CN110256684A - A kind of tetrapyridylporphine metal-organic framework materials and preparation method and purposes - Google Patents
A kind of tetrapyridylporphine metal-organic framework materials and preparation method and purposes Download PDFInfo
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Abstract
A kind of tetrapyridylporphine metal-organic framework materials and preparation method and purposes, the present invention relates to a kind of pyridyl group porphyrin metal-organic framework materials (MOFs), the object of the present invention is to provide a kind of tetrapyridylporphine metal-organic framework materials, that is MOFs, the organic framework materials include porphyrin containing pyridine substituents and the metal ion being coordinated by the nitrogen-atoms on the pyridine substituents on porphyrin ring, corresponding preparation method and purposes are also provided, it is compared with existing technology, the advantage of MOFs prepared by the present invention is as follows: 1. can synthesize at room temperature, can exist steadily in the long term in water;2. the range of metal used is very wide;3. palladium metal-the organic framework materials obtained when using palladium as coordinating metal can carry hydrogen after carrying out reduction, hydrogen atom and the palladium of monatomic distribution are coordinated, higher than there is the palladium particle of record to carry hydrogen amount;4. obtained Pd-MOFs is with porous structure;5. the porphyrin in porphyrin MOFs is a kind of photosensitizer, there is fluorescent emission.
Description
Technical field
The present invention relates to a kind of pyridyl group porphyrin metal-organic framework materials (MOFs), and in particular to a kind of pyridyl group porphin
Quinoline MOFs and preparation method thereof as well as functional material are applied to the purposes of medicine, imaging, catalysis, sensing etc..
Background technique
Self-assembled material with specific shape and structure is the research hotspot of field of functional materials, in electricity, optics, energy
The fields such as amount conversion, gas absorption separation, catalysis have been widely used.In field of biomedicine, metal-organic framework materials exist
Drug delivery, bio-imaging, sensing and diagnosis etc. have important application.The good characteristic of MOFs is on the one hand from its knot
Structure feature, such as porosity, high-ratio surface, modifiability, thermal stability etc., on the other hand from the metal of coordination, these gold
Belong to and assigns the special performance of MOFs.There is good application using MOFs as catalyst, artificial enzyme, but its performance is often depending on
How the metal of load is coordinated the metallicity realization functionalization of node by adjusting, is a problem.Meanwhile it is existing
MOFs is easily hydrolyzed in the presence of aqueous vapor since coordinate bond is weaker and structure collapse is occurred, and influences its use.And MOFs generally with
Hydrothermal synthesis, reaction process are longer.Therefore, a kind of rapid synthesis and the MOFs material that can be stabilized in water at room temperature are explored
It is necessary to.Tetrapyridylporphine is a kind of neutral ligand, has very strong coordination ability to many metals, can be with a variety of gold
Belong to coordination and obtain the MOFs of different metal, is provided convenience to provide more diverse catalytic performance.
Summary of the invention
Mentioned above to overcome the problems, such as, the present invention provides a kind of the following technical solution:
An object of the present invention is to provide a kind of a kind of tetrapyridylporphine metal-organic framework materials, i.e. MOFs, institute
The organic framework materials stated include porphyrin containing pyridine substituents and by the nitrogen-atoms on the pyridine substituents on porphyrin ring
The metal ion being coordinated.
Preferably, the porphyrin containing pyridine substituents be 5,10,15,20- tetra- (4- pyridyl group) porphyrins (TPyP) and/
Or its metal complex (MTPyP).If metalloporphyrin, then intermetallic metal ion is zinc ion, copper ion, iron ion, ferrous iron
Ion, manganese ion, platinum ion, lead ion, cobalt ions, aluminium ion, gadolinium ion, iridium ion and gold ion etc..
Further, the metal ion is palladium ion, platinum ion, bismuth ion, gold ion, silver ion, cadmium ion, nickel
Ion more than one.Specific metal salt includes Na2PdCl4、K2PdCl4、H2PtCl6、Bi(NO3)3、BiCl3、HAuCl4、
AgNO3、Cd(NO3)2、CdCl2、NiCl2、Ni(NO3)2Deng.
