CN109535436A - A kind of metalloporphyrin frame material and its preparation method and application with hollow nanostructures - Google Patents
A kind of metalloporphyrin frame material and its preparation method and application with hollow nanostructures Download PDFInfo
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- CN109535436A CN109535436A CN201811610166.XA CN201811610166A CN109535436A CN 109535436 A CN109535436 A CN 109535436A CN 201811610166 A CN201811610166 A CN 201811610166A CN 109535436 A CN109535436 A CN 109535436A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
- A61K41/0076—PDT with expanded (metallo)porphyrins, i.e. having more than 20 ring atoms, e.g. texaphyrins, sapphyrins, hexaphyrins, pentaphyrins, porphocyanines
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
Abstract
The invention belongs to field of nanometer material technology, are related to a kind of metalloporphyrin frame material and its preparation method and application with hollow nanostructures.The material has huge cavity and shell, and the shell is made of metalloporphyrin frame material.The size of the nano material is 20-200nm, shell thickness 5-50nm, cavity diameter 10-200nm.For loading perfluocarbon, perfluocarbon has high dissolved oxygen performance, can provide more oxygen with high-efficient carrier oxygen for optical dynamic therapy the huge cavity of hollow PMOF nanoparticle, to generate more singlet oxygens, enhances light power curative effect.The huge cavity of hollow PMOF nanoparticle and shell hole can be with high-efficient carrier diagnosis and treatment reagents, including chemotherapeutic, photothermal reagent, imaging molecule etc..Hollow PMOF has broad application prospects as a kind of novel nano medicament carrying system.
Description
Technical field
The invention belongs to field of nanometer material technology, in particular to a kind of metalloporphyrin frame with hollow nanostructures
Frame material and its preparation method and application.
Background technique
Metal organic framework (Metal-organic frameworks, MOFs) material is a kind of novel organic and inorganic
Hybridization porous material is formed by connecting by metal ion or metal cluster node and organic ligand.MOFs material, which has, greatly compares table
Area and the good characteristics such as porosity, the chemical structure in adjustable aperture and controlled shape and composition, good biological degradability,
Therefore the MOFs material nano-carrier platform novel as one, shows huge application potential in field of biomedicine.
Metalloporphyrin frame material (porphyrin metal-organic frameworks, PMOF) is one kind by gold
Belong to ion or metal ion cluster and the carboxylic acid porphyrin ligand with photosensitive activity by being coordinated the orderly sky of the three-dimensional stability formed
Between reticular structure.Photosensitizer porphyrin molecule directly participates in the building of PMOF as organic ligand, realizes the efficient negative of photosensitizer
It carries, while avoiding active oxygen quantum yield decline caused by photosensitizer molecule is assembled, therefore PMOF has excellent photocatalysis
Activity and light power effect.
Photodynamic therapy is a kind for the treatment of means emerging in recent years, has many advantages, such as that controllability is good, Small side effects.It is former
Reason is photosensitizer under the excitation of light source, and the oxygen molecule for activating surrounding generates active oxygen, with the important feature of this damaging cells and
Function is finally reached the purpose for destroying pathological tissues.Oxygen is that photoactivation generates an indispensable essential condition of active oxygen.
But the weary oxygen feature of most of pathological tissues makes the decline significant in efficacy of light power, moreover, optical dynamic therapy is one quick
The process of oxygen consumption, and then cause Domino effect, further suppress optical dynamic therapy.Therefore, it is protected during optical dynamic therapy
The sufficient oxygen of card is supplied in a great problem urgently to be resolved for photodynamic therapy.
The use of nano medicament carrying system promote drug especially hydrophobic drug in vivo in conveying, improve drug
Stability and targeting, improve the bioavailability of drug, significantly reduce the toxic side effect of drug, while can realize medicine
The sustained release of object becomes the hot spot in current medical research field.Realize drug high-efficient carrier be still nano medicament carrying system always
The target of unremitting pursuit.
Summary of the invention
To solve the above problems, the present invention provides a kind of metalloporphyrin frame material with hollow nanostructures.This hair
The bright shell hole of the metalloporphyrin frame material with hollow nanostructures with huge cavity and high-sequential, one
Aspect can be used for loading perfluocarbon, and sufficient oxygen is provided for optical dynamic therapy, enhance light power effect；It on the other hand can
With the various diagnosis and treatment reagents of high-efficient carrier.
