oblique that the crystal of the material belongs to three
Crystallographic system, space group is P-1, and cell parameter is： α
=113.869 (2) °, β=95.216 (2) °, γ=90.096 (2) °；Ir data (KBr) is：3416cm-1,
2982cm-1, 1612cm-1, 1565cm-1, 1520cm-1, 1358cm-1, 1218cm-1, 1154cm-1, 1047cm-1, 1025cm-1,
982cm-1, 879cm-1, 792cm-1, 722cm-1, 684 cm-1, 638cm-1, 462cm-1。
The second aspect of the invention additionally provides the preparation method of described zinc metal-organic framework materials.
Preparation method of the present invention comprises the following steps：
(1) zinc nitrate hexahydrate of equimolar amounts and the dicarboxylic acids of furans -2,5 are added to DMAC N,N' dimethyl acetamide and water is mixed
Close solution；
(2) material in step 1 is added in 23mL ptfe autoclaves, 100 DEG C of perseverances is kept at autogenous pressures
Temperature reaction 72 hours, is then down to room temperature according to certain speed；
(3) product obtained step 2 is filtered, and collects crystal, and drying after wash with DMA solvents, obtain described in one
Plant has load-slow-release function and the stable zinc metal of low toxicity water resistant to 5 FU 5 fluorouracil drug molecule based on the dicarboxylic acids of furans -2,5
Organic framework material.
Zinc metal-organic framework materials of the present invention have advantages below：
(1) product raw material sources of the present invention extensively, are readily available；
(2) reaction condition of Product formation method of the present invention is gentle, and purity is high, and low toxicity has accomplished Green Chemistry, without lazy
Property gas shield；
(3) the zinc metal organic framework water stability that prepared by the present invention is good, MTT toxicity tests and zebra fish toxicity test
Show hypotoxicity；
(4) Zn (II) metal organic framework be based on the dicarboxylic acids of furans -2,5 have to 5 FU 5 fluorouracil drug molecule load -
Slow-release function, shows good drug loading and slow releasing function, can be applied to pharmaceutical carrier.
Brief description of the drawings
Fig. 1 is the structure chart of the asymmetric cell of the zinc metal-organic framework materials of the present invention；
Fig. 2 is H2The coordination mode figure of FDC Carboxylic acid ligands；
Fig. 3 is the three-dimensional network view of the zinc metal-organic framework materials of the present invention；
Fig. 4 is zinc metal-organic framework materials thermogravimetric curve figure of the invention；
X-ray powder diffraction figures of the Fig. 5 for zinc metal-organic framework materials of the invention under different pH concentration；
Fig. 6 water vapor adsorption-desorption thermoisopleths in 298K for zinc metal-organic framework materials of the invention
Ns of the Fig. 7 for zinc metal-organic framework materials of the invention under 77k2Suction-desorption isotherm；
Fig. 8 is sustained release-time diagram after the zinc metal-organic framework materials carrying medicament of the present invention；
Fig. 9 is the N of the zinc metal-organic framework materials of the present invention2Adsorb pore size figure；
Figure 10 is 24h MTT toxicity detections materials to NIH-3T3 and HEK-293 impact cell figures；
Figure 11 is 48h MTT toxicity detections materials to NIH-3T3 and HEK-293 impact cell figures；
Figure 12 is toxic effect figure of the material to zebra fish of various concentrations.
Embodiment
Embodiment 1：The preparation of zinc metal-organic framework materials of the present invention
1st, the preparation method of zinc metal-organic framework materials
Preparation method comprises the following steps：
(1) by the zinc nitrate hexahydrate (0.089g, 0.3mmol) and the dicarboxylic acids of furans -2,5 of equimolar amounts (0.047g,
0.3mmol) it is added to 6mLH2In O and 6mL DMA solvents；
(2) material in step 1 is added in the ptfe autoclave that volume is 23mL, kept at autogenous pressures
100 DEG C of isothermal reactions 72 hours, are then down to room temperature with 5 DEG C/h speed；
(3) mixture in step 2 is filtered, collects crystal, and drying after wash with DMA solvents, acquisition clear crystal.