The second object of the present invention is to provide the preparation method of a kind of tetrapyridylporphine metal-organic framework materials, institute
The preparation method stated comprises the following steps that
(1) it reacts: by the metal salt of coordination and four pyridylporphyrin solution hybrid reactions, stirring, after fully reacting, obtain simultaneously
To MOFs, then pass through washing, ethanol washing and vacuum drying;According to different situations, it can be used heating or do not heat
Mode is reacted, and reaction temperature is in 0~200 DEG C.
Quantitative reaction is carried out between metal salt and TPyP or MTPyP, wherein between the metal salt and four pyridylporphyrins
Molar ratio range is 0.25~4;
Dry temperature is controlled at 20~60 DEG C;
The reaction solution is water or chloroform, methylene chloride, methanol, ethyl alcohol, toluene, n,N-Dimethylformamide etc.,
Reaction carries out at room temperature, without heating.
(2) it restores: MOFs and reducing agent is mixed, the molar ratio of reducing agent and coordinating metal is 2:1~20:1.Instead
It should be centrifuged and wash 2~3 times after the completion, it is dry.
Wherein the molar ratio of reducing agent and coordinating metal is 2:1~20:1.
The reducing agent used in step (2) is sodium borohydride, ascorbic acid, hydrogen or hydrazine hydrate, and wherein sodium borohydride is also
Original carries out under room temperature or ice-water bath, and hydrazine hydrate and hydrogen are restored at room temperature, and ascorbic acid reduction needs to add at 80 DEG C
It is carried out under heat condition.
Then washing is dried in vacuo using washing or ethanol washing, dry temperature is controlled at 20~60 DEG C.
For moieties, the preparation method, which still further comprises, carries hydrogen step (3): coordinating metal Pd, Pt's
Porphyrin MOFs carries hydrogen, before use, hydrogen will be passed through at room temperature in the porphyrin MOFs aqueous dispersions after reduction, the time continue to
15 minutes few, gained is the porphyrin MOFs hydrogenated.
The third object of the present invention is to provide a system of above-mentioned a kind of tetrapyridylporphine metal-organic framework materials
The new application of column, the substance can be used as nano-functional material applied to fields such as medicine, chemical catalysis, photocatalysis, in medicine
Field can be used as hydrogen drug and carry out hydrogen delivering, as the photothermal conversion reagent of photo-thermal therapy and making for photoacoustic imaging
Shadow agent.Realize the image supervisory control of tumour hydrogen heat cure.Specific purposes is as follows:
1. the photosensitizer as photodynamic therapy uses.
2. the porphyrin MOFs for the palladium containing zeroth order that coordinating metal restores when being palladium, has good affinity to hydrogen atom,
It can be used as hydrogen treating drug, for providing reproducibility hydrogen.
3. the porphyrin MOFs for the palladium containing zeroth order that coordinating metal restores when being palladium is used as photothermal conversion agent after adding hydrogen, uses
In the photo-thermal therapy and photoacoustic imaging contrast-enhancing agent of tumour.
4. the porphyrin MOFs for the palladium containing zeroth order that coordinating metal restores when being palladium, purposes can be catalyzed ammonia borine
Fast hydrolyzing.
5. being used as the catalyst of hydrogenation reaction.
6. being used as the catalyst of photodissociation aquatic products hydrogen.
7. being used as the functional component of chemical sensor.
8. partial size can be controlled by using surfactant, nanometer and micron particles is made.
