CN110025596A - A kind of Nano composite granules and preparation method thereof - Google Patents
A kind of Nano composite granules and preparation method thereof Download PDFInfo
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- CN110025596A CN110025596A CN201910337124.1A CN201910337124A CN110025596A CN 110025596 A CN110025596 A CN 110025596A CN 201910337124 A CN201910337124 A CN 201910337124A CN 110025596 A CN110025596 A CN 110025596A
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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
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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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
- A61K41/0071—PDT with porphyrins having exactly 20 ring atoms, i.e. based on the non-expanded tetrapyrrolic ring system, e.g. bacteriochlorin, chlorin-e6, or phthalocyanines
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/51—Nanocapsules; Nanoparticles
- A61K9/5107—Excipients; Inactive ingredients
- A61K9/5123—Organic compounds, e.g. fats, sugars
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/51—Nanocapsules; Nanoparticles
- A61K9/5107—Excipients; Inactive ingredients
- A61K9/513—Organic macromolecular compounds; Dendrimers
- A61K9/5146—Organic macromolecular compounds; Dendrimers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, polyamines, polyanhydrides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
Abstract
The present invention provides a kind of Nano composite granules and preparation method thereof, by by ZrCl4It is dissolved in N,N-dimethylformamide and forms ZrCl4Solution, then sequentially add terephthalic acid (TPA), benzoic acid, hydrochloric acid and in-four (4- carboxyl phenyl) porphines, obtain the metal organic frame nano particle for being embedded in Porphyrin Molecule, metal organic frame nano particle is added in buffer again, then dopamine is added, dopamine molecule polymerize to form poly-dopamine, it is wrapped in the outer surface of metal organic frame, to form the Nano composite granules of core-shell structure, wherein, poly-dopamine layer with a thickness of 5nm~50nm, the size of Nano composite granules is 60nm~500nm.The Nano composite granules pattern that the present invention is prepared is uniform, favorable dispersibility, and bio-toxicity is low, has good photo-thermal effect, Photodynamic Therapy, good to the therapeutic effect of tumour.
Description
Technical field
The invention belongs to materialogy fields, and in particular to a kind of Nano composite granules and preparation method thereof.
Background technique
Cancer becomes the chief threat of human health, and the traditional therapy for cancer includes chemotherapy, radiotherapy and surgery
Operation etc., and these treatment methods have various defects and deficiency.With the development of science and technology, the photo-thermal therapy based on nano-carrier
(PTT) it is used as a kind of minimum noninvasive laser therapy method, there is unique advantage.The light thermit powder of PTT, such as noble metal, have
Machine polymer, c-based nanomaterial and semiconducting compound etc., can be absorbed light it are made to be converted into thermal energy and distribute to making part
Temperature increases, and selectivity kills target tumor.Organic polymer species light thermit powder is lower because having preferable biocompatibility
Bio-toxicity, obtained extensive concern.One of organic polymer species light thermit powder poly-dopamine (PDA), is by human body
A kind of interior biomolecules of dopamine is polymerized, and has preferable biological safety and biodegradability, itself is also
Preferable photothermal conversion effect.
Photosensitizer for PDT also has very much, and wherein Porphyrin Molecule and its derivative are a kind of common photosensitizer, life
Object toxicity is low, and having strong absorption in visible-range, (a stronger B band including 400~450 absorbs and 500~700
Four Q band absorb), in the presence of illumination and oxygen, active singlet state oxygen can be converted the oxygen to, tumour can be killed
Cell.However, Porphyrin Molecule water solubility is poor, Porphyrin Molecule easy to reunite to cause to quench therefore simple is low for PDT effect.
Up to now, various nano-carriers have been synthesized for loading or connecting Porphyrin Molecule, overcome the defect of itself.Nanometer
The metal organic frame (Metal-Organic Frameworks, NMOFs) of rank is used as nano-carrier, high with lift-launch amount,
The features such as functional more, targeting is good, degradable.Studies have shown that Zn, Fe, Zr plasma were constituted as metal ion center
MOFs good biocompatibility, bio-toxicity are low.Therefore, metal organic frame nano particle shows huge in terms of biologic medical
Potentiality.
To sum up, the metal organic frame and poly-dopamine composite nanometer particle for preparing insertion Porphyrin Molecule how are designed,
As collaboration photo-thermal therapy, photodynamic therapy in the key of one, it is expected to improve treatment tumor effect and bringing new breakthrough.
Summary of the invention
The present invention is to carry out to solve the above-mentioned problems, and it is an object of the present invention to provide a kind of Nano composite granules and its preparation
Method is used for oncotherapy.