According to H2It is 55% that FDC, which calculates its yield,.
2nd, the sign of zinc metal-organic framework materials
Analyzed and identified by following elementary analyses, IR spectrum and X-ray single crystal diffraction, obtained by above-mentioned preparation method
The chemical formula of clear crystal is [(Me2NH2)2Zn3(fdc)4]n·DMA。
(1) elementary analysis Zn3C32H33N3O21：Theoretical value：C,38.7；H,3.3；N, 4.2. experiment value:C,38.5； H,
3.9；N,3.8.
(2) infrared spectrum (KBr pellet, cm-1)：3416(s),2982(w),1612(vs),1565(s),1520(s),
1358(vs),1218(m),1154(m),1047(m),1025(w),982(w),879(w),792(s),722(w), 684(w),
638(m),462(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 knot
Fruit shows, 3 Zn are contained in the asymmetric constitutional repeating unit in above-mentioned Zn (II) metal organic framework2+Cation, 4 FDC
Anion and 1 DMA part.Zn2+For four, five, hexa-coordinate structure, Zn1 and Zn3 are six to match somebody with somebody configuration, and from six differences
Carboxyl oxygen coordination on furans -2,5 dicarboxylates, forms an octahedral geometric configuration；Zn2 is pentacoordinate configuration, by
Carboxyl oxygen atom coordination on five different furans -2,5 dicarboxylates is formed, and takes the trigonal biyramid ball structure of distortion
Type；Zn4 is four-coordination configuration, by four different furans -2,5 dicarboxylates four carboxyl oxygen atoms coordination and
Into being tetrahedral configuration.Fdc parts have three kinds of connected modes, respectively μ4Bridging, μ3Bridging and μ3Bridging-chelating.Based on carboxylic
The connected mode of sour part, material is connected to the porous network structure of three-dimensional.In three-dimensional net structure comprising one aboutMicropore cavity of the size along b direction of principal axis.
[(the Me of table 1.2NH2)2Zn3(fdc)4]nDMA crystallographic parameter
R=∑s (‖ Fo︱-︱ Fc‖)/∑ ︱ Fo︱ .wR=[∑ w (Fo 2–Fc 2)2/∑w(Fo)2]1/2.
[(the Me of table 2.2NH2)2Zn3(fdc)4]nDMA part bond distance's bond angle
Regular symmetric:I=-x ,-y ,-z；ii x,-1+y,z；iii x,1+y,1+z；iv 1-x,-y,-z；v 1-x,1-
y,1-z；vi 1+x,1+y,z.
Embodiment 2：The heat endurance and chemical stability of zinc metal-organic framework materials of the present invention
The zinc metal-organic framework materials obtained using embodiment 1 carry out the research of heat endurance and chemical stability, tool
Body research method is as described below：
1st, the thermally-stabilised research of zinc metal-organic framework materials
(sample is placed in 150 DEG C of vacuum after weighing the zinc metal-organic framework materials prepared by 3mg and activation respectively
Dried in drier and produce activation products in 12 hours) zinc metal-organic framework materials, with 10 DEG C/min heating rate, measurement
Its heat endurance in the range of 25-800 DEG C.(Fig. 4)
Experimental result is as shown in Figure 4：Zinc metal-organic framework materials lose two charge balances at 250 DEG C or so
[Me2NH2]+The loss of cation and a DMA molecule, mass loss 15.1% or so；In 200-250 DEG C, lose one and match somebody with somebody
Position hydrone, mass loss 27.28%；After about 360 DEG C, the frame structure of zinc metal-organic framework materials starts to decompose, finally
It is changed into metal oxide ZnO.Zinc metal-organic framework materials after activation can be stabilized in 360 DEG C.
2nd, the chemical stability based on pH value of zinc metal-organic framework materials
The 50mg zinc metal-organic framework materials synthesized are immersed in the aqueous solution of different pH value, and are stirred at room temperature 3
My god.Then its stability is studied using X-ray powder diffraction.