It is compared with existing technology, the advantage of MOFs prepared by the present invention is as follows:
1. porphyrin MOFs prepared by the present invention can be synthesized at room temperature, the strong coordination between pyridine and metal makes it can
And can exist steadily in the long term in water;
2. the range of metal that porphyrin MOFs prepared by the present invention is used is very wide, and can restore the metal of coordination, obtain
To the metal outside porphyrin ring inner ring with mixed valence, metal species can arbitrarily arrange in pairs or groups, feature-rich adjustable, can apply
In fields such as medicine, analytical chemistry, materials chemistry, synthesis chemistry, energy chemistries;
3. palladium metal-the organic framework materials for being when using palladium as coordinating metal can carry hydrogen, hydrogen atom after carrying out reduction
It is coordinated with the palladium of monatomic distribution, H/Pd atomic ratio theoretical value is 2:1, and measured value reaches 1:1, than there is record at present
It is high that palladium particle carries hydrogen amount;
4. obtained Pd-MOFs is with porous structure, high-ratio surface can be also used for carrying medicine, realize hydrogen treating with
The joint of the other treatments mode such as chemotherapy;
5. the porphyrin in porphyrin MOFs is a kind of photosensitizer, there is fluorescent emission, photodynamic therapy and fluorescence can be used
Tracer is imaged.
Detailed description of the invention
Fig. 1 is PdCl2The transmission electron microscope picture of-MOF
Fig. 2 is PdCl2The scanning electron microscope (SEM) photograph of-MOF
Fig. 3 is PdCl2The distribution of the hydrodynamic force size of-MOF, Pd-MOF and PdH-MOF
Fig. 4 is TPyP, PdCl2The uv absorption spectra of-MOF, Pd-MOF and PdH-MOF
Fig. 5 is TPyP, PdCl2The excitation of the fluorescence of-MOF, Pd-MOF and PdH-MOF, transmitting figure
Fig. 6 is TPyP, PdCl2- MOF, Pd-MOF, PdH-MOF and Na2PdCl4Near infrared absorption spectrogram
Fig. 7 is PdCl2The x-ray diffractogram of powder of-MOF is composed
Fig. 8 is PdCl2The X-ray electronic energy spectrum of-MOF and Pd-MOF
Fig. 9 is that the near infrared light of PdH-MOF nano particle is calculated according to heating and photothermal conversion efficiency
Figure 10 is the dynamic process that hydrogen is discharged by MB probe in detecting PdH-MOF nano particle
Figure 11 is the cell survival rate that PdH-MOF is used for cellular level tumour hydrogen heat integration treatment
Figure 12 is effect picture of the PdH-MOF for hydrogen heat integration treatment in mouse tumor body
Figure 13 is the mouse tumor heating and photothermal imaging comparison after PBS, Pd-MOF and PdH-MOF injection
Figure 14 is that photoacoustic imaging and signal of the PdH-MOF nano particle at mouse tumor position change over time trend
Figure 15 is PdCl2Fluorescence imaging and distribution of-the MOF nano particle in mouse main organs and tumour
Figure 16 is HE coloration result of the PdH-MOF for mouse main organs after mouse tumor treatment
Figure 17 is the transmission electron microscope picture of platinum organic framework materials prepared by the present invention.
Specific embodiment
It is beneficial to understand the present invention by following specific embodiments, but does not limit the contents of the present invention.
Embodiment 1
(1) PdCl is prepared2- MOF nano particle
(4- pyridyl group) porphyrin of 5,10,15,20- tetra- (TPyP) of 20mg (0.032mmol) is weighed first in the burning of 100mL
In cup, the hydrochloric acid solution and stirring that 10mL 10mM is added dissolve it sufficiently, separately weigh 19mg's (0.064mmol)
Na2PdCl4, it is dissolved into 10mL pure water.Na is added in above-mentioned TPyP hydrochloric acid solution while agitating2PdCl4In solution, stir
Mix 4 hours, stop reaction, reaction solution is transferred to centrifuge tube and is centrifuged 20 minutes with the revolving speed of 12000rpm, outwell supernatant, precipitating after
It is continuous to be washed with water centrifugation 2~3 times.Precipitating, which is distributed in pure water, to be saved backup.
(2)PdCl2The reduction of-MOF nano particle
By PdCl obtained above2- MOF nano particle 10mL (10mg) aqueous dispersions cooling 30min in ice-water bath,
It is added with stirring 10 microlitres of hydrazine hydrates, by the way that product is collected by centrifugation after 8h, and is washed with water 3 times and removes extra reducing agents, obtain
Pd-MOF after to reduction.
