CN105031669B - A kind of nuclear-shell structured nano-composite material and the preparation method and application thereof - Google Patents
A kind of nuclear-shell structured nano-composite material and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of nuclear-shell structured nano-composite materials and the preparation method and application thereof.The composite material is with BaGdF5Nanocrystalline is core, using mesoporous silicon oxide as shell, and in the surface modification photosensitizer silicon phthalocyanine dihydroxide and targeting agent hyaluronic acid of mesoporous silicon oxide.Compared with prior art, the present invention prepares oil-soluble five fluorine gadolinium barium nano-particle by solvent-thermal method, and oil-soluble five fluorine gadolinium barium nano-particle is carried out water-soluble modified, pass through the coating mesoporous silica of sol-gal process again, its surface has a large amount of amino can be in conjunction with targeted molecular HA, while can be bonded photosensitizer silicon phthalocyanine dihydroxide on the surface of mesoporous silicon oxide.The uniform particle diameter of prepared nano material, favorable dispersibility, T1Weighted imaging and CT imaging effects are apparent, which has the function of nuclear-magnetism radiography, CT radiographies, photo-thermal therapy and photodynamic therapy simultaneously.The composite material has potential application in terms of the imaging of tumour and treatment.
Description
Technical field
The present invention relates to a kind of nanocomposites, more particularly, to a kind of nuclear-shell structured nano-composite material and its preparation
Method and application.
Background technology
The nano material of Water-soluble paramagnetic can be used as mri contrast agent, and paramagnetic metal ion includes Fe3 +、Fe2+、Gd3+And Dy3+.Wherein Gd3+There are 7 unpaired electrons, spin magnetic moment is big, and electric field is symmetrical, and relaxation rate is high, and Yi Yushui matches
Position, and water of coordination molecule is 8-9, is the preferable selection of contrast agent.MRI technique can highly desirable show soft tissue
Anatomical details, and contrast agent can be such that image becomes apparent from, to realize the real-time observation of physiological activity.
The contrast agent of Ba bases is a kind of very traditional and clinically widely applied CT contrast agent, Ba elements have
Larger atomic number (ZBa=56), X-ray attenuation coefficients are big, have good CT contrasting effects, can be used for preparing CT and make
Shadow agent.
Mesopore silicon dioxide nano material skeleton structure is stablized, and aperture rule, surface is easy to modify rich in hydroxyl, Ke Yiyou
Effect ground loads and transports different size and various types of drugs.The mesoporous silicon oxide of multifunction has good biofacies
Capacitive and the chemical property stablized, can be modified targeted molecular, fluorescent molecular, chemicals etc., be prepared into multifunction
Medicament transport system.
Photodynamic therapy (Photodynamic Therapy, PDT) is another after operative treatment, radiotherapy chemotherapy
The brand-new therapy of kind.It is a kind of new technology that medical diagnosis on disease and treatment are carried out using photodynamic effect.This is a kind of aerobic
The Photosensitive reaction for the adjoint biological effect that molecule participates in.Its process is：With the laser irradiation of specific wavelength, make photosensitizer by
Energy transmission to the oxygen of surrounding, is generated highly active active oxygen, singlet oxygen makes adjacent by excitation, the photosensitizer of excitation state
Oxidation reaction occurs for large biological molecule, so as to cause cell damage or even death.
Photo-thermal therapy (Photothermal therapy, PTT) is that one kind can be by photothermal conversion reagent by near-infrared
Light transforms into heat, a kind of method for treating disease.It is a kind of energy suction usually as photothermal conversion reagent nano material
Certain light especially near infrared light is received, the heat generated by plasma resonance or energy jump band, to cause locally
High temperature, the final functional material for killing tumour cell.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of nuclear shell structure nanos
Composite material and preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of nuclear-shell structured nano-composite material, the composite material is with BaGdF5Nanocrystalline is core, with mesoporous silicon oxide
For shell, and in surface modification photosensitizer silicon phthalocyanine dihydroxide (the Silicon phthalocyanine of mesoporous silicon oxide
Dihydroxide, SPCD) and targeting agent hyaluronic acid.
The grain size of the composite material is 60-70nm, and the grain size of core is 13-17nm, and uniform particle sizes, good dispersion,
With excellent biocompatibility, drugloading rate is big, T1Weighted imaging and CT imaging effects are good.