The present invention provides a kind of Nano composite granules, have a feature in that the Nano composite granules include that metal has
Machine frame, Porphyrin Molecule and poly-dopamine layer, wherein Porphyrin Molecule is embedded in inside metal organic frame, poly-dopamine layer chela
Close on metal organic frame outer surface, poly-dopamine layer with a thickness of 5nm~50nm, the size of Nano composite granules is 60nm
~500nm.
It in Nano composite granules provided by the invention, can also have the following features: wherein, metal organic frame is
The porous structure formed is coordinated by zirconium metal cluster and terephthalic acid (TPA).
In Nano composite granules provided by the invention, can also have the following features: wherein, Porphyrin Molecule be in-
Four (4- carboxyl phenyl) porphines.
The present invention also provides a kind of preparation methods of Nano composite granules, which comprises the following steps:
Step 1, by ZrCl4It is dissolved in N,N-dimethylformamide and forms ZrCl4Solution, then in ZrCl4In solution successively
Be added terephthalic acid (TPA), benzoic acid, hydrochloric acid and in-four (4- carboxyl phenyl) porphines, obtain green solution after dissolution；
Green solution is transferred in water heating kettle by step 2, and room temperature is cold after reacting 12~48 hours at 100~150 DEG C
But, the first suspension is obtained；
First suspension is centrifuged to obtain purple precipitating by step 3, is cleaned with the first solvent to purple precipitating, and will
After cleaning the purple precipitating is dried in vacuo, be embedded in-four (4- carboxyl phenyl) porphines metal organic frame
Nano particle；
Metal organic frame nano particle is added in buffer by step 4, and the dopamine of predetermined amount is then added,
12h~48h is stirred at room temperature, is obtained the second suspension, is centrifuged the second suspension to obtain black precipitate, with the first solvent to this
Black precipitate is cleaned, and the black precipitate after cleaning is dried in vacuo, and obtains having the nanometer of core-shell structure multiple
Particle is closed,
Wherein, pH > 7 of the buffer in step 4.
In the preparation method of Nano composite granules provided by the invention, it can also have the following features: wherein, step
ZrCl in one4, terephthalic acid (TPA), benzoic acid, hydrochloric acid and in-four (4- carboxyl phenyl) porphines molar ratio be 20:10:100:
100:1~20:30:600:100:1.
In the preparation method of Nano composite granules provided by the invention, it can also have the following features: wherein, step
The mass ratio of metal organic frame nano particle and dopamine in four is 1:0.25~1:5.
In the preparation method of Nano composite granules provided by the invention, it can also have the following features: wherein, step
Buffer in four is tris-HCI buffer, the pH=of the tris-HCI buffer
8.0~10.0.
In the preparation method of Nano composite granules provided by the invention, it can also have the following features: wherein, step
Three and step 4 in solvent include N,N-dimethylformamide, ethyl alcohol and deionized water.
The action and effect of invention
Related Nano composite granules according to the present invention, because of base of the metal organic frame as Nano composite granules
Body, Porphyrin Molecule TCPP are embedded in the inside of metal organic frame, and poly-dopamine layer is sequestered in metal organic frame outer surface, so
The Nano composite granules have core-shell structure, and pattern is uniform, favorable dispersibility.And because of poly-dopamine layer with a thickness of 5nm
~50nm, the sizes of Nano composite granules are 60nm~500nm, and light thermit powder poly-dopamine by convert light energy into thermal energy from
And local temperature is increased, selectivity kills target tumor, the light of the thickness of poly-dopamine layer for Nano composite granules
Heat, photodynamics performance have important influence, and thickness is too low, and it is weaker to will lead to photo-thermal effect, and thickness is too high, and fine and close is poly-
Close nitride layer block oxygen entrance so that photodynamics effect disappear, therefore only poly-dopamine thickness degree this be suitable for ruler
It just can guarantee preferable photo-thermal effect, photodynamics synergy under very little, in addition, the size of Nano composite granules is only fitted herein
Just there is the good targeting of better lift-launch amount under suitable size, therefore can preferably play its effect for treating tumour.
Further, Porphyrin Molecule can convert the oxygen to active singlet state oxygen as photosensitizer under light illumination, be applicable in
In tumor photo-thermal, photodynamics synergistic treatment, the therapeutic effect to tumour can be improved.
Further, metal organic frame has good biocompatibility and bio-toxicity low as nano-carrier
Advantage.