(3) preparation of PdH-MOF
It is continually fed into 30min hydrogen into Pd-MOF nano particle 10mL (10mg) aqueous dispersions, process is observed that
Nano suspending liquid darkens to get to PdH-MOF nanoparticles solution, and obtained PdH-MOF suspension needs to make as early as possible
With or sealing after be kept in dark place.
The MOF obtained using palladium as coordinating metal is uniform spherical structure, and Fig. 1 and Fig. 2 show PdCl2- MOF nanometers
The transmission electron microscope and scanning electron microscope pattern of particle, Fig. 3 show its hydrodynamics size, it may be said that bright obtained MOFs is equal
Even spherical nanostructure, and palladium is reduced rear pattern without significant change.Pd-MOF after reduction is inhaled with stronger near-infrared
It receives, adds hydrogen influx and translocation (see Fig. 4).Fig. 5 illustrates the fluorescence excitation and emission spectra of palladium porphyrin MOFs, it can be seen that PdCl2-
MOF nano particle has the fluorescent emission similar with TPyP, can be used for fluorescence imaging, and fluorescent emission disappears after restoring.From
From the point of view of infrared absorption spectrum (Fig. 6), compared with porphyrin, with the peak pyridine N-H after metal coordination from 1593cm-1It is moved to
1609cm-1, and in 970cm-1The peak N-H in place's porphyrin pyridine ring on pyrroles does not change, and illustrates that palladium is and the pyrrole outside porphyrin ring
Pyridine nitrogen is coordinated, rather than is coordinated in the ring of porphyrin.Fig. 7 is PdCl2The X ray diffracting spectrum of-MOF, it can be seen that
There are three groups of characteristic diffraction peaks.XPS analysis (Fig. 8) shows PdCl2- MOF reduction front and back Pd/Cl element ratio is reduced to 0.02 from 0.41,
Pd-MOF after reduction shows Pd03d3/2(341.1eV) and 3d5/2The peak (335.8eV).Meanwhile stronger near infrared absorption is assigned
Its good photothermal conversion ability is given, measuring PdH-MOF in the photothermal conversion efficiency of 808nm is 44.2% (see Fig. 9).It utilizes
PdH-MOF measures hydrogen release process, entire release process continues 5 days the catalytic reduction performance of methylene blue
Reach balance, with the reaction of hydrogen water and methylene blue as a comparison, illustrate release is reproducibility hydrogen, H/Pd ratio be 0.98 (see
Figure 10).The hydrogen heat cure of in vitro and in vivo is carried out with PdH-MOF, it can be seen that in cell (see Figure 11) and animal (see Figure 12)
There is good curative effect to breast cancer in level, and photothermal imaging (Figure 13), photoacoustic imaging (Figure 14), fluorescence imaging can be utilized
(Figure 15) is monitored treatment.Cell and zoopery also confirm material to normal cell (see Figure 11) and the nontoxic (figure of tissue
16)。
Embodiment 2
(4- pyridyl group) porphyrin of 5,10,15,20- tetra- (TPyP) of 20mg (0.032mmol) is weighed first in the burning of 100mL
In cup, the hydrochloric acid solution and stirring that 10mL 10mM is added dissolve it sufficiently, separately weigh 66mg's (0.128mmol)
H2PtCl6·6H2O is dissolved into 10mL pure water.H is added in above-mentioned TPyP hydrochloric acid solution while agitating2PtCl6In solution,
Stirring 12 hours stops reaction, and reaction solution is transferred to centrifuge tube and is centrifuged 20 minutes with the revolving speed of 12000rpm, and supernatant is outwelled, and sinks
Shallow lake order water and ethanol washing are centrifuged 2~3 times, and 40 DEG C of vacuum drying 12h obtain porphyrin-platinum-gold category organic framework materials.
Figure 17 shows that porphyrin-platinum-gold category organic framework materials transmission electron microscope picture, pattern are ribbon nano junction
Structure.
Claims (17)
1. a kind of tetrapyridylporphine metal-organic framework materials, which is characterized in that the organic framework materials include to contain
The porphyrin of pyridine substituents and the metal ion being coordinated by the nitrogen-atoms on the pyridine substituents on porphyrin ring.