A kind of preparation method of nuclear-shell structured nano-composite material, includes the following steps：
(1) nano-particle BaGdF is prepared5；
(1.1) ethyl alcohol, oleic acid, oleyl amine are added in NaOH aqueous solutions, stirs to get uniform solution；
(1.2) by Gd (NO3)3·6H2O、BaCl2·2H2O、NH4It is molten that the aqueous solution of F is added sequentially to mixing obtained by (1.1)
Liquid, stirring, obtains colloidal solution；
(1.3) colloidal solution that (1.2) obtain is transferred in the high-temperature high-pressure reaction kettle with polytetrafluoroethyllining lining,
200 DEG C of -220 DEG C of reaction 30-40h, obtain nano-particle BaGdF5；
(1.4) the nano-particle BaGdF that will be obtained in (1.3)5, with the mixed liquor centrifuge washing 3 times of ethyl alcohol and n-hexane,
And by obtained BaGdF5It is distributed in chloroform, obtains oil-soluble BaGdF5Nano-particle；
(1.5) by the oil-soluble BaGdF in step (1.4)5Nano-particle is added dropwise to cetyl trimethylammonium bromide water
It in solution, stirs 2-3 hours, is heated to 50 DEG C -70 DEG C, kept for 5-15 minutes, steam organic solvent, obtain water-soluble BaGdF5
Nano-particle.
Preferably, in step (1.1), oleic acid, oleyl amine, ethyl alcohol, sodium hydroxide amount ratio be 40mL:3mL:24mL：
1.2g；In step (1.2), the dosage molar ratio of tri- kinds of elements of Gd, Ba, F is 1:1:5；In step (1.5), BaGdF5With 16
The addition proportioning of alkyl trimethyl ammonium bromide is 1mmol：16-20g.
(2) in nano-particle BaGdF5The coating mesoporous silica in surface, obtains to surface and is coated with mesoporous silicon oxide
BaGdF5Nano-particle, i.e. BaGdF5@mSiO2Nano-particle；
(2.1) water solubility BaGdF will be contained5For the solution of nano-particle under the conditions of 50-70 DEG C, pH value is adjusted to 8-9, according to
Then secondary addition tetraethyl orthosilicate and ethyl acetate add 3- aminopropyls-triethoxysilane, keep reacting liquid temperature
To 50 DEG C -70 DEG C, stirs 10-24 hours, make BaGdF5The coating mesoporous silica of nanoparticle surface；
(2.2) product obtained step (2.1) cools down, and with ethyl alcohol centrifuge washing 6 times, obtained product is dispersed in two
In secondary water.
Preferably, in step (2.1), BaGdF5, tetraethyl orthosilicate, ethyl acetate and 3- aminopropyls-triethoxy
The addition proportioning of silane is 1mmol：4-8mL：25-40mL：0.5-3mL；In step (2.2), BaGdF5With the amount ratio of ethyl alcohol
For 1mmol：500mL.
(3) SPCD is dissolved in n,N-Dimethylformamide, obtained SPCD solution is added drop-wise to surface and is coated with Jie dropwise
The BaGdF of hole silica5In nano-particle solution, it is protected from light 10-24 hours, centrifuge washing, obtaining surface modification has light
The BaGdF of quick dose of SPCD5Nano-particle, i.e. surface modification have the BaGdF of photosensitizer SPCD5@mSiO2Nano-particle；
Preferably, SPCD and the amount ratio of n,N-Dimethylformamide are 15mg：10mL；SPCD and BaGdF5Amount ratio
For 60mg：1mmol.
In the present invention, the structural formula of SPCD is as follows：
(4) surface modification obtained by step (3) has the BaGdF of photosensitizer SPCD5Continue to modify target in the surface of nano-particle
To agent hyaluronic acid, target product nuclear-shell structured nano-composite material is obtained：
1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimine hydrochloric acid, N- hydroxysuccinimides are dissolved in 2- (N-
Quinoline) in ethanesulfonic acid monohydrate (MES) buffer solution, sequentially add hyaluronic acid (HA), surface modification has photosensitizer SPCD's
BaGdF5@mSiO2Nano-particle is protected from light 6 hours, and solution is dialysed for 24 hours with secondary water after reaction, finally uses Rotary Evaporators
Concentration can be obtained target product nuclear-shell structured nano-composite material；
Preferably, a concentration of 0.5M of 2- (N- morpholines) ethanesulfonic acid monohydrate buffer solution, 1- ethyls-(3- dimethyl
Aminopropyl) phosphinylidyne diimine hydrochloric acid, N- hydroxysuccinimides, hyaluronic acid and 2- (N- morpholines) ethanesulfonic acid monohydrate it is molten
The amount ratio of liquid is 8-10mg：8-10mg：10mg：5mL；Hyaluronic acid and BaGdF5Addition proportioning be 50mg：0.025-
0.05mol。
Above-mentioned nuclear-shell structured nano-composite material is the nuclear-shell structured nano-composite material of photosensitizer Direct Bonding modification, can
To apply in preparing mri contrast agent and CT contrast agent.