In a first aspect, the present invention provides a kind of metalloporphyrin frame material with hollow nanostructures, by cavity and
Shell composition, the shell is by Zr6Cluster (Zr6O4(OH)4(H2O)6(OH)6(COO)6) and tetrabasic carboxylic acid ligand with photosensitive activity
5,10,15,20- tetra- (4- carboxyl phenyl) porphyrin (5,10,15,20-tetrakis (4-carboxyphenyl)
Porphyrin(H2TCPP the orderly space net structure of the three-dimensional stability)) formed by coordination.
Preferably, the size of the metalloporphyrin frame material with hollow nanostructures is 20-200nm, and shell is thick
Degree is 5-50nm.
Second aspect, the present invention provides a kind of metalloporphyrin frame material (hollow PMOF) with hollow nanostructures
Preparation method, comprising the following steps:
(a) inorganic nano-particle is prepared to sacrifice template；
(b) it disperses inorganic nano-particle made from step (a) in solvent, the source zirconium (Zr), organic ligand H is added2TCPP and
Auxiliary adjustment ligand, the auxiliary adjustment ligand are benzoic acid, acetic acid, formic acid, trifluoroacetic acid or hydrochloric acid, and 70-150 DEG C of heating is anti-
Answer, after be collected by centrifugation product, it is core that washing, which obtains inorganic nano-particle, and metalloporphyrin frame material is the nanocomposite of shell；
(c) nanocomposite that etch step (b) obtains removes inorganic nano-particle core to get described with hollow
The metalloporphyrin frame material of nanostructure.
Step (a) inorganic nano-particle includes cuprous oxide, silica, titanium dioxide three-iron, ferroso-ferric oxide, two
Titanium oxide, manganese oxide, aluminium oxide, zinc oxide, calcium phosphate etc..
Preferably, the size of step (a) inorganic nano-particle is 10-200nm, and the size of inorganic nano-particle determines
The size of hollow PMOF cavity.Cavity diameter is 10-200nm.
The solvent that step (b) disperses inorganic nano-particle is one of N,N-dimethylformamide, water, methanol, ethyl alcohol
Or it is several.
Step (b) reaction temperature is preferably 80-120 DEG C.
The source zirconium (Zr), organic ligand H2TCPP and auxiliary adjustment ligand are the precursor of metalloporphyrin frame material.
The source Zr is soluble compound containing Zr, it is preferable that the source Zr is ZrCl4、ZrOCl2·8H2O.Preferably,
The auxiliary adjustment ligand is benzoic acid.
The source Zr, organic ligand H in PMOF precursor2The molar ratio of TCPP and auxiliary adjustment ligand is (5-10): 1:(100-
300).
Change the source Zr, organic ligand H in the PMOF precursor being added2The available difference of the amount of TCPP and auxiliary adjustment ligand
The PMOF of shell thickness.
In step (c), the nanocomposite that etch step (b) obtains removes inorganic nano-particle core, to aoxidize Asia
Copper, titanium dioxide three-iron, ferroso-ferric oxide, titanium dioxide, manganese oxide, aluminium oxide, zinc oxide, calcium phosphate are the nano combined of core
Material uses acid etch, uses alkaline etching or hf etching by the nanocomposite of core of silica, in addition to this, also
Different lithographic methods can be used according to different inorganic nano-particle cores.
The acid of the acid etch is hydrochloric acid, sulfuric acid, hydrofluoric acid or nitric acid.
The alkali of alkaline etching is sodium hydroxide, potassium hydroxide or sodium carbonate.
Preferably, the pH of the acid of the acid etch is 0-3.The pH of the alkali of alkaline etching is 7-11.
The third aspect, the present invention provide a kind of application of metalloporphyrin frame material with hollow nanostructures, including
Below two aspect:
(a) present invention has the huge cavity in the metalloporphyrin frame material of hollow nanostructures for loading perfluocarbon,
Using the high dissolved oxygen performance of perfluocarbon, sufficient oxygen is provided for hollow PMOF, to generate more singlet oxygens, is enhanced
Light power effect.
(b) present invention has huge cavity and shell hole in the metalloporphyrin frame material of hollow nanostructures can
With high-efficient carrier diagnosis and treatment reagent, including chemotherapeutic, photothermal reagent, imaging molecule etc..
To sum up, beneficial effect of the present invention includes the following aspects.
1, the present invention has metalloporphyrin frame material, that is, hollow PMOF of hollow nanostructures, due to photosensitizer porphyrin
Molecule directly participates in the building of hollow PMOF as organic ligand, realizes the high-efficient carrier of photosensitizer, while avoiding photosensitive
The decline of active oxygen quantum yield caused by agent molecule is assembled, therefore there is hollow PMOF excellent photocatalytic activity and light power to imitate
Fruit.
