CN106970059A - A kind of preparation and its application of efficient two-photon nanometer diagnosis and treatment agent - Google Patents
A kind of preparation and its application of efficient two-photon nanometer diagnosis and treatment agent Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000003745 diagnosis Methods 0.000 title abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000010521 absorption reaction Methods 0.000 claims abstract description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002428 photodynamic therapy Methods 0.000 claims abstract description 9
- 230000012010 growth Effects 0.000 claims abstract description 7
- 239000003814 drug Substances 0.000 claims abstract 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
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- 239000002105 nanoparticle Substances 0.000 claims description 26
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
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- 229910021529 ammonia Inorganic materials 0.000 claims 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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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
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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Abstract
The invention belongs to nano biological medical judgement category, a kind of preparation of organic/inorganic composite nano materials system with good biocompatibility is mainly concerned with and its in biological two photon imaging and the application in double photosensitizer photodynamic therapies.The present invention is driven using the Supramolecular self assembly of porphyran complex, constructs the metal-organic framework material ZnTPyP MOF of functionalization, imparts new optics and architectural characteristic again while former assembling molecule ZnTPyP physicochemical characteristics is remained.Using MOF as interior nucleus growth shell titanium oxide, then one layer of poly-D-lysine is coated, obtain a kind of high performance two-photon diagnosis and treatment class nanometer bio probe.The nano-probe has good biological safety and dispersiveness, and ZnTPyP MOF have good two-photon absorption and fluorescent emission performance, realizes the sensitization photodynamic therapy under two-photon activation；It the method can be widely used in the fluorescence in situ diagnosis of various diseases especially cancer and treat, there is extremely important meaning in clinical medicine.
Description
Technical field
The invention belongs to nano biological medical imaging technology field, it is mainly concerned with a kind of with good biocompatibility
The preparation of efficient two-photon fluorescence probe and its application in two-photon sensitization photodynamic therapy.
Background technology
Porphines and porphyran are the knots of a variety of porphyrin tetrapyrroles such as naturally occurring chlorophyll and ferroheme
Structure skeleton, is the material of relying that life is present.Porphines quasi-molecule generally has good biocompatibility, while in opto-electronic conversion
During play key player.As the family member of big ring organic molecule, porphines quasi-molecule can pass through as basic molecule
The effect of pi-pi accumulation, hydrogen bond and Van der Waals force etc., realizes self assembly between supermolecule, and can obtain the nanocrystalline of different morphologies.From
Nanocrystalline after basic molecule to assembling, the photoelectricity performance of material changes therewith, and new performance also emerges in an endless stream, and then widens
The concrete application of porphines quasi-molecule.Zinc 5,10,15,20- tetra- (4- pyridine radicals) -21H, 23H, porphines (ZnTPyP) is as good
Photoactivation molecular matrix, available for assembling construct different-shape and the micrometer/nanometer metal-organic framework materials of size
(ZnTPyP-MOF), the progress for all kinds of photovoltaic reactions.In fact, no matter light-catalyzed reaction or photodynamic therapy mistake
Journey, light induced electron is most important for the carry out of reaction.However, emphasis is placed in such assembled material electronics by rare research at present
Efficiently generate and utilize, photoelectric properties abundant ZnTPyP-MOF are not yet fully excavated.
Multiphoton Absorbtion process refers to that under light laser effect, material absorbs multiple photons simultaneously, to activate electronics.
Compared with traditional single-photon process, the multi-photon laser of long wavelength has higher tissue penetration depths, and two-photon absorption
The main focal point in the ultra-intense laser produced by pulse laser of generation, therefore, biphotonic process has good space
Selectivity, injures smaller to sample, can obtain the imaging effect of high-resolution, realize to the optical diagnostics of disease in situ with controlling
Treat.With the development of research, current organic dyestuff (FITC, DAPI, diiodocosin) and inorganic nano material (gold nanorods,
Carbon quantum dot, ZnS), the potentiality in terms of Multiphoton Absorbtion are gradually disclosed.Organic two-photon absorption dyestuff generally has
Higher quantum yield, but the water delivery property of dye molecule, easy fluorescent quenching of cytotoxicity and in vivo extreme environment etc.