The nuclear-shell structured nano-composite material of above-mentioned photosensitizer Direct Bonding modification can be applied in pharmaceutical carrier.
The nuclear-shell structured nano-composite material of above-mentioned photosensitizer Direct Bonding modification can be applied in photo-thermal and the treatment of light power
Tumour is treated in ruling by law.
Compared with prior art, the present invention prepares oil-soluble five fluorine gadolinium barium nano-particle by solvent-thermal method, and to oil
The five fluorine gadolinium barium nano-particles progress of dissolubility is water-soluble modified, then passes through the coating mesoporous silica of sol-gal process, surface
There is a large amount of amino can be in conjunction with targeted molecular HA, while photosensitizer SPCD can be bonded on the surface of mesoporous silicon oxide.Institute
Obtained nano material while having the function of nuclear-magnetism radiography, CT radiographies, photo-thermal therapy, optical dynamic therapy.It is targeted by being bonded
Agent HA while improving material water dissolution properties, also makes material have certain targeting.Synthesized nanocomposite is in tumour
Imaging and treatment in terms of have potential application prospect.
The exposed Si-O keys of the composite material surface can be the same as the group Si-OH of photosensitizer SPCD (silicon phthalocyanine dihydroxide) institute band
Hydrolysis occurs, photosensitizer is made to pass through the surface that covalent effect is bonded directly to silica.Laser of the SPCD in 660nm swashs
Singlet oxygen can be generated by giving, and can be used for photodynamic therapy.Meanwhile SPCD can be by light under the laser irradiation of 808nm
It can be converted into thermal energy.Two kinds of therapies, which combine, can more effectively kill cancer cell.Simultaneously in the surface bond HA (hyalomitomes of material
Acid) improve its biocompatibility, extend circulation time in vivo.And HA is a kind of common targeted molecular, can treated
It is specific in journey to be targeted to cancer cell, such as：HeLa, and combine that photo-thermal, that light power synergistic treatment effectively kills cancer is thin
Born of the same parents.The material is expected to, as a kind of multifunctional material integrating diagnoses and treatment, to obtain further in nanosecond medical science field
Research and application.
Description of the drawings
Fig. 1 is to prepare BaGdF in embodiment 15@mSiO2The preparation flow figure of-SPCD-HA.
Fig. 2 is BaGdF obtained in embodiment 15XRD.
Fig. 3 is BaGdF obtained in embodiment 15TEM image.
Fig. 4 is BaGdF obtained in embodiment 15@mSiO2TEM image.
Fig. 5 is BaGdF obtained in embodiment 15@mSiO2Particle diameter distribution.
Fig. 6 is BaGdF in embodiment 25@mSiO2The singlet oxygen test map of-SPCD-HA.
Fig. 7 is various concentration BaGdF in embodiment 35@mSiO2The photo-thermal curve of-SPCD-HA.
Fig. 8 is BaGdF in embodiment 35@mSiO2The solar thermochemical cycle curve of-SPCD-HA.
Fig. 9 is BaGdF in embodiment 35@mSiO2Uv-vis spectra before and after the photo-thermal of-SPCD-HA.
Figure 10 is BaGdF in embodiment 45@mSiO2The T of-SPCD-HA1NMR imaging figure.
Figure 11 is the photo-thermal therapy effect contrast figure of HeLa cells.
Figure 12 is the optical dynamic therapy effect contrast figure of HeLa cells.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The nuclear shell structure nano composite wood of photosensitizer Direct Bonding modification is prepared according to preparation flow figure as shown in Figure 1
Material, is abbreviated as BaGdF5@mSiO2-SPCD-HA.Include the following steps：
(1) capacity be 150mL beaker be added 1.2gNaOH, 4mL secondary waters, 24mL absolute ethyl alcohols, 40mL oleic acid,
3mL oleyl amines, stir evenly, and then sequentially add 1mmolGd (NO3)3·6H2O、1mmolBaCl2·2H2O、5mmolNH4F is stirred
30min is mixed, is transferred in polytetrafluoroethylene (PTFE) in the reaction kettle in village, then reaction kettle sealing is placed in 220 DEG C of atmosphere and is reacted
36h pours out supernatant liquid after being cooled to room temperature, and obtains the product for sinking to reactor bottom.With the mixed liquor of ethyl alcohol and n-hexane
Oil-soluble GdBaF is made in washed product 2~3 times5Nano-particle is placed in chloroform (CHCl3) in preserve.