Therefore, Nano composite granules according to the present invention combine the advantages of three, and a kind of nucleus has been prepared
The Nano composite granules of shell structure, bio-toxicity is low, has good photo-thermal effect, Photodynamic Therapy, enhances pair
The therapeutic effect of tumour.
The preparation method of related Nano composite granules according to the present invention, because by ZrCl4It is dissolved in N, N- dimethyl methyl
Amide forms ZrCl4Solution, then in ZrCl4Sequentially added in solution terephthalic acid (TPA), benzoic acid, hydrochloric acid and in-four (4-
Carboxyl phenyl) porphines, so through solvent thermal reaction, be embedded in-four (4- carboxyl phenyl) porphines metal organic frame
Nano particle.Organic ligand terephthalic acid (TPA) and Zr metal cluster are self-assembly of the metal with porous structure by coordinate bond
Organic frame, matrix of the metal organic frame as Nano composite granules, Porphyrin Molecule TCPP are embedded in the interior of metal organic frame
Portion.Again because metal organic frame nano particle is added in buffer, the dopamine of predetermined amount is then added, so utilizing
The metal chelation abilities of catechol combine the Zr metal cluster on metal organic frame surface on dopamine molecule, then exist
Dopamine molecule polymerize to form poly-dopamine PDA under alkaline condition, is wrapped in the outer surface of metal organic frame, to form core
The Nano composite granules of shell structure.The Nano composite granules pattern is uniform, favorable dispersibility, has core-shell structure.
Therefore, a kind of new type structure of hud has been prepared in the preparation method of Nano composite granules according to the present invention
Nano composite granules, bio-toxicity is low, has good photo-thermal effect, Photodynamic Therapy, enhances and control tumour
Therapeutic effect.
Detailed description of the invention
Fig. 1 is transmission electron microscope (TEM) figure of UiO-66@TCPP nano particle prepared by the embodiment of the present invention 1；
Fig. 2 is the transmission electron microscope (TEM) of UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 1
Figure；
Fig. 3 is the X-ray diffraction of nano particle prepared by the embodiment of the present invention 1 and metal organic frame UiO-66 comparison
(XRD) map；
Fig. 4 is that nano particle prepared by the embodiment of the present invention 1 is received with Porphyrin Molecule, TCPP metal organic frame UiO-66
UV absorption (UV) map of rice grain comparison；
Fig. 5 is UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 1 in 808nm laser irradiation
Under photo-thermal effect curve；
Fig. 6 is UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 1 in 660nm laser irradiation
Under active singlet state oxygen generate result；
Fig. 7 is the transmission electron microscope (TEM) of UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 2
Figure；
Fig. 8 is the transmission electron microscope (TEM) of UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 3
Figure；And
Fig. 9 is the transmission electron microscope (TEM) of UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 4
Figure.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Examples and drawings are closed to be specifically addressed a kind of Nano composite granules of the present invention and preparation method thereof.
Nano composite granules provided by the invention the preparation method is as follows:
Step 1, by ZrCl4It is dissolved in N,N-dimethylformamide and forms ZrCl4Solution, then in ZrCl4In solution successively
Be added terephthalic acid (TPA), benzoic acid, hydrochloric acid and in-four (4- carboxyl phenyl) porphines, obtain green solution after dissolution；
Green solution is transferred in water heating kettle by step 2, and room temperature is cold after reacting 12~48 hours at 100~150 DEG C
But, the first suspension is obtained；
First suspension is centrifuged to obtain purple precipitating by step 3, is cleaned with the first solvent to purple precipitating, and will
After cleaning the purple precipitating is dried in vacuo, be embedded in-four (4- carboxyl phenyl) porphines metal organic frame
Nano particle；
Metal organic frame nano particle is added in the buffer of pH > 7 by step 4, and the more of predetermined amount are then added
Bar amine, is stirred at room temperature 12h~48h, obtains the second suspension, be centrifuged the second suspension to obtain black precipitate, with first
Solvent cleans the black precipitate, and the black precipitate after cleaning is dried in vacuo, and obtains with core-shell structure
Nano composite granules.
It include metal organic frame, Porphyrin Molecule and poly-dopamine through the Nano composite granules that the above method is prepared
Layer, wherein Porphyrin Molecule is embedded in inside metal organic frame, and poly-dopamine layer is sequestered on metal organic frame outer surface, is gathered
DOPA amine layer with a thickness of 5nm~50nm, the size of Nano composite granules is 60nm~500nm.