Limit its application in biology.Inorganic nonlinear two-photon absorption nano material, generally have stable chemical constitution and
It is easy to surface modification, is relatively specific for biological species research.But the optical property of inorganic material is typically more single, this is to actually grinding
It is quite restricted for studying carefully.ZnTPyP-MOF cladding co-catalysts TiO2, obtain ZnTPyP-MOF@TiO2(ZMT), remaining
While ZnTPyP-MOF two-photon absorptions and high quantum fluorescent yield, TiO is efficiently combined2Inorganic material easily modification and catalysis
The advantage of function admirable, the final two-Photon Absorption Properties using ZnTPyP-MOF realize the high-resolution pair of light to cell
Sub- fluorescence imaging and double photosensitizer TiO2Photodynamic therapy.
In summary, suitable organic/inorganic complex is prepared, each body advantage and tool can be given full play to by building one kind
The ZMT for having good biocompatibility is vital, and it is to the fluorescence imaging and TiO under two-photon driving2It is sensitized dynamics
Control significant.
The content of the invention
The purpose of the present invention be a kind of good biocompatibility of synthesis have efficient two-photon fluorescence concurrently and double photosensitizers are dynamic
The organic/inorganic hetero-nanocrystals of mechanics curative properties.
In order to solve the above technical problems, the present invention is achieved through the following technical solutions：
A kind of organic/inorganic heterogeneous nanometer of the two-photon fluorescence of novel and high-efficiency and double photosensitizer photodynamic therapy performances
Crystalline substance, is based on ZnTPyP-MOF assembling particles, to be provided by it two-photon absorption and activated by dye performance.TiO2Parcel energy
Enough ensure the hydrophily and biological safety of whole particle, in addition, joint ZnTPyP-MOF kernel collective effects, by interior nuclear excitation
Electronics imports outer layer TiO2Conduction band, to strengthen electronically active, collaboration is directed to the generation of active oxygen.
The preparation method of the nanometer two-photon biocrystal, is to use acid-base neutralization method first, in surfactant
Assembling preparation ZnTPyP-MOF is nanocrystalline in micella；Then, by titanium source hydrolysis, uniformly wrapped up on ZnTPyP-MOF surfaces
One layer of good water solubility, the high amorphous TiO of catalytic performance2；Finally, then by the effect of Electrostatic Absorption, in TiO2One layer of external sheath
Poly-D-lysine (PLL) with good biocompatibility, final obtain has the organic/inorganic of good biological security heterogeneous
It is nanocrystalline.
The technique that metal-organic framework nano material is prepared using molecular self-assembling method, is comprised the following specific steps that：Will
ZnTPyP is dissolved in the hydrochloric acid solution of 2 mM/ls (mM), and ZnTPyP Molecular Mass obtains ZnTPyP-H4 4+, it is added into
NaOH and CTAB mixed solution, ZnTPyP-H4 4+Alkali deprotonation is met, the ZnTPyP of water delivery enters in CTAB micellas, passed through
Zn-N bonding actions, obtain ZnTPyP-MOF nanocrystalline from group.Ethanol is cleaned 2~3 times, removes nanocrystal surface activating agent.
The ZnTPyP meets H+Protonation, adjusts ZnTPyP and H+Mol ratio, fully to turn to ZnTPyP protons
ZnTPyP-H4 4+, with the ZnTPyP-H being completely dissolved4 4+Presoma.
The ZnTPyP-H4 4+Add CTAB NaOH solution, system stir about 5 minutes, ZnTPyP-H4 4+With OH-
Fully neutralize, assembling process is completed, product immediately need to be collected by centrifugation.
PH, CTAB of the reaction assembling solution concentration and built-up time can significantly affect the pattern and size of product,
Must strictly it control.
Product ZnTPyP-MOF after the assembling is cleaned repeatedly using ethanol, is removed after surfactant, eccentric cleaning
It is scattered in standby in ethanol.