(2) cetyl trimethylammonium bromide (CTAB) for weighing 400mg, is dissolved in 20mLH2In O, cetyl three is made
Methyl bromide aqueous ammonium will contain GdBaF in step (1)5The CHCl of nano-particle3Solution 1mL (a concentration of 0.025-
0.05mmol/mL), it is added dropwise in cetyl trimethylammonium bromide aqueous solution, stirs 2-3 hours, be then heated to 60 DEG C, dimension
It holds 30 minutes, steams CHCl3, colourless transparent solution is obtained, as water solubility BaGdF5Nano-particle solution.
(3) 40mL water is added in 100mL three-neck flasks, adds the NaOH solution of 100 μ L (2mol/L), stirring is equal
It is even, it is heated to 60 DEG C；By the water-soluble BaGdF in step (2)5It is added drop-wise in above-mentioned solution, by water-soluble BaGdF5Nano-particle
The pH value of solution is adjusted to 8-9；Then the tetraethyl orthosilicate of 0.2mL, the ethyl acetate of 1.0mL are added dropwise respectively, adds after 10min
The 3- aminopropyls of 0.2mL-triethoxysilane (APS) maintain 60 DEG C, are stirred overnight.By its cooled to room temperature, pass through
Centrifuge washing for several times, obtains to surface and is coated with the BaGdF of mesoporous silicon oxide5Nano material (is abbreviated as BaGdF5@mSiO2), most
After be scattered in 20mL ethyl alcohol, it is spare.
(4) surface obtained in step (3) is coated with to the BaGdF of mesoporous silicon oxide5Nano material is centrifuged with ethyl alcohol
Washing 6 times, template agent removing CTAB.
(5) SPCD is dissolved in n,N-Dimethylformamide, the cladding obtained SPCD solution being added drop-wise to dropwise in (4)
In the material of mesoporous silicon oxide, it is protected from light 12h.
(6) 100mg 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimine hydrochloric acid (EDC), 58mgN- hydroxyls are weighed
Succimide (NHS) is dissolved in the MES buffer solutions of 50mL, and 50mg HA are then added, and is then added in 20mg steps (5)
The nano-particle (BaGdF in nano-particle5Actual content is 6-8mg), it is protected from light 12h, obtains product BaGdF5@
mSiO2-SPCD-HA.After the completion of reaction, product is sealed in bag filter, is placed in secondary water and dialyses for 24 hours.
It can illustrate that the nano-particle prepared is BaGdF by Fig. 25Nano-particle.As can be seen from Figure 2 the oil prepared
Dissolubility BaGdF5The XRD of nano-particle matches with standard card.
As seen from Figure 3, the BaGdF of synthesis5The size of the uniform particle sizes of nano material, nano-particle are 14nm left
It is right.
It can be seen that synthesized BaGdF from the TEM image in Fig. 45@mSiO2Nano particle diameter is uniform, exists apparent
Nucleocapsid.Fig. 5 is that the particle diameter distribution of material counts, it is known that size is 63nm or so.
Embodiment 2
By 9,10 dimethylanthracenes (DMA) of 50 μ L, it is added drop-wise to BaGdF obtained in the embodiment 1 of 200 μ L5@mSiO2-
In the solution of SPCD-HA, BaGdF5@mSiO2- SPCD-HA is dispersed in ethyl alcohol：Water=4:1 in the mixed solvent.To mixed solution
With 660nm laser irradiations, the fluorescence of a solution is detected per 5min.Fluorescence exciting wavelength is 360nm, and launch wavelength is 380-
550nm.Cycle detection 1h, the generation for examining singlet oxygen.
Regularity variation is presented in the fluorescence intensity downward trend of DMA as can be seen from Figure 6, illustrates that SPCD is excited in 660nm
Under can generate singlet oxygen.
