CN108409977A - Synthesis with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture - Google Patents
Synthesis with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture Download PDFInfo
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- CN108409977A CN108409977A CN201810159937.1A CN201810159937A CN108409977A CN 108409977 A CN108409977 A CN 108409977A CN 201810159937 A CN201810159937 A CN 201810159937A CN 108409977 A CN108409977 A CN 108409977A
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Abstract
The present invention relates to a kind of synthetic methods with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture, and axial extension, the ligand that synthesis phenyl ring number is 1~5 will be first carried out with the ligand material of salicylic acid structure；Ligand and nickel salt are dissolved in N, in N dimethylformamides, then water is added, the mixed solution of ethyl alcohol and triethylamine, room temperature reaction certain time obtains nano level 74 materials of Ni bases IRMOF, finally 74 materials of Ni bases IRMOF of preparation are activated, obtain 74 nano materials of Ni bases IRMOF of the non-interspersed system of low cytotoxicity.The present invention utilizes the designability of MOFs itself, by the increase of phenyl ring number in ligand chain come the accurate length for adjusting ligand, to the size of accurate adjustment aperture, by selecting suitable metal node, high stability, the Ni base MOFs nano materials of low cytotoxicity are synthesized.
Description
Technical field
The invention belongs to materials synthesis field more particularly to a series of aperture accuracy controllings of MOFs materials.
Background technology
Metal-organic framework materials [Metal-organic Frameworks, MOFs, also known as metal organic frame, metal
Organic framework material, metal organic complex or coordination polymer (coordination polymer)] be by inorganic metal from
The crystalline state porous material that son or metal cluster and organic ligand are formed by connecting has both organic material and the common characteristic of inorganic material.
The method for reporting a kind of apertures accuracy controlling MOFs from Yaghi projects in 2012 has synthesized a series of with homeomorphism knot
The IRMOF-74 of structure.(H.Deng,S.Grunder,K.E.Cordova,C.Valente,H.Furukawa,M.Hmadeh,
F.Gandara,A.C.Whalley,Z.Liu,S.Asahina,H.Kazumori,M.O’Keffe,O.Terasaki,
J.F.Stoddart, O.M.Yaghi, Science.2012,336,1018) its pore diameter range is continuous accurate by 1.4-9.8 nanometers
Regulation and control, and can successfully load green fluorescent protein macromolecular.The huge specific surface area of MOF and abundant structure diversity make it
It is loaded in guest molecule, it is especially with important application prospects in terms of the load and release of biomolecule.And it applies in biology
The material in field is mostly biased into nano-scale, is had the characteristics that hypotoxicity and is easy to be absorbed by cell.
Current MOFs material structures are difficult accuracy controlling particle size while keeping the same topology, hole
Diameter, most structures can be interted because of the increase in aperture, and stability can also be affected.
Invention content
Technical problem to be solved by the present invention lies in developing a series of nanometer particle sizes, stable structure, it is non-interspersed,
The MOFs materials of aperture accuracy controlling.
Technical scheme of the present invention can be realized by following technical measures：
Synthetic method with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture, includes the following steps：
(1) axial extension, the ligand that synthesis phenyl ring number is 1~5 will be carried out with the ligand material of salicylic acid structure；
(2) ligand and nickel salt are dissolved in n,N-Dimethylformamide, water, the mixing of ethyl alcohol and triethylamine is then added
Solution, room temperature reaction certain time obtain nano level Ni bases IRMOF-74 materials；
(3) the Ni base IRMOF-74 materials of preparation are activated, removes remaining organic solvent in duct, exposed interior
Portion duct obtains the Ni base IRMOF-74 nano materials of the non-interspersed system of low cytotoxicity.
Preferably, Suzuki coupling reactions are used in step (1), using palladium catalyst, are reacted in argon gas protects atmosphere,
The purified product by way of column chromatography realizes the incremented by successively of phenyl ring.
Preferably, the ligand material in step (1) is 2,5-Dihydroxyterephthalic acid.
Preferably, ligand phenyl ring number used is 2 or 3 in step (2).
Preferably, the volume ratio of water in step (2), ethyl alcohol and triethylamine is 9：9：1.
Preferably, the molar ratio of nickel salt and ligand is (2.5~3) in step (2)：1.
Preferably, nickel salt described in step (2) is six water nickel nitrates.
Preferably, Ni base IRMOF-74 materials repeatedly are washed with n,N-Dimethylformamide in step (3), then repeatedly used
Ethyl alcohol washs, and passes through supercritical carbon dioxide activated sample.
The invention also discloses one kind having the adjustable Ni bases MOF nano materials in low cytotoxicity aperture, using above-mentioned
Method is prepared.