Titanium source hydrolysis process under being aided in using CTAB, in ZnTPyP-MOF nano particles outer surface, one layer of growth is unformed
TiO2, comprise the following steps：ZnTPyP-MOF dissolvings are scattered in the 0.2mM CTAB NaOH aqueous solution；Again by diisopropoxy
Bis-acetylacetonate titanium (TDAA) presses 1 with methanol:100 volume dilutions, add in ZnTPyP-MOF solution by batch, slowly stir on a small quantity
Mix so that TDAA slowly hydrolyzes growth TiO on ZnTPyP-MOF surfaces2, ethanol clean 2~3 times, remove nanocrystal surface activity
Agent.
The ZnTPyP-MOF@TiO of the CTAB assisting growths synthesis2(being abbreviated as ZMT) particle has good water solubility
And dispersiveness.
TiO in the ZMT particles2Successful cladding, need to be about side in 0.2mM, the solution that pH is about 10 in CTAB concentration
It can be achieved, the CTAB of excessive concentrations will hinder TiO2Superficial growth, cross low concentration CTAB can then cause in ZnTPyP-MOF
The soft aggregation of core, so as to influence the pattern of final product.
Product ZMT after the assembling is cleaned repeatedly using ethanol, and water is scattered in after removing surfactant, eccentric cleaning
In it is standby.
Using Electrostatic Absorption mode, the good PLL of one layer of biocompatibility is modified in ZMT nano particles outer surface.Including
Following steps：The ZMT aqueous solution is added to PLL PBS solution, is slowly stirred 20 minutes, the nanometer after water washing collection PLL modifications
Particle.
The PLL solution systems are to be formed by PLL and NaCl is miscible in PBS, and maintain the temperature at 4 degree.
The ZMT particles are added after PLL systems, are slowly stirred 20 minutes, are washed 2~3 times, are obtained PLL and are uniformly coated, point
Dissipate the good ZMT@PLL of property.
The beneficial effects of the invention are as follows：
(1) organic porphines molecule assembling kernel ZnTPyP-MOF can provide absorption Near-infrared Double photon and swash in the present invention
Light, for launching fluorescence, its phototoxicity very little, mainly its a small amount of singlet oxygen for exciting electronics and oxygen effect generation.
(2) Surface coating TiO of the present invention2Afterwards, the electronics produced under ZnTPyP-MOF two-photon excitations, can efficiently inject table
Face TiO2, to strengthen electronically active, so as to reduce ambient oxygen for superoxide anion, cytotoxicity drastically strengthens, the two association
With the double photosensitizer photodynamic therapies that can be achieved to deep tissue in situ tumour.
(3) present invention is widely used in fluorescence diagnosis and the optical dynamic therapy of various diseases especially cancer, and this should in clinic
There is extremely important meaning in.
Brief description of the drawings
Fig. 1 is transmission (TEM) and ESEM (SEM) photo that nano particle is made in embodiment 1；
Fig. 2 is hydration kinetics chi of the ZnTPyP-MOF and ZMT nano particles made from embodiment 1 before and after PLL is modified
The comparison diagram of very little (DLS)；
Fig. 3 is ZnTPyP monomer molecules made from embodiment 1, the abosrption spectrogram of ZnTPyP-MOF and ZMT nano particles.
Fig. 4 is active oxygen of the ZnTPyP-MOF and ZMT nano particles under 500nm radiation of visible light made from embodiment 1
Testing result figure.
Fig. 5 be ZnTPyP-MOF with ZMT nano particles made from embodiment 1 by " street cleaner's experiment " detection active oxygen into
The testing result figure divided.
Fig. 6 is active oxygen inspection of the ZnTPyP-MOF and ZMT nano particles made from embodiment 1 under the irradiation of 808nm laser
Survey result figure.
Fig. 7 is ZnTPyP made from embodiment 1, ZnTPyP-MOF, ZMT single photons and two-photon laser fluorescence spectra.
Fig. 8 is fluorescence of the ZnTPyP-MOF and ZMT nano particles under 830nm two-photon excitations made from embodiment 1
Figure.
Fig. 9 is square value and transmitting fluorescence intensity of the ZMT nano particles made from embodiment 1 in different double luminous intensities
Linear relationship chart.
Figure 10 is the two-photon fluorescence on ZMT nano particles made from embodiment 1 in the cell different aspects.