<embodiment 1>
Embodiment 1 is that the preparation of Nano composite granules of the invention is tested, comprising the following steps:
Step 1, by 0.3mmol ZrCl4It is dissolved in 6ml N,N-dimethylformamide and forms ZrCl4Then solution exists
ZrCl4It is sequentially added in solution-four in 0.3mmol terephthalic acid (TPA), 5mmol benzoic acid, 1.5mmol hydrochloric acid and 0.015mmol
(4- carboxyl phenyl) porphines (TCPP), ultrasonic 10min obtain green solution to being completely dissolved after dissolution.
Green solution is transferred to water heating kettle (polytetrafluoroethyllining lining, stainless steel autoclave body) by step 2, molten at 120 DEG C
It after agent thermal response 24 hours, is cooled to room temperature, obtains the first suspension.
First suspension is centrifuged under 10000rpm revolving speed and obtains purple precipitating, with N, N- dimethyl formyl by step 3
Amine, ethyl alcohol, deionized water are respectively washed purple precipitating three times, and then purple precipitating is placed in a vacuum drying oven at 100 DEG C
Dry 12h, be embedded in-four (4- carboxyl phenyl) porphines metal organic frame nano particle UiO-66@TCPP.
20mg metal organic frame nano particle UiO-66@TCPP is dispersed 40ml trihydroxy methyl amino first by step 4
In alkane-hydrochloric acid (Tris-HCl) buffer (10mM, pH=8.0), the dopamine (DA) of 20mg, ultrasonic disperse is then added
It after 10min, is stirred at room temperature 24 hours, obtains the second suspension, which is centrifuged under 10000rpm revolving speed,
It is collected into black precipitate, the black precipitate being collected into is respectively washed with ethyl alcohol, deionized water three times, then sets the black precipitate
The dry 12h at 60 DEG C in a vacuum drying oven, obtains the Nano composite granules UiO-66@TCPP@PDA with core-shell structure.
Fig. 1 is transmission electron microscope (TEM) figure of UiO-66@TCPP nano particle prepared by the embodiment of the present invention 1.
As shown in Figure 1, UiO-66@TCPP nano particle pattern prepared by embodiment 1 is uniform, favorable dispersibility, surface
It is more smooth, average grain diameter about 110nm.
Fig. 2 is the transmission electron microscope (TEM) of UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 1
Figure.
As shown in Fig. 2, UiO-66@TCPP@PDA Nano composite granules pattern prepared by embodiment 1 is uniform, dispersibility is good
Good, surface concave-convex surface, average grain diameter about 120nm is become larger relative to UiO-66@TCPP nanoparticle size, it was demonstrated that
The package of poly-dopamine layer, thickness about 10nm.
Fig. 3 is the X of nano particle prepared by the embodiment of the present invention 1 and the comparison of metal organic frame UiO-66 nano particle
X ray diffraction (XRD) map.Wherein, abscissa is x-ray diffraction angle, and ordinate is X-ray diffraction intensity.Related metal
The preparation of organic frame UiO-66 nano particle is similar with metal organic frame UiO-66@TCPP nano particle, and difference is that
The no addition for having TCPP.
As shown in figure 3, the X of UiO-66@TCPP nano particle prepared by embodiment 1 and simple UiO-66 nano particle
The derivative peak of radiation characteristic is consistent, it was demonstrated that the UiO-66@TCPP nano particle after insertion TCPP maintains simple UiO-66 and receives
The crystalline texture of rice grain.The X ray diffracting spectrum for observing UiO-66@TCPP@PDA prepared by embodiment 1, it can be found that absolutely
Most of characteristic peak disappears, and only has a faint characteristic diffraction peak 8 ° or so of position, corresponds to UiO-66@TCPP and receive
Strong characteristic diffraction peak of the rice grain in 7~9 ° of ranges, it was demonstrated that amorphous poly-dopamine is in UiO-66@TCPP nano particle appearance
The successful package in face.
Fig. 4 is that nano particle prepared by the embodiment of the present invention 1 is received with Porphyrin Molecule, TCPP metal organic frame UiO-66
UV absorption (UV) map of rice grain comparison.Wherein, abscissa is absorbing wavelength, and ordinate is absorption intensity；Involved porphin
Quinoline molecule TCPP and prepare used in nano particle consistent, the preparation of metal organic frame UiO-66 nano particle has with metal
Machine frame UiO-66 TCPP nano particle is similar, and difference is the addition for whether having TCPP.