By selecting non-interspersed MOFs structures, it is found that Ni-IRMOF-74 systems have prolongable potentiality and good
Stability, this is the material currently without report, Mg the and Zn system stability ratio Ni systems reported are low.
The present invention utilizes the designability of MOFs itself, and accurately ligand is adjusted by the increase of phenyl ring number in ligand chain
Length, to which the size of accurate adjustment aperture has synthesized high stability, low cell toxicant by selecting suitable metal node
The Ni base MOFs nano materials of property.
Description of the drawings
Using attached drawing, the invention will be further described, but the embodiment in attached drawing does not constitute any limit to the present invention
System.
Fig. 1 is the powder crystal diffraction pattern of Ni bases nanometer IRMOF-74-II and large scale Ni-IRMOF-74-II of the present invention,
Wherein it is actual test data, crystal face indexes (vertical line) respectively from top to bottom；
Fig. 2 is the powder crystal diffraction of Ni bases nanometer IRMOF-74-III and large scale Ni-IRMOF-74-III of the present invention
Figure, wherein being actual test data, crystal face indexes (vertical line) respectively from top to bottom；
Fig. 3 is the grain size distribution of Ni bases nanometer IRMOF-74-II of the present invention；
Fig. 4 is the grain size distribution of Ni bases nanometer IRMOF-74-III of the present invention；
Fig. 5 is the scanning electron microscope (SEM) photograph of Ni base nanometers IRMOF-74-II, 300 nanometers of left side engineer's scale, right side engineer's scale 100
Nanometer；
Fig. 6 is the scanning electron microscope (SEM) photograph of Ni base nanometers IRMOF-74-III, 300 nanometers of left side engineer's scale, right side engineer's scale 100
Nanometer；
Fig. 7 is that the cell survival rate of Ni base nanometers IRMOF-74-II is with material concentration variation diagram, Lipo and Neofect
Commercialization reagent is as reference；
Fig. 8 is that the cell survival rate of Ni base nanometers IRMOF-74-II changes over time figure, and Lipo and Neofect are business
Change reagent as reference；
Fig. 9 is Ni base nanometer IRMOF-74-II treated in different pH solution powder crystal diffraction patterns.
Specific implementation mode
To keep the present invention easier to understand, specific embodiments of the present invention are further illustrated below.
Embodiment 1
It uses Suzuki coupling reactions to extend synthesis phenyl ring number as 2 ligand 2,5-Dihydroxyterephthalic acid, remembers
For ligand i I, ligand i I is added to together with six water nickel nitrates in n,N-Dimethylformamide, ethyl alcohol, water and three second are added
Amine, agitated, exchange of solvent is dry, and activation obtains Ni base nanometer IRMOF-74-II samples.
Embodiment 2
It uses Suzuki coupling reactions to extend synthesis phenyl ring number as 3 ligand 2,5-Dihydroxyterephthalic acid, remembers
For ligand i II, ligand i II is added to together with six water nickel nitrates in n,N-Dimethylformamide, ethyl alcohol, water and three are added
Ethamine, agitated, exchange of solvent is dry, and activation obtains Ni base nanometer IRMOF-74-III samples.
Comparative example
Using achievement Hexiang Deng et al., the Supplementary Material before this seminar
for Large-Pore Apertures in a Series of Metal-Organic Frameworks.Science.336,
Large scale Ni-IRMOF-74-II and the Ni-IRMOF-74-III material that method disclosed in 1018 (2012) is prepared.
The test of particle diameter distribution：
Dried sample deionized water is disperseed, then ultrasound tests grain size point on the instrument of dynamic light scattering
Cloth.
Analysis of experimental results：
Fig. 1 is large scale Ni-IRMOF- obtained by 1 gained Ni base nanometer IRMOF-74-II of the embodiment of the present invention and comparative example
The powder crystal diffraction pattern of 74-II, the Ni base nanometer IRMOF-74-II grain sizes synthesized as seen from the figure significantly reduce.
Fig. 2 is large scale Ni-IRMOF- obtained by 2 gained Ni base nanometer IRMOF-74-III of the embodiment of the present invention and comparative example
The powder crystal diffraction pattern of 74-III, the Ni base nanometer IRMOF-74-III grain sizes synthesized as seen from the figure significantly reduce.
Fig. 3 is the grain size distribution of 1 gained Ni base nanometers IRMOF-74-II of the embodiment of the present invention, illustrates Ni base nanometers
The hydration grain size of IRMOF-74-II is less than 200 nanometers.
Fig. 4 is that the grain size distribution of 2 gained Ni base nanometers IRMOF-74-III of the embodiment of the present invention illustrates Ni base nanometers
The hydration grain size of IRMOF-74-III is less than 200 nanometers.