Figure 11 in the cell, utilizes synchronous light stimulus side for ZnTPyP-MOF and ZMT nano particles made from embodiment 1
Method, active oxygen variation diagram of the monitoring cell under the irradiation of 830nm two-photons.
Figure 12 is ZnTPyP-MOF and ZMT nano particles made from embodiment 1 and simple TiO2To dense in different ions
When spending, the influence (mtt assay) to cell survival rate.
Figure 13 is ZnTPyP-MOF and ZMT nano particles made from embodiment 1 and simple TiO2In same ion concentration
Under, the cell survival rate (mtt assay) after the irradiation of 830nm two-photons femto-second laser.
Embodiment
With reference to embodiment, the invention will be further described：
Fig. 1 a are the specific preparation flow figure for the ZMT that PLL is coated
First, the preparation of ZnTPyP-MOF hydrophobic nanoparticles：
1.ZnTPyP-H4 4+Preparation：ZnTPyP is dissolved in 0.2mol/L hydrochloric acid solution, obtains 0.01mol/L's
ZnTPyP solution.
The preparation of 2.CTAB micellar solutions：CTAB is dissolved in 10mmol/L NaOH solution, and the CTAB for obtaining 2mmol/L is molten
Liquid.
3. the ZnTPyP solution for measuring 0.5mL rapidly joins 9.5mL CTAB solution, it is slowly stirred 5 minutes, adds alcohol,
10000 revs/min, product is quickly collected by centrifugation.
During Fig. 1 b-c are the nanocrystalline SEM spectrums of ZnTPyP-MOF manufactured in the present embodiment, figure：The ZnTPyP-MOF is
Hexagon nanometer plate.
Fig. 1 d are that the present embodiment is prepared in the nanocrystalline Elemental redistribution EDS figures of ZnTPyP-MOF, figure：Carbon and Zn-ef ficiency are significantly deposited
Titanium and oxygen element are nearly no detectable.
Fig. 1 h are that the present embodiment is prepared in the nanocrystalline Elemental redistribution TEM figures of ZnTPyP-MOF, figure：The ZnTPyP-MOF chis
Very little about 300nm.
2nd, ZnTPyP-MOF@TiO2The preparation of hydrophilic nano：
The preparation of 1.TDAA methanol solutions：Measure 10 μ LTDAA to be dissolved in 500 μ L methanol solutions, be kept in dark place in room temperature
Under.
The preparation of 2.CTAB alkaline solutions：The NaOH solution that configuration pH is 11.0 first, the alkaline solution is dissolved in by CTAB
In, it is made into the CTAB reaction solutions that concentration is 0.2mmol/L.
3.5 micromolar ZnTPyP-MOF (in terms of ZnTPyP) are dissolved in 8mL CTAB alkaline solutions, add 25 μ LTDAA first
Alcoholic solution, reacts 30 minutes, adds 25 μ LTDAA methanol solutions, continues to react 2 hours, product is collected by centrifugation.
Fig. 1 c-f are the SEM spectrum of ZMT nano particles manufactured in the present embodiment, in figure：Described nano particle disperses good
It is good, and without homogenous nucleation.
Fig. 1 g scheme for the Elemental redistribution EDS of ZMT nano particles manufactured in the present embodiment, in figure：Carbon, zinc, titanium and oxygen are notable
In the presence of.
Fig. 1 i-j scheme for the TEM of ZMT nano particles manufactured in the present embodiment, in figure：Described nano particle outer layer is uniform
Coat TiO2, and without homogenous nucleation.
3rd, PLL modifies nano particle：
The preparation of 1.PLL systems：NaCl is dissolved in pH=7.4 PBS solution, then PLL is dissolved in the PBS, is prepared
Concentration is 1mg/mL PLL solution.
2.ZnTPyP-MOF or ZMT are dissolved in 200 μ L water or ethanol respectively, rapidly join 1mL PLL systems, slowly stir
Mix 20 minutes, centrifugation washing, and final product is dispersed in water.
Fig. 2 a, b are that DLS of the ZnTPyP-MOF nano particles manufactured in the present embodiment before and after PLL is modified is composed, in figure：Institute
The ZnTPyP-MOF nano particles stated are well dispersed after PLL modifications, and grain size reaches unanimity.