As shown in figure 4, simple Porphyrin Molecule TCPP has stronger B band absorption peak in 415nm or so, in 500~700nm
There are four weaker Q band absorption peaks, and simple metal organic frame UiO-66 nano particle is not obvious in 400~700nm
Characteristic absorption peak.Relative to metal organic frame UiO-66 nano particle, TCPP nanometers of UiO-66@prepared by embodiment 1
Particle and UiO-66@TCPP@PDA Nano composite granules all occur the stronger B band absorption peak and 500 of 430nm or so~
Four of 700nm weaker Q band absorption peak, it was demonstrated that Porphyrin Molecule TCPP in metal organic frame UiO-66 nano particle at
Function insertion.
Nano composite granules manufactured in the present embodiment photo-thermal effect confirmatory experiment has been subjected to again.
Photo-thermal effect confirmatory experiment process are as follows:
Disperse Nano composite granules UiO-66@TCPP@PDA in the solution that six groups of various concentrations are configured in PBS solution, and
It is packaged in the test tube of 2mL, compound concentration is successively are as follows: 0 μ g/mL (PBS group), 50 μ g/mL, 100 μ g/mL, 200 μ g/mL, 400 μ
g/mL,800μg/mL.The photo-thermal effect of the Nano composite granules is measured using infrared light thermal imaging system.Select 808nm laser
Light source is provided, the light source density of setting is 1.5W/cm2, 8 centimetres of irradiation distance.It is taken respectively from the solution of six groups of various concentrations
Volume is the solution of 1mL out, records temperature change with 808nm laser irradiation 300 seconds, and with infrared light thermal imaging system.
Experimental result is as shown in Figure 5.
Fig. 5 is UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 1 in 808nm laser irradiation
Under photo-thermal effect curve.
As shown in figure 5, abscissa is the time in Fig. 5, ordinate is temperature change.Relative to PBS group, 1mL is nano combined
Particle solution (50 μ g/mL, 100 μ g/mL, 200 μ g/mL, 400 μ g/mL, 800 μ g/mL) is in laser (intensity of light source 1.5W/
cm2, wavelength 808nm, 8 centimetres of irradiation distance) and lower temperature apparent increase is irradiated, illustrate prepared by embodiment 1 nano combined
Grain UiO-66@TCPP@PDA has good photo-thermal effect, and as concentration increases, photo-thermal effect is obviously improved.Such as 1mL
400 μ g/mL Nano composite granules solution after 808nm laser irradiation 300 seconds temperature quickly increase 25 DEG C, can be used for tumour
Photo-thermal therapy.
Nano composite granules manufactured in the present embodiment active singlet state oxygen confirmatory experiment has been subjected to again.
Active singlet state oxygen confirmatory experiment process are as follows: disperse PBS solution for Nano composite granules UiO-66@TCPP@PDA
In, the solution that configuration Nano composite granules UiO-66@TCPP@PDA concentration is 100 μ g/mL, with PBS solution as control group: i.e.
Nano composite granules UiO-66@TCPP@PDA concentration is 0ug/mL, respectively takes 2mL in quartz colorimetric utensil.Utilize DPBF (1,3- bis-
Phenyl benzofurans) molecule can react and cause the property of its ultraviolet characteristic absorption peak reduction with active singlet state oxygen, to detect
The active singlet state oxygen production of Nano composite granules UiO-66@TCPP@PDA under 660nm illumination.Add in the solution before test
Enter the DPBF/DMSO test fluid that 10uL concentration is 10mM.660nm laser is selected to provide light source, the source current of setting
900mA, power 4mW, 8 centimetres of irradiation distance.With 660nm laser irradiation 15min, surveyed every 3min using UV-2550 instrument
Try solution in DPBF 350nm~500nm range ultraviolet absorption peak, and record its 410nm ultraviolet characteristic absorption value become
Change.
Experimental result is as shown in Figure 6.
Fig. 6 is UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 1 in 660nm laser irradiation
Under active singlet state oxygen generate result.
As shown in fig. 6, in Fig. 6 abscissa be the time, ordinate be solution in DPBF 410nm ultraviolet characteristic absorption value
Variation.Relative to control group, 2mL concentration is the Nano composite granules solution of 100 μ g/mL in laser (light source power 4mW, wave
A length of 660nm, 8 centimetres of irradiation distance) under irradiation, DPBF in solution the ultraviolet characteristic absorption value of 410nm reduction more
Significantly, illustrate that Nano composite granules UiO-66@TCPP@PDA prepared by embodiment 1 has the ability for generating active singlet state oxygen.
And as the extension of light application time, active singlet state oxygen yield increase, such property can be used for the light of tumour
Photodynamic therapy.