Experimental result is as shown in Figure 5：Zn-MOF main peaks are matched very much with analog result, illustrate zinc metal organic framework
Material is that can be stabilized in the range of 5-9 in pH value；Can not be steady under the conditions of strong acid (pH=2-3) and highly basic (pH=13-14)
It is fixed to exist.
3rd, the water stability of zinc metal-organic framework materials.
Binding molecule is simulated and experimental result, have studied zinc metal-organic framework materials under 298K to H2O adsorptivity
Matter.
Experimental result is as shown in Figure 6：Zinc metal-organic framework materials have very low adsorption rate (18.5 to hydrone
), and the filling of hole will (about P/P under relatively high pressure wt%0=1) carry out.Therefore, zinc metal organic framework
Hole in material is hydrophobic pores, with good water stability.
Embodiment 3：The encapsulation of the 5 FU 5 fluorouracil of zinc metal-organic framework materials of the present invention is tested with sustained release
The zinc metal-organic framework materials obtained using embodiment 1 carry out the encapsulation and the research of sustained release of 5 FU 5 fluorouracil.
Specific research method is as described below：
1st, the N of zinc metal-organic framework materials2- physics suction-detachment assays.
Under 77K, determine respectively after the activation of zinc metal-organic framework materials, soaked 3 days in water after and loaded 5-
N after fluorouracil medicine molecule2Physics suction-desorption isotherm.
N2Adsorption isotherm shows the I types feature (Fig. 7) of microporous materials, the zinc after being activated by theoretical calculation
The specific surface area in the hole of metal-organic framework materials is 850m2g-1.Meanwhile, in zinc metal-organic framework materials soaking water after 3 days
Its specific surface area is basically unchanged (820m2g-1), therefore the loose structure of zinc metal-organic framework materials is to be stabilized in water
, illustrate that the hydrophobic grouping methyl in zinc metal-organic framework materials framework is close apart from cadmium metal center, and can hinder
Hydrone for Zn-O and Zn-N keys attack, so as to improve the water-resistance of material.
N2Absorption measurement shows that the pore size of zinc metal-organic framework materials is(Fig. 9), its pore size (With) it is adapted to load 5 FU 5 fluorouracil (molecular size )。
2nd, load of the zinc metal-organic framework materials to 5 FU 5 fluorouracil is tested with sustained release.
(1) after 25mg is activated (sample is placed in dry in 150 DEG C of vacuum desiccator and produces activation products within 12 hours)
5 FU 5 fluorouracil is dispersed in the dilute hydrochloric acid solution that 25mL contains 5 FU 5 fluorouracil (pH=5-6), is then stirred at room temperature
72h。
(2) (5600g/10min) 5min is centrifuged, is cleaned with dilute hydrochloric acid solution, is then dried in vacuo 1 at 25 DEG C
My god, obtain the zinc metal-organic framework materials of maximum encapsulation 5 FU 5 fluorouracil amount.
(3) experiment is repeated 4 times.The 5 FU 5 fluorouracil being adsorbed onto in the zinc metal-organic framework materials hole after activation
Amount is measured by the uv-visible absorption spectra under 265nm.
The packaging efficiency of 5 FU 5 fluorouracil is calculated by below equation and obtained：
(4) the 25mg zinc metal-organic framework materials for loading 5 FU 5 fluorouracil are put into bottle, add 2mL dissolvings and be situated between
Matter (phosphate buffer solution (PBS), pH=7.4).Do not stop to stir the suspension at 37 DEG C.Pass through centrifugation at each time point
Separation (5600g/10min) takes 1mL supernatants, while being replaced with isometric (37 DEG C) fresh of PBS.The release of 5 FU 5 fluorouracil
The uv-visible absorption spectra that amount passes through under 265nm excitation wavelengths is quantified.