Fig. 2 c, d are that DLS of the ZMT nano particles manufactured in the present embodiment before and after PLL is modified is composed, in figure：Described ZMT
Nano particle is well dispersed after PLL modifications, and particle size range is more concentrated.
4th, in solution active oxygen detection：
Prepared ZnTPyP-MOF and ZMT can produce active oxygen under excited by visible light, and the presence of titanium oxide can
ZnTPyP-MOF activation electronics is significantly increased, reduction oxygen generates superoxide anion, and this is ZMT in biological optical dynamic therapy
Application provide condition.
Fig. 3 is ZnTPyP-MOF manufactured in the present embodiment and ZMT and the abosrption spectrogram of assembling matrix ZnTPyP molecules, figure
In：The nanocrystalline absorption in visible region after assembling is significantly increased.
Fig. 4 is ZnTPyP-MOF, ZMT and TiO manufactured in the present embodiment2Active oxygen is produced under 500nm radiation of visible light
Detection spectrogram.1,3- diphenyl isobenzofuran (DPBF) is active oxygen (superoxide anion and singlet oxygen) capture probe,
By monitoring the reduction of absorption peak strength at DPBF 410nm, the generation to judge active oxygen, in figure：Identical illumination condition
Under, ZMT active oxygen yields are significantly higher than ZnTPyP-MOF and TiO2Independent role result.
Fig. 5 is the test experience result of the specific composition of the present embodiment active oxygen.1,4-benzoquinone is superoxide anion capturing agent, plus
Enter the DPBF detection solution of active oxygen, just can effectively exclude in influence of the superoxide anion to DPBF absworption peaks, figure：Same light is shone
Under the conditions of, the addition of 1,4-benzoquinone so that ZMT group active oxygen yields and ZnTPyP-MOF and TiO2Compared during independent role, without aobvious
Write difference.Verify under same light photograph, ZnTPyP-MOF and ZMT combinations oxygen effect product is respectively that singlet oxygen and super oxygen are cloudy
Ion, absolutely proves TiO2As co-catalyst, ZnTPyP-MOF photocatalytic activity can be significantly increased.
Fig. 6 is the present embodiment ZnTPyP-MOF, ZMT and TiO2Work is produced under the irradiation of 830nm near-infrared single photons laser
The detection spectrogram of property oxygen.1,3 diphenyl isobenzofuran (DPBF) is that active oxygen (superoxide anion and singlet oxygen) captures spy
Pin, by monitoring the reduction of absorption peak strength at DPBF 410nm, the generation to judge active oxygen, in figure：Same light shines bar
Under part, ZMT active oxygens yield and ZnTPyP-MOF and TiO2Independent role is without significant difference.
5th, the detection of two-photon fluorescence imaging：
Prepared ZnTPyP-MOF can absorb multiple photons, transmitting under the irradiation of 830nm two-photons femtosecond laser
650nm or so hyperfluorescences, this is that ZnTPyP assemblies apply the condition of providing in terms of biological two-photon fluorescence imaging.
Fig. 7 is the present embodiment ZnTPyP monomer molecules, and ZnTPyP-MOF is in 415nm ultraviolet lights and 830nm two-photon lasers
In the lower fluorogram produced of irradiation, figure：Difference is excited under light irradiation, and ZnTPyP monomer molecules, ZnTPyP-MOF transmitting is glimmering
Light is basically identical, illustrates that ZnTPyP-MOF has been sufficiently reserved the fluorescence excitation and emission characteristic of ZnTPyP monomer molecules.
Fig. 8 is the present embodiment ZnTPyP monomer molecules, and transmittings of the ZnTPyP-MOF under the irradiation of 830nm two-photon lasers is glimmering
In light figure, figure：Under identical two-photon excitation, ZnTPyP monomer molecules and ZnTPyP-MOF transmitting fluorescence signal are basically identical.
Fig. 9 is transmitting fluorescence intensity figures of the present embodiment ZnTPyP-MOF under different two-photon excitations, in figure：Two-photon
Laser intensity it is square linear with ZnTPyP-MOF transmitting fluorescence signal, it was demonstrated that ZnTPyP-MOF two-photon fluorescence
Characteristic.