<embodiment 2>
Embodiment 2 is that the preparation of Nano composite granules of the invention is tested, comprising the following steps:
Step 1, by 0.3mmol ZrCl4It is dissolved in 6ml N,N-dimethylformamide and forms ZrCl4Then solution exists
ZrCl4It is sequentially added in solution-four in 0.3mmol terephthalic acid (TPA), 9mmol benzoic acid, 1.5mmol hydrochloric acid and 0.015mmol
(4- carboxyl phenyl) porphines (TCPP), ultrasonic 10min obtain green solution to being completely dissolved after dissolution.
Green solution is transferred to water heating kettle (polytetrafluoroethyllining lining, stainless steel autoclave body) by step 2, molten at 130 DEG C
It after agent thermal response 12 hours, is cooled to room temperature, obtains the first suspension.
First suspension is centrifuged under 8000rpm revolving speed and obtains purple precipitating by step 3, cleans purple precipitating with ethyl alcohol
Three times, purple precipitating is then placed in a vacuum drying oven at 100 DEG C dry 12h, be embedded in-four (4- carboxyl phenyls)
The metal organic frame nano particle UiO-66@TCPP of porphines.
20mg metal organic frame nano particle UiO-66@TCPP is dispersed 40ml trihydroxy methyl amino first by step 4
In alkane-hydrochloric acid (Tris-HCl) buffer (10mM, pH=8.5), the dopamine (DA) of 5mg, ultrasonic disperse 5min is then added
Afterwards, it is stirred at room temperature 12 hours, obtains the second suspension, which is centrifuged under 8000rpm revolving speed, is collected into
Black precipitate is respectively washed the black precipitate being collected into ethyl alcohol and deionized water three times, is then placed in the black precipitate very
12h is dried in empty drying box at 60 DEG C, obtains the Nano composite granules UiO-66@TCPP@PDA with core-shell structure.
Fig. 7 is the transmission electron microscope (TEM) of UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 2
Figure.
As shown in fig. 7, UiO-66@TCPP@PDA Nano composite granules prepared by embodiment 2 are in cubic, average ruler
Very little about 130nm；With apparent core-shell structure, gather bar amine layer thichness about 5nm.
<embodiment 3>
Embodiment 3 is that the preparation of Nano composite granules of the invention is tested, comprising the following steps:
Step 1, by 0.3mmol ZrCl4It is dissolved in 6ml N,N-dimethylformamide and forms ZrCl4Then solution exists
ZrCl4It is sequentially added in solution-four in 0.3mmol terephthalic acid (TPA), 2mmol benzoic acid, 1.5mmol hydrochloric acid and 0.015mmol
(4- carboxyl phenyl) porphines (TCPP), ultrasonic 10min obtain green solution to being completely dissolved after dissolution.
Green solution is transferred to water heating kettle (polytetrafluoroethyllining lining, stainless steel autoclave body) by step 2, molten at 120 DEG C
It after agent thermal response 48 hours, is cooled to room temperature, obtains the first suspension.
First suspension is centrifuged under 11000rpm revolving speed and obtains purple precipitating, with N, N- dimethyl formyl by step 3
Amine, ethyl alcohol and deionized water are respectively washed purple precipitating three times, and then purple precipitating is placed in a vacuum drying oven in 100 DEG C
Lower dry 12h, be embedded in-four (4- carboxyl phenyl) porphines metal organic frame nano particle UiO-66@TCPP.
20mg metal organic frame nano particle UiO-66@TCPP is dispersed 40ml trihydroxy methyl amino first by step 4
In alkane-hydrochloric acid (Tris-HCl) buffer (10mM, pH=9.0), the dopamine (DA) of 40mg, ultrasonic disperse is then added
It after 15min, is stirred at room temperature 24 hours, obtains the second suspension, which is centrifuged under 10000rpm revolving speed,
It is collected into black precipitate, the black precipitate being collected into is respectively washed with ethyl alcohol and deionized water three times, then the black sinks
Shallow lake is placed in a vacuum drying oven at 60 DEG C dry 12h, obtains the Nano composite granules UiO-66@TCPP@with core-shell structure
PDA。
Fig. 8 is the transmission electron microscope (TEM) of UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 3
Figure.
As shown in figure 8, UiO-66@TCPP@PDA Nano composite granules prepared by embodiment 3 are spherical, average-size
About 100nm；With apparent core-shell structure, gather bar amine layer thichness about 15nm.