2, the metalloporphyrin frame material of the invention with hollow nanostructures has huge cavity, complete for loading
Fluorocarbons provides sufficient oxygen for hollow PMOF, to generate more singlets using the high dissolved oxygen performance of perfluocarbon
Oxygen enhances optical dynamic therapy effect.
3, the present invention has the huge cavity of metalloporphyrin frame material of hollow nanostructures and shell hole can be high
Effect load diagnosis and treatment reagent.
Detailed description of the invention
Fig. 1 is Cu prepared by embodiment 12The transmission electron microscope picture of O@PMOF nanocomposite；
Fig. 2 is the transmission electron microscope picture of hollow PMOF prepared by embodiment 1；
Fig. 3 is the X-ray powder diffraction pattern of hollow PMOF prepared by embodiment 1；
Fig. 4 is the grain size distribution of hollow PMOF prepared by embodiment 1；
Fig. 5 is the hollow PMOF of 3 mean quality concentration of embodiment and has loaded the singlet oxygen production of the hollow PMOF of perfluoro-compound
Raw situation.
Specific embodiment
The following is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principle of the present invention, some improvements and modifications can also be made, these improvement and modification are also considered as
Protection scope of the present invention.
Embodiment 1:
A kind of preparation of the metalloporphyrin frame material with hollow nanostructures, comprising the following steps:
(1) by 0.001molCuAc2·3H2It is dissolved in O and 0.01mol polyvinylpyrrolidone (PVP, MW30000)
30.0mL ethylene glycol.Then, 10.0mL NaOH(2.0molL is added dropwise into above-mentioned solution-1), continue to stir 0.5h, be added
10.0mL ascorbic acid solution (0.3molL-1), then reacted 30 minutes at 55 DEG C.After product is collected by centrifugation, it is washed with water
It washs 3 times, obtains Cu2O nanoparticle.
(2) by 10mg Cu2O nanoparticle is scattered in 10mL DMF, and 0.093mmol ZrOCl is added2·8H2O、
0.013mmol H2TCPP and 2.30mmol benzoic acid, heating reaction 5h is cooled to room temperature after reaction at 90 DEG C, from
It after the heart collects product, then is washed 3 times with DMF, is obtained with Cu2O is core, and PMOF is the nanocomposite Cu of shell2O@PMOF。
(3) by Cu2O@PMOF is scattered in 50mL HCl(0.1molL-1) in, it is stirred at room temperature for 24 hours, product is collected by centrifugation
Afterwards, 5 times are washed to get hollow PMOF with one-stage water wash.
Fig. 1 is Cu prepared by embodiment 12The transmission electron microscope picture of O@PMOF nanocomposite, it can be seen from the figure that this
Cu obtained by embodiment2The partial size of O@PMOF nanocomposite is 110-150nm, shell thickness 20-25nm.
Fig. 2 is the transmission electron microscope picture of hollow PMOF prepared by embodiment 1, it can be seen from the figure that obtained by the present embodiment
Hollow PMOF be the nanosphere with hollow structure, partial size 110-150nm, shell thickness 20-25nm.
Fig. 3 is the X-ray powder diffraction pattern of hollow PMOF prepared by embodiment 1, it can be seen from the figure that the present embodiment
Obtained hollow PMOF is 4.5o、6.4o、7.9o、9.1o、11.2oThere is characteristic diffraction peak, and diffraction maximum peak type is more sharp, diffraction
Intensity is high, shows that obtained hollow PMOF crystallinity is preferable.
Fig. 4 is the grain size distribution that hollow PMOF made from embodiment 1 is measured using dynamic light scattering, can from figure
Out, hollow-PMOF particle diameter distribution made from the present embodiment is more uniform, averagely hydration partial size be 255.1nm, PDI 0.089,
Monodispersity is good.
Embodiment 2:
A kind of preparation of the metalloporphyrin frame material with hollow nanostructures, comprising the following steps:
(1) by 74mL ethyl alcohol, 10mL H2O and 3.14mL ammonia solution mixes and stirs 0.5h at 30 DEG C.Then, by 6mL silicic acid
Ethyl ester is added rapidly in above-mentioned solution, and the reaction was continued 1 hour.After product is collected by centrifugation, is respectively washed 3 times, obtained with second alcohol and water
To SiO2Nanoparticle.