Figure 10 is after the present embodiment ZnTPyP-MOF@PLL are co-cultured with human cervical carcinoma cell (HeLa), under two-photon excitation
Different cell aspects material transmitting fluorogram, in figure：Change Z axis height, collect the material fluorescence letter in different focal planes
Breath, it was demonstrated that ZnTPyP-MOF is phagocytized by cells in arrival cytoplasm, rather than is attached to cell surface.
6th, in cell active oxygen detection：
Prepared ZnTPyP-MOF and ZMT can significantly absorb Near-infrared Double photon, while transmitting fluorescence, with reference to TiO2
A large amount of active oxygens can be produced, for killing tumour cell.
Figure 11 is the present embodiment ZnTPyP-MOF, ZMT and TiO2It is intracellular under the irradiation of 830nm two-photons femto-second laser
The active oxygen testing result of generation.Using the Strength Changes of active oxygen kit fluorescence dyestuff, monitoring 830nm two-photons are stimulated
Under, the change of reactive oxygen species yield, in figure：In synchronizable optical stimulation test, the pretreated cells of ZMT, active oxygen yield
It is significantly higher than ZnTPyP-MOF and TiO2Result under individually cultivating.
By active oxygen detection probe, on a cellular level, ZnTPyP-MOF and TiO are demonstrated2Under synergy, activity
The generation efficiency of oxygen is greatly improved, and cytotoxicity greatly strengthens, and demonstrates ZnTPyP-MOF and can absorb 830nm two-photons, realizes
ZMT photosensitizer photodynamic therapies under two-photon excitation.
7th, cell survival rate is tested：
Prepared ZnTPyP-MOF, ZMT and TiO2, under being co-cultured with cell under various concentrations, the mtt assay detection of standard
Cell survival rate under each treatment conditions.Stimulated with reference to 830nm two-photon lasers, detect the pretreated cell of different materials
Survival condition.
Figure 12 is the present embodiment ZnTPyP-MOF, ZMT and TiO2Cytotoxicity testing result after being co-cultured with cell.Figure
In：Under suitable ion concentration, ZnTPyP-MOF, ZMT and TiO2Without notable cytotoxicity after being co-cultured with cell.
Figure 13 is the present embodiment ZnTPyP-MOF, ZMT and TiO2Cell after the irradiation of 830nm two-photons femto-second laser
Survival rate.In figure：In same light stimulation test, the pretreated cells of ZMT, ZMT cell lethality is significantly higher than ZnTPyP-
MOF and TiO2Result under independent role.
In summary, contrasted with existing two-photon fluorescence and sensitization dynamics diagnosis and treatment probe, the metal that the present invention is provided
Porphines super-molecule assembling body can give full play to kernel ZnTPyP-MOF and shell TiO while biocompatibility is ensured2's
Respective advantage.ZnTPyP-MOF can launch stronger fluorescence under Near-infrared Double photon excitation, and with significant advantage：(1) it is long
The near infrared light of wavelength is influenceed smaller than short-wavelength light by scattering, easily penetrates sample；(2) exciting light can reach focal plane, burnt
Out-of-plane fluorescence molecule is not excited, and image resolution ratio is high；(3) near infrared light at long wave than the light of short wavelength to cell toxicant
Property is small.ZnTPyP-MOF@TiO2Middle ZnTPyP-MOF can activate dye molecule, activated state electron injection TiO after absorbing two-photon2,
Electronically active is significantly increased, and goes back primary electron for superoxide anion, for killing cancer cell, this for disease in situ clinically very
It is significant with optical therapeutic to being accurately positioned for tumour.
Above example is served only for being described in further detail technical scheme, it is impossible to be interpreted as to the present invention
The limitation of protection domain, some nonessential improvement and tune that those skilled in the art makes according to the above of the present invention
It is whole to belong to protection scope of the present invention.
Claims (8)
1. a kind of novel two-photon fluorescent is imaged Nanoscale assemblies, it is characterised in that：Efficient two-photon fluorescence imaging performance is come
Come from the effect that ZnTPyP-MOF assembles porphines molecule.