<embodiment 4>
Embodiment 4 is that the preparation of Nano composite granules of the invention is tested, comprising the following steps:
Step 1, by 0.3mmol ZrCl4It is dissolved in 6ml N,N-dimethylformamide and forms ZrCl4Then solution exists
ZrCl4Sequentially added in solution in 0.45mmol terephthalic acid (TPA), 1.5mmol benzoic acid, 1.5mmol hydrochloric acid and 0.015mmol-
Four (4- carboxyl phenyl) porphines (TCPP), ultrasonic 10min obtain green solution to being completely dissolved after dissolution.
Green solution is transferred to water heating kettle (polytetrafluoroethyllining lining, stainless steel autoclave body) by step 2, molten at 100 DEG C
It after agent thermal response 24 hours, is cooled to room temperature, obtains the first suspension.
First suspension is centrifuged under 13000rpm revolving speed and obtains purple precipitating, with N, N- dimethyl formyl by step 3
Amine, ethyl alcohol and deionized water are respectively washed purple precipitating three times, and then purple precipitating is placed in a vacuum drying oven in 100 DEG C
Lower dry 12h, be embedded in-four (4- carboxyl phenyl) porphines metal organic frame nano particle UiO-66@TCPP.
20mg metal organic frame nano particle UiO-66@TCPP is dispersed 40ml trihydroxy methyl amino first by step 4
In alkane-hydrochloric acid (Tris-HCl) buffer (10mM, pH=10.0), then plus the dopamine of 80mg (DA), ultrasonic disperse 5min
Afterwards, it is stirred at room temperature 12 hours, obtains the second suspension, which is centrifuged under the revolving speed of 13000rpm, receive
Collect black precipitate, the black precipitate being collected into is cleaned with ethyl alcohol and deionized water three times, is then placed in the black precipitate
12h is dried in vacuum oven at 60 DEG C, obtains the Nano composite granules UiO-66@TCPP@PDA with core-shell structure.
Fig. 9 is the transmission electron microscope (TEM) of UiO-66@TCPP@PDA Nano composite granules prepared by the embodiment of the present invention 4
Figure.
As shown in figure 9, UiO-66@TCPP@PDA Nano composite granules prepared by embodiment 4 are in near-spherical, surface is significant
It is uneven, average-size about 70nm；With more obvious core-shell structure, gather bar amine layer thichness about 10nm.
The action and effect of embodiment
Illustrate the effect of Nano composite granules made from the embodiment of the present invention below in conjunction with the performance of the various embodiments described above
With effect.
The preparation method of related Nano composite granules according to the present invention, because by ZrCl4It is dissolved in N, N- dimethyl methyl
Amide forms ZrCl4Solution, then in ZrCl4Sequentially added in solution terephthalic acid (TPA), benzoic acid, hydrochloric acid and in-four (4-
Carboxyl phenyl) porphines, so through solvent thermal reaction, be embedded in-four (4- carboxyl phenyl) porphines metal organic frame
Nano particle.The gold with porous structure that organic ligand terephthalic acid (TPA) and Zr metal cluster are self-assembly of by coordinate bond
Belong to organic frame, matrix of the metal organic frame as Nano composite granules, Porphyrin Molecule TCPP, which is entrenched in metal, machine frame
The inside of frame.Again because metal organic frame nano particle is added in buffer, the dopamine of predetermined amount, institute is then added
With the Zr metal cluster that the metal chelation abilities of catechol on dopamine molecule are utilized to combine metal organic frame surface,
Then dopamine molecule polymerize to form poly-dopamine PDA under alkaline condition, is wrapped in the outer surface of metal organic frame, thus
Form the Nano composite granules of core-shell structure.
TEM characterization test is carried out it is found that system of the present invention by the Nano composite granules prepared to embodiment 1 to embodiment 4
Standby obtained Nano composite granules pattern is uniform, favorable dispersibility, has core-shell structure, be successfully embed into Porphyrin Molecule TCPP with
And package poly-dopamine layer.The size of metal organic frame nano particle is by organic ligand, sour small molecule additional amount and reaction
Temperature and reaction time influence, and poly-dopamine thickness degree is influenced by dopamine molecule additional amount and reaction time, 5~
It is adjustable between 50 nanometers, so that the size of Nano composite granules can be adjustable between 60~500 nanometers.For example, passing through
Change benzoic acid additional amount, reaction temperature, reaction time and dopamine additional amount, nano combined prepared by embodiment 2
The size of grain is 130nm, the poly-dopamine layer of package with a thickness of 5nm, and in embodiment 1 Nano composite granules obtained size
It is smaller, it is 110nm, but the poly-dopamine thickness degree wrapped up is big, is 10nm.