(2) by 10mg SiO2It is scattered in 10mL level-one water, 10mL PVP(20mgmL is added-1), 12h is stirred at room temperature,
After product is collected by centrifugation, is washed 3 times with one-stage water wash, obtain the SiO of surface modification PVP2Nanoparticle SiO2@PVP。
(3) by 10mg SiO2@PVP nanoparticle is scattered in 10mL DMF, and 0.093mmol ZrOCl is added2·8H2O、
0.013mmol H2TCPP and 2.3mmol benzoic acid, heating reaction 5h is cooled to room temperature after reaction at 110 DEG C, from
It after the heart collects product, then is washed 3 times with DMF, is obtained with SiO2For core, PMOF is the nanocomposite SiO of shell2@PMOF。
(4) by SiO2@PMOF is scattered in 50mL Na2CO3(0.4molL-1) in solution, 10h is reacted at 50 DEG C, it reacts
After, it is cooled to room temperature, after product is collected by centrifugation, washs 5 times with one-stage water wash to get hollow PMOF.
Embodiment 3: the light power effect of the metalloporphyrin frame material with hollow nanostructures of perflexane is loaded
Perfluor is loaded with the metalloporphyrin frame material (hollow PMOF) made from the embodiment of the present invention 1 with hollow nanostructures
Hexane (PFH) obtains the hollow hollow PMOF of PMOF(PFH@of load perflexane (PFH)), carry out the verifying of light power effect.With
For hollow PMOF as control, operating procedure is as follows:
(1) toward the hollow PMOF(10ugmL of 3mL-1) 15uLDPBF solution (10molL is added in dispersion liquid-1), 660nm laser
(500mWcm-2) irradiation different time, with UV-Vis measurement 1,3- diphenyl isobenzofuran (DPBF) at 467nm wavelength
Absorption value variation, measure the case where hollow PMOF generates singlet oxygen, as a result as shown in Figure 5.
(2) toward the hollow PMOF(10ugmL of 3mLPFH@-1) 15uL DPBF solution (10molL is added in dispersion liquid-1),
660nm laser (500mWcm-2) irradiation different time, changed with absorption value of the UV-Vis measurement DPBF at 467nm wavelength,
The case where hollow PMOF of PFH@generates singlet oxygen is measured, as a result as shown in Figure 5.
From fig. 5, it can be seen that the speed ratio of the light absorption value decline of the DPBF of the hollow PMOF of PFH@is hollow under same concentrations
PMOF is fast, and the overall amplitude of decline is also more than hollow PMOF, this is because PFH has high dissolved oxygen performance, it can be hollow PMOF
Sufficient oxygen is provided, to generate more singlet oxygens, enhances light power effect, the above result shows that, it loads perfluorinated
The hollow PMOF singlet oxygen of carbon generates ability and is better than hollow PMOF, thus hollow PMOF load perfluocarbon can be improved it is hollow
The optical dynamic therapy effect of PMOF.
The hollow PMOF of embodiment 4 is used for high-efficient carrier chemotherapeutic adriamycin
Ah mould is loaded with the metalloporphyrin frame material (hollow PMOF) made from the embodiment of the present invention 1 with hollow nanostructures
Plain (Dox), measuring hollow PMOF is 2.2mg Dox/mg MOF to the load capacity of adriamycin, much higher than the metal reported at present
Organic backbone nano material is to the load capacity of Dox, this is because hollow PMOF has the shell of huge cavity and high-sequential
Hole, therefore a large amount of drug can be loaded, the above result shows that hollow PMOF is that a great application potential novel nano carries
Medicine system.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.
Claims (10)
1. a kind of metalloporphyrin frame material with hollow nanostructures, which is characterized in that it is made of cavity and shell, it is described
Shell is by Zr6Cluster and tetrabasic carboxylic acid ligand 5,10,15,20- tetra- (4- carboxyl phenyl) porphyrin with photosensitive activity pass through coordination type
At the orderly space net structure of three-dimensional stability.
2. the metalloporphyrin frame material according to claim 1 with hollow nanostructures, which is characterized in that in described
The size of the metalloporphyrin frame material of empty nanostructure is 20-200nm, shell thickness 5-50nm.
3. the preparation method of the metalloporphyrin frame material described in claim 1 with hollow nanostructures, which is characterized in that
The following steps are included:
(a) inorganic nano-particle is prepared；
(b) it disperses inorganic nano-particle made from step (a) in solvent, zirconium source, organic ligand H is added2TCPP and auxiliary are adjusted
Ligand is saved, the auxiliary adjustment ligand is benzoic acid, acetic acid, formic acid, trifluoroacetic acid or hydrochloric acid, and 70-150 DEG C of heating is reacted, after
Product is collected by centrifugation, it is core that washing, which obtains inorganic nano-particle, and metalloporphyrin frame material is the nanocomposite of shell；
(c) nanocomposite that etch step (b) obtains removes inorganic nano-particle core to get described with hollow
The metalloporphyrin frame material of nanostructure.