2. a kind of preparation method of the two-photon fluorescence imaging Nanoscale assemblies described in claim 1, it is characterised in that：Protonation
Porphines meet alkali in micella self-organizing growth be hydrophobic nanoparticles technique, comprise the following specific steps that：ZnTPyP is dissolved in
In certain density hydrochloric acid, protonation obtains ZnTPyP-H4 4+, add after alkaline cetyl trimethylammonium bromide solution, delay
Slow stirring, is collected by centrifugation assembling product ZnTPyP-MOF.
3. the preparation method of two-photon fluorescence imaging Nanoscale assemblies according to claim 2, it is characterised in that：Will be hydrophobic
ZnTPyP add and put in certain density hydrochloric acid solution, protonation product ZnTPyP-H4 4+It is changed into hydroaropic substance, solution is ink
Green liquid.
4. a kind of novel two-photon is sensitized dynamics organic/inorganic hetero-nanocrystals, it is characterised in that：Efficient light power production is lived
Property oxygen performance derive from ZnTPyP-MOF and TiO2Collective effect.
5. a kind of preparation method of the nano biological organic/inorganic hetero-nanocrystals described in claim 4, it is characterised in that：Will
ZnTPyP-MOF and the cetyl trimethylammonium bromide solution of alkalescence are mixed, and add the double second of diisopropoxy by batch by several times
The methanol dilution solution of acyl acetone titanium, 280~330 revs/min of lasting stirrings, built-up time is 4~6 minutes, after assembling terminates
It need at once centrifuge, terminate assembling process, obtain amorphous TiO2The ZnTPyP-MOF@TiO uniformly coated2, referred to as ZMT finally leads to
Electrostatic Absorption mode is crossed, one layer of good biocompatibility, water-soluble high poly are uniformly coated in ZnTPyP-MOF nanocrystal surfaces
Rely ammonia.
6. the preparation method of nano biological organic/inorganic hetero-nanocrystals according to claim 5, it is characterised in that：Two
Isopropoxy bis-acetylacetonate titanium and methanol 1:100 volume dilutions, add the hydrolysis solution of alkalescence, and TDAA is slowly hydrolyzed,
And in the uniform apposition growth in ZnTPyP-MOF surfaces.
7. a kind of application of the two-photon fluorescence imaging Nanoscale assemblies described in claim 1, it is characterised in that：It is double in 830nm
Under photon excitation, the hyperfluorescence that two-photon produces 640~660nm is can absorb, the original position available for clinical or clinical translational medicine
The fluorescence imaging detection of tissue, ultrahigh resolution.
8. a kind of application of the nano biological organic/inorganic hetero-nanocrystals described in claim 4, it is characterised in that：In double light
It is sensitized in photodynamic therapy, while ZMT kernels absorb two photon emission fluorescence, produces enough electronics, the shell of regrowth can
Interior nuclear electron is exported to TiO2Surface, significantly increases electronically active, can activate ambient oxygen, produces superoxide anion, is used for
Kill unfavorable tissue or cell.
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| CN109265701A (en) * | 2018-10-22 | 2019-01-25 | 江西理工大学 | A kind of pair of acetylacetone,2,4-pentanedione has the zinc-base metal organic frame and preparation method thereof of selective fluorescence identifying |
| CN109738406A (en) * | 2019-01-03 | 2019-05-10 | 中南民族大学 | A method of quantitative determination catechins |
| CN114788863A (en) * | 2022-03-16 | 2022-07-26 | 苏州深得源健康科技有限公司 | Method for preparing zinc porphyrin nanospheres and application thereof |
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| CN109265701A (en) * | 2018-10-22 | 2019-01-25 | 江西理工大学 | A kind of pair of acetylacetone,2,4-pentanedione has the zinc-base metal organic frame and preparation method thereof of selective fluorescence identifying |
| CN109265701B (en) * | 2018-10-22 | 2021-03-16 | 江西理工大学 | Zinc-based metal organic framework with selective fluorescence recognition on acetylacetone and preparation method thereof |
| CN109738406A (en) * | 2019-01-03 | 2019-05-10 | 中南民族大学 | A method of quantitative determination catechins |
| CN114788863A (en) * | 2022-03-16 | 2022-07-26 | 苏州深得源健康科技有限公司 | Method for preparing zinc porphyrin nanospheres and application thereof |
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