Show that Nano composite granules prepared by the present invention include light with active singlet state oxygen experiment by photo-thermal effect experiment
Thermit powder poly-dopamine can convert light energy into thermal energy, can convert the oxygen to live under light illumination comprising photosensitizer porphyrin molecule
Property singlet oxygen, be suitable for tumor photo-thermal, photodynamics synergistic treatment, can be improved the therapeutic effect to tumour.Wherein, gather more
The thickness of bar amine layer has important influence for the photo-thermal of Nano composite granules, photodynamics performance.Thickness is too low, will lead to
Photo-thermal effect is weaker, and thickness is too high, and fine and close polymeric layer blocks the entrance of oxygen so that photodynamics effect disappears,
Poly-dopamine thickness degree only appropriate just can guarantee preferable photo-thermal effect, photodynamics synergy.
In addition, metal organic frame UiO-66 is as nano-carrier, with low excellent of good biocompatibility, bio-toxicity
Point, for Porphyrin Molecule as photosensitizer, bio-toxicity is low, and organic polymer species light thermit powder poly-dopamine (PDA), is by human body
A kind of biomolecules of dopamine be polymerized, have preferable biological safety and biodegradability, itself there are also compared with
Good photothermal conversion effect.Therefore, the present invention combines the advantages of three, and a kind of nanometer of new type structure of hud has been prepared
Composite particles UiO-66@TCPP@PDA, bio-toxicity is low, has good photo-thermal effect, Photodynamic Therapy, enhances
To the therapeutic effect of tumour.
Above embodiment is preferred case of the invention, the protection scope being not intended to limit the invention.
Claims (8)
1. a kind of Nano composite granules, it is characterised in that:
The Nano composite granules include metal organic frame, Porphyrin Molecule and poly-dopamine layer,
Wherein, the Porphyrin Molecule is embedded in inside the metal organic frame,
The poly-dopamine layer is sequestered on the metal organic frame outer surface,
The poly-dopamine layer with a thickness of 5nm~50nm,
The size of the Nano composite granules is 60nm~500nm.
2. Nano composite granules according to claim 1, it is characterised in that:
Wherein, the metal organic frame is to be coordinated the porous structure formed by zirconium metal cluster and terephthalic acid (TPA).
3. Nano composite granules according to claim 1, it is characterised in that:
Wherein, the Porphyrin Molecule be in-four (4- carboxyl phenyl) porphines.
4. a kind of preparation method of Nano composite granules, which comprises the following steps:
Step 1, by ZrCl4It is dissolved in N,N-dimethylformamide and forms ZrCl4Solution, then in the ZrCl4In solution successively
Be added terephthalic acid (TPA), benzoic acid, hydrochloric acid and in-four (4- carboxyl phenyl) porphines, obtain green solution after dissolution；
The green solution is transferred in water heating kettle by step 2, and room temperature is cold after reacting 12~48 hours at 100~150 DEG C
But, the first suspension is obtained；
First suspension is centrifuged to obtain purple precipitating by step 3, is cleaned with the first solvent to purple precipitating,
And be dried in vacuo the purple precipitating after cleaning, obtain being embedded in the metal of (4- carboxyl phenyl) porphines-four in described
Organic frame nano particle；
The metal organic frame nano particle is added in buffer by step 4, and the dopamine of predetermined amount is then added,
12h~48h is stirred at room temperature, is obtained the second suspension, is centrifuged second suspension to obtain black precipitate, with described first
Solvent cleans the black precipitate, and the black precipitate after cleaning is dried in vacuo, and obtains with core-shell structure
Nano composite granules,
Wherein, pH > 7 of the buffer in the step 4.
5. the preparation method of Nano composite granules according to claim 4, it is characterised in that:
Wherein, ZrCl described in the step 14, the terephthalic acid (TPA), the benzoic acid, the hydrochloric acid and it is described in-four
The molar ratio of (4- carboxyl phenyl) porphines is 20:10:100:100:1~20:30:600:100:1.
6. the preparation method of Nano composite granules according to claim 4, it is characterised in that:
Wherein, the mass ratio of the metal organic frame nano particle in the step 4 and the dopamine be 1:0.25~
1:5。
7. the preparation method of Nano composite granules according to claim 4, it is characterised in that:
Wherein, the buffer in the step 4 is tris-HCI buffer, the trihydroxy methyl amino
Methane-hydrochloride buffer pH=8.0~10.0.
8. the preparation method of Nano composite granules according to claim 4, it is characterised in that:
Wherein, the solvent in the step 3 and the step 4 include n,N-Dimethylformamide, ethyl alcohol and go from
Sub- water.
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