Test result indicates that：The specific surface area loaded in the zinc metal-organic framework materials after 5 FU 5 fluorouracil is
55m2g-1, the specific surface area reduction by 93.5% of zinc metal-organic framework materials illustrate that 5 FU 5 fluorouracil almost takes zinc completely golden
Belong to hole and the duct of organic framework material.The mass ratio of zinc metal-organic framework materials after 5 FU 5 fluorouracil is with activation is
1:3, when being contacted 3 days in 25mL dilute hydrochloric acid solutions, it can reach the preferred package effect to 5 FU 5 fluorouracil, maximum packaging efficiency
For 32.9wt%, higher than the carrier of other encapsulation 5- fluorouracils with similar aperture.
The sustained release process of the 5 FU 5 fluorouracil loaded in zinc metal-organic framework materials is as shown in Figure 8：The 5- in 30h
FU sustained release process does not occur drug release rate after " phenomenon of burst release ", 180h and reaches 93%, and release rate has phase higher than other
Like the metal-organic framework materials of result.This result that slowly discharges is probably the change due to 5 FU 5 fluorouracil molecule and hole
Caused by the superposition of interaction of hydrogen bond between environment, this is quite similar with molecular simulation result.Show the organic bone of zinc metal
Frame material has very strong suction-operated to 5 FU 5 fluorouracil.(Fig. 8)
The effective encapsulation ratio of table 3.5- fluorouracils is by 5 FU 5 fluorouracil and quality of materials than being influenceed relation table
Embodiment 4：The toxicity test of zinc metal-organic framework materials of the present invention
There are load-slow-release function and low toxicity water resistant stable to 5 FU 5 fluorouracil drug molecule using what embodiment 1 was obtained
Zinc metal-organic framework materials carry out toxicity test research.Specific research method is as described below：
1st, zinc metal-organic framework materials are obtained using embodiment 1 and carries out in vitro toxicity experiment.
Using 96 hole flat-bottom microtiter plates, using mtt assay, choose 7 kinds of various concentrations (0,0.005,0.05,0.5,5,
50 and 500 μ g/mL), Zn-MOF is determined to NIH-3T3 (mouse bone marrow cells fibroblast), and HEK-293 be (Study of Exogenous gene
Cell line) toxic effect.After incubating 24 and 48 hours, its sensitiveness is defined as 5mg/mL.
Test result indicates that, when the concentration of the zinc metal-organic framework materials after activation reaches 500 μ g/mL, zinc metal has
Machine framework material does not have toxicity (cytoactive to two kinds of selected cells>80%).
2nd, the research that zinc metal-organic framework materials carry out zebra fish live body toxicity test is obtained using embodiment 1.
(1) culture of zebra fish and the selection of embryo
The Adult Zebrafish of experiment fluorescence labeling used is provided by Nanfang Medical Univ, and daily feeding two is eaten with business fish
Secondary, holding periodicity of illumination is day (14h)/night (10h).Before laying eggs every night, 2 males and one are placed respectively in 5 incubators
Bar female adult zebra fish, and promote spawning in the next morning opening lamp.Embryonated egg is cleaned twice with fish culture medium, and
Detected under stereoscope.By normal growth and reach that the embryo of blastocyst stage is classified and collected, for subsequent experimental.
(2) 2mg/mL zinc metal-organic framework materials suspension is prepared
Zinc metal-organic framework materials are put into the water breeded fish and (include 64.75mg/L, NaHCO3；5.75mg/L, KCl；
123.25mg/L,MgSO4·7H2O and 294mg/L, CaCl2·2H2O in), and 30min is handled with ultrasonic degradation.In zebra
A series of exposure suspension (10,20,40,80 and 160 μ g/mL etc.) are prepared using dilution method step by step in fish culture medium, final
The morphological abnormalities behavior of zinc metal-organic framework materials state of aggregation in working solution detected by transmission electron microscope,
And measured using Image J softwares.