Fig. 5 is the scanning electron microscope (SEM) photograph of 1 gained Ni base nanometers IRMOF-74-II of embodiment, and 300 nanometers of left side engineer's scale is right
100 nanometers of side engineer's scale illustrates Ni base nanometer IRMOF-74-II granular sizes in 100 rans.
Fig. 6 is the scanning electron microscope (SEM) photograph of 2 gained Ni base nanometers IRMOF-74-III of embodiment, and 300 nanometers of left side engineer's scale is right
100 nanometers of side engineer's scale illustrates Ni base nanometer IRMOF-74-III granular sizes in 100 rans.
Fig. 7 is the cell survival rate of 1 gained Ni base nanometers IRMOF-74-II of embodiment with material concentration variation diagram, Lipo
With Neofect be commercialization reagent as reference, illustrate Ni base nanometer IRMOF-74-II cytotoxicities compared with traditional commerce reagent
It is lower.
Fig. 8 is that the cell survival rate of 1 gained Ni base nanometers IRMOF-74-II of embodiment changes over time figure, Lipo and
Neofect be commercialization reagent as reference, Ni base nanometer IRMOF-74-II cytotoxicities are lower compared with traditional commerce reagent.
Fig. 9 is 1 gained Ni base nanometer IRMOF-74-II of embodiment treated in different pH solution powder crystal diffraction
Figure illustrates that the material of gained is relatively stable in acidity, alkaline environment.
The stable system for the Ni-IRMOF-74 systems ratio Mg and Zn that the present invention uses, by the number for increasing phenyl ring in ligand
Amount, the aperture of the MOFs materials of accuracy controlling synthesis realize and are continuously adjusted in the same topological system aperture.Dynamic optical
Scattering experiment and scanning electron microscope experiment say its nanoparticle size in 100 rans.The data of X-ray diffraction illustrate structure with
The structure of simulation is consistent, and under different conditions, and the ratio traditional commerce reagent of such MOFs material is with lower thin
Cellular toxicity.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than is protected to the present invention
The limitation of range is protected, although being explained in detail to the present invention with reference to preferred embodiment, those skilled in the art should
Understand, technical scheme of the present invention can be modified or replaced equivalently, without departing from the essence of technical solution of the present invention
And range.
Claims (9)
1. the synthetic method with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture, which is characterized in that including walking as follows
Suddenly：
(1) axial extension, the ligand that synthesis phenyl ring number is 1~5 will be carried out with the ligand material of salicylic acid structure；
(2) ligand and nickel salt are dissolved in n,N-Dimethylformamide, water is then added, the mixing of ethyl alcohol and triethylamine is molten
Liquid, room temperature reaction certain time obtain nano level Ni bases IRMOF-74 materials；
(3) the nanoscale Ni base IRMOF-74 materials of preparation are activated, obtains the Ni JiIRMOF-74Na of low cytotoxicity
Rice material.
2. the synthetic method according to claim 1 with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture,
It is characterized in that, Suzuki coupling reactions is used in step (1), using palladium catalyst, reacted in argon gas protects atmosphere, pass through column
The mode purified product of chromatography, realizes the incremented by successively of phenyl ring.
3. the synthetic method according to claim 1 with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture,
It is characterized in that, the ligand material in step (1) is 2,5-Dihydroxyterephthalic acid.
4. the synthetic method according to claim 1 with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture,
It is characterized in that, ligand phenyl ring number used is 2 or 3 in step (2).
5. the synthetic method according to claim 1 with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture,
It is characterized in that, water in step (2), the volume ratio of ethyl alcohol and triethylamine is 9：9：1.
6. the synthetic method according to claim 1 with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture,
It is characterized in that, the molar ratio of nickel salt and ligand is (2.5~3) in step (2)：1.
7. the synthetic method according to claim 1 with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture,
It is characterized in that, nickel salt described in step (2) is six water nickel nitrates.
8. the synthetic method according to claim 1 with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture,
It is characterized in that, Ni base IRMOF-74 materials is activated by supercritical carbon dioxide in step (3).
9. one kind having the adjustable Ni bases MOF nano materials in low cytotoxicity aperture, which is characterized in that use claim 1-8
Any one of them method is prepared.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105457A (en) * | 2021-03-29 | 2021-07-13 | 深圳大学 | Thermal activation delayed fluorescence crystalline framework material and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105457A (en) * | 2021-03-29 | 2021-07-13 | 深圳大学 | Thermal activation delayed fluorescence crystalline framework material and preparation method and application thereof |
| CN113105457B (en) * | 2021-03-29 | 2022-03-15 | 深圳大学 | Thermal activation delayed fluorescence crystalline framework material and preparation method and application thereof |
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