2. one kind tetrapyridylporphine metal-organic framework materials as described in claim 1, which is characterized in that described contains
The porphyrin of pyridine substituents is (4- pyridyl group) porphyrin of 5,10,15,20- tetra- and/or its metal complex.
3. one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 2, which is characterized in that described 5,
The intermetallic metal ion of 10,15,20- tetra- (4- pyridyl group) porphyrin metal complex is zinc ion, copper ion, iron ion, ferrous iron
One or more of ion, manganese ion, platinum ion, lead ion, cobalt ions, aluminium ion, gadolinium ion, iridium ion and gold ion.
4. one kind tetrapyridylporphine metal-organic framework materials as described in claim 1, which is characterized in that the gold
Category ion be palladium ion, platinum ion, bismuth ion, gold ion, silver ion, cadmium ion, nickel ion more than one.
5. one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 4, which is characterized in that corresponding gold
Belonging to salt includes Na2PdCl4、K2PdCl4、H2PtCl6、Bi(NO3)3、BiCl3、HAuCl4、AgNO3、Cd(NO3)2、CdCl2、
NiCl2、Ni(NO3)2。
6. the preparation method of a kind of tetrapyridylporphine metal-organic framework materials, which is characterized in that the preparation method packet
Include following step:
(1) it reacts: by the metal salt of coordination and four pyridylporphyrin solution hybrid reactions, stirring, after fully reacting, obtain simultaneously
Then MOFs passes through washing, ethanol washing and vacuum drying;
Wherein the molar ratio range between the metal salt and four pyridylporphyrins is 0.25~4;
Dry temperature is controlled at 20~60 DEG C;
(2) it restores: MOFs and reducing agent is mixed, the molar ratio of reducing agent and coordinating metal is 2:1~20:1.It has reacted
At rear centrifugation and wash 2~3 times, it is dry.
7. the preparation method of one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 6, feature exist
In the preparation method, which still further comprises, carries hydrogen step (3): the porphyrin MOFs of coordinating metal Pd, Pt carry hydrogen, are using
Before, hydrogen will be passed through at room temperature in the porphyrin MOFs aqueous dispersions after reduction, the time continues at least 15 minutes, and gained is hydrogen
The porphyrin MOFs of change.
8. the preparation method of one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 6, feature exist
In the reaction solution used in step (1) is water, chloroform, methylene chloride, methanol, ethyl alcohol or toluene, N, N- dimethyl formyl
Amine, reaction carry out at room temperature.
9. the preparation method of one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 6, feature exist
In the reducing agent used in step (2) is sodium borohydride, ascorbic acid, hydrogen or hydrazine hydrate.
10. the new use of a kind of tetrapyridylporphine metal-organic framework materials as claim in any one of claims 1 to 9
On the way.
11. the new application of one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 10, feature exist
In the machine frame frame material is used as the photosensitizer of photodynamic therapy.
12. the new application of one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 10, feature exist
In the porphyrin MOFs for the palladium containing zeroth order that the coordinating metal restores when being palladium is as hydrogen treating drug, for providing
Reproducibility hydrogen.
13. the new application of one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 10, feature exist
In the porphyrin MOFs for the palladium containing zeroth order that coordinating metal restores when being palladium is used as photothermal conversion agent after adding hydrogen, for tumour
Photo-thermal therapy and photoacoustic imaging contrast-enhancing agent.
14. the new application of one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 10, feature exist
In the porphyrin MOFs for the palladium containing zeroth order that coordinating metal restores when being palladium is used as the fast hydrolyzing for promoting catalysis ammonia borine.
15. the new application of one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 10, feature exist
In the machine frame frame material is used as the catalyst of hydrogenation reaction.
16. the new application of one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 10, feature exist
In the machine frame frame material is used as the catalyst of photodissociation aquatic products hydrogen.
17. the new application of one kind tetrapyridylporphine metal-organic framework materials as claimed in claim 10, feature exist
In the machine frame frame material is used as the functional component of chemical sensor.
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