(3) toxicity of the zinc metal-organic framework materials of detection various concentrations to zebra fish
The experimental comparison group be nutrient solution, experimental group for various concentrations Zn-MOF suspension (31.25,62.5,125,
With 250 μ g/mL).Embryo is put on 24 well culture plates, per one, hole embryo, 20 embryos are used for exposure experiment on each plate,
4 embryos control as internal fish and water.Then culture plate is put into illumination box, according to 14/10h at 28 ± 1 DEG C
The periodicity of illumination of (day night) carries out illumination.Zinc metal-organic framework materials suspension each 24h during testing updates once.
At the appointed time point, is observed (t=24,48hpf) using the stereoscope equipped with digital camera.Terminal is used to assess zinc
Toxic effect of the metal-organic framework materials in zebra fish growth course, including embryo or larva it is whether lopsided.(Figure 10,11)
Test result indicates that：In 24h and 48h, the zebra fish form in control group is normal, such as has obvious fluorescence mark
Blood vessel, the backbone of note, without phenomenons such as pericardium oedema；Test results (such as Figure 12), compared with control group, do not cause substantially
Morphological variant, illustrate that zinc metal-organic framework materials do not have toxicity to zebra fish.
Claims (3)
1. a kind of zinc metal-organic framework materials, its feature as：The framework material has below formula：
[(Me2NH2)2Zn3(fdc)4]nDMA, wherein, fdc is furans -2,5 dicarboxylates, and DMA is N, N- dimethylacetamides
Amine, (Me2NH2)+For dimethylamine cation；
Contain 3 Zn in the asymmetric constitutional repeating unit of the zinc metal organic framework2+Cation, 4 FDC anion and 1
Individual DMA parts；
Zn2+For four, five, hexa-coordinate structure, Zn1 and Zn3 are six to match somebody with somebody configuration, are matched somebody with somebody from from six different furans -2,5 dicarboxylic acids
Carboxyl oxygen coordination on body, forms an octahedral geometric configuration；Zn2 is pentacoordinate configuration, by from five different furans
The coordination of the carboxyl oxygen atom on -2,5 dicarboxylates of muttering is formed, and takes the trigonal biyramid ball configuration of distortion；Zn4 is four-coordination structure
Type, is formed by four carboxyl oxygen atoms coordination on four different furans -2,5 dicarboxylates, is tetrahedral configuration；
The connected mode of the fdc parts is to be selected from：μ4Bridging, μ3Bridging and μ3Bridging-chelating；
The material is connected to the porous network structure of three-dimensional, wherein including oneMicropore of the size along b direction of principal axis
Cavity.
2. zinc metal-organic framework materials according to claim 1, it is characterised in that：It is oblique that the crystal of the material belongs to three
Crystallographic system, space group is P-1, and cell parameter is： α
=113.869 (2) °, β=95.216 (2) °, γ=90.096 (2) °；Ir data (KBr) is：3416cm-1,
2982cm-1, 1612cm-1, 1565cm-1, 1520cm-1, 1358cm-1, 1218cm-1, 1154cm-1, 1047cm-1, 1025cm-1,
982cm-1, 879cm-1, 792cm-1, 722cm-1, 684cm-1, 638cm-1, 462cm-1。
3. the preparation method of zinc metal-organic framework materials as claimed in claim 1, it is characterised in that methods described include with
Lower step：
(1) zinc nitrate hexahydrate of equimolar amounts and the dicarboxylic acids of furans -2,5 are added to DMAC N,N' dimethyl acetamide and water mixes molten
Liquid；
(2) material in step 1 is added in 23mL ptfe autoclaves, keeps 100 DEG C of constant temperature anti-at autogenous pressures
Answer 72 hours, be then down to room temperature according to certain speed；
(3) product obtained step 2 is filtered, and collects crystal, and drying after wash with DMA solvents, obtain described in zinc metal
Organic framework material.
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| CN112058237A (en) * | 2020-09-02 | 2020-12-11 | 蚌埠学院 | Preparation method of chiral metal organic framework material and application of chiral metal organic framework material in tetracycline hydrochloride sustained release |
| CN115281140A (en) * | 2022-08-12 | 2022-11-04 | 复旦大学 | Aquatic product biological marker culture method |
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