4. preparation method according to claim 3, which is characterized in that the inorganic nano-particle includes cuprous oxide, two
Silica, titanium dioxide three-iron, ferroso-ferric oxide, manganese oxide, titanium dioxide, aluminium oxide, zinc oxide or calcium phosphate.
5. preparation method according to claim 3, which is characterized in that step (b) dispersion inorganic nano-particle solvent be
One or more of N,N-dimethylformamide, water, methanol, ethyl alcohol.
6. preparation method according to claim 3, which is characterized in that the source Zr, organic ligand H2TCPP and auxiliary adjustment are matched
The molar ratio of body is (5-10): 1:(100-300).
7. preparation method according to claim 3, which is characterized in that in step (c), nanometer that etch step (b) obtains
Composite material removes inorganic nano-particle core, with cuprous oxide, titanium dioxide three-iron, ferroso-ferric oxide, titanium dioxide, oxidation
Manganese, aluminium oxide, zinc oxide, the nanocomposite that calcium phosphate is core use acid etch, using silica as the nanometer of core
Composite material uses alkaline etching or hf etching.
8. material of any of claims 1 or 2 is preparing the application on nano medicament carrying system.
9. application according to claim 8, the nano medicament carrying system is for loading perfluocarbon.
10. application according to claim 8, the nano medicament carrying system for load chemotherapeutics, photothermal reagent or
Imaging molecule.
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| CN110038128A (en) * | 2019-04-25 | 2019-07-23 | 南京邮电大学 | A kind of Au@Se@Pt-Ce6 nanometer compound probe and preparation method thereof |
| CN110124034A (en) * | 2019-05-29 | 2019-08-16 | 浙江大学 | A kind of nano metal organic frame cavitation material, synthetic method and application |
| CN111514937A (en) * | 2020-05-13 | 2020-08-11 | 中国石油大学(华东) | Preparation method of porphyrin-based metal organic framework material sensitized oxide catalyst |
| CN112706170A (en) * | 2019-10-25 | 2021-04-27 | 湖南早晨纳米机器人有限公司 | Shell type nano robot and preparation method thereof |
| CN113522363A (en) * | 2021-06-29 | 2021-10-22 | 北京科技大学 | Preparation method and application of metal ion modified MOF micro/nano structure in hydrogel |
| CN113831544A (en) * | 2021-09-22 | 2021-12-24 | 同济大学 | Non-linear nano hybrid material of titanium carbide quantum dots and vanadium metal organic framework and preparation method thereof |
| CN115192762A (en) * | 2022-08-15 | 2022-10-18 | 浙江理工大学 | Medical composite material and preparation method and application thereof |
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| CN110038128A (en) * | 2019-04-25 | 2019-07-23 | 南京邮电大学 | A kind of Au@Se@Pt-Ce6 nanometer compound probe and preparation method thereof |
| CN110124034A (en) * | 2019-05-29 | 2019-08-16 | 浙江大学 | A kind of nano metal organic frame cavitation material, synthetic method and application |
| CN112706170A (en) * | 2019-10-25 | 2021-04-27 | 湖南早晨纳米机器人有限公司 | Shell type nano robot and preparation method thereof |
| CN111514937A (en) * | 2020-05-13 | 2020-08-11 | 中国石油大学(华东) | Preparation method of porphyrin-based metal organic framework material sensitized oxide catalyst |
| CN113522363A (en) * | 2021-06-29 | 2021-10-22 | 北京科技大学 | Preparation method and application of metal ion modified MOF micro/nano structure in hydrogel |
| CN113522363B (en) * | 2021-06-29 | 2022-11-15 | 北京科技大学 | Preparation method and application of metal ion modified MOF micro/nano structure in hydrogel |
| CN113831544A (en) * | 2021-09-22 | 2021-12-24 | 同济大学 | Non-linear nano hybrid material of titanium carbide quantum dots and vanadium metal organic framework and preparation method thereof |
| CN115192762A (en) * | 2022-08-15 | 2022-10-18 | 浙江理工大学 | Medical composite material and preparation method and application thereof |
| CN115192762B (en) * | 2022-08-15 | 2023-11-28 | 浙江理工大学 | Medical composite material and preparation method and application thereof |
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