Embodiment 3
By BaGdF prepared in embodiment 15@mSiO2- SPCD-HA composite materials are configured to different concentration, use
The laser irradiation of 808nm tests the photo-thermal heating curve and solar thermochemical cycle curve of solution.It can be seen from figure 7 that in 808nm
Under the irradiation of laser, the lift-off value of solution temperature increases with the increase of concentration.From figure 8, it is seen that the photo-thermal of material is steady
It is qualitative fine.
Fig. 9 is the UV, visible light atlas of near infrared spectra before and after material illumination.From fig. 9, it can be seen that illumination is front and back to material
Absorption spectrogram also do not influence.
Embodiment 4
By BaGdF obtained in embodiment 15@mSiO2- SPCD-HA composite nano materials are configured to 6 groups of various concentrations
BaGdF5@mSiO2- SPCD-HA solution is detected in the Nuclear Magnetic Resonance of 0.5T, and the results are shown in Figure 10.
Embodiment 5
In order to detect BaGdF obtained in embodiment 15@mSiO2The cell photo-thermal therapy of-SPCD-HA composite nano materials
Effect is divided into the experiment of HeLa cells：The BaGdF of blank group, blank group+808nm laser 10 minutes, various concentration5@
mSiO2- SPCD-HA group+808nm laser 10 minutes.With the survival rate of mtt assay test cell, to reflect the treatment effect of material
Fruit.Materials Cell level photo-thermal therapy is with obvious effects as can be seen from Figure 11.
In order to detect the cell optical dynamic therapy effect of composite nano materials obtained in embodiment 1, to HeLa cells
Experiment is divided into：The BaGdF of blank group, blank group+660nm laser 20 minutes, various concentration5@mSiO2- SPCD-HA groups+660nm
Laser 20 minutes, with the survival rate of mtt assay test cell, to reflect the therapeutic effect of material, material as can be seen from Figure 12
There is obvious optical dynamic therapy effect.
The above-mentioned description to embodiment is for ease of ordinary skill in the art to understand and use the invention.It is ripe
The personnel for knowing art technology obviously easily can make various modifications to these embodiments, and general original described herein
It ought to use in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, this field
Technical staff's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in the guarantors of the present invention
Within the scope of shield.
Claims (7)
1. a kind of nuclear-shell structured nano-composite material, which is characterized in that the composite material is with BaGdF5Nanocrystalline is core, with mesoporous
Silica is shell, and in the surface modification photosensitizer silicon phthalocyanine dihydroxide and targeting agent hyaluronic acid of mesoporous silicon oxide；
The preparation method of nuclear-shell structured nano-composite material includes the following steps：
(1) nano-particle BaGdF is prepared5；
(2) in nano-particle BaGdF5The coating mesoporous silica in surface, obtains to surface and is coated with the BaGdF of mesoporous silicon oxide5
Nano-particle is coated with the BaGdF of mesoporous silicon oxide5Nano-particle BaGdF5@mSiO2It indicates；
(3) the surface modification photosensitizer silicon phthalocyanine dihydroxide of the mesoporous silicon oxide of nano-particle obtained by step (2), obtains table
Face is modified with the BaGdF of photosensitizer silicon phthalocyanine dihydroxide5@mSiO2Nano-particle；
(4) surface modification obtained by step (3) has the BaGdF of photosensitizer silicon phthalocyanine dihydroxide5@mSiO2The surface of nano-particle after
Continuous modification targeting agent hyaluronic acid, obtains target product nuclear-shell structured nano-composite material；
Step (1) prepares nano-particle BaGdF5Method it is as follows：
(1.1) ethyl alcohol, oleic acid, oleyl amine are added in NaOH aqueous solutions, stirs to get uniform solution；
(1.2) by Gd (NO3)3·6H2O、BaCl2·2H2O、NH4The aqueous solution of F is added sequentially to mixed solution obtained by (1.1),
Stirring, obtains colloidal solution；
(1.3) colloidal solution that (1.2) obtain is transferred in the high-temperature high-pressure reaction kettle with polytetrafluoroethyllining lining, 200 DEG C-
220 DEG C of reaction 30-40h, obtain nano-particle BaGdF5；
(1.4) the nano-particle BaGdF that will be obtained in (1.3)5, with the mixed liquor centrifuge washing 3 times of ethyl alcohol and n-hexane, and will
Obtained BaGdF5It is distributed in chloroform, obtains oil-soluble BaGdF5Nano-particle；
(1.5) by the oil-soluble BaGdF in step (1.4)5Nano-particle is added dropwise to cetyl trimethylammonium bromide aqueous solution
In, it stirs 2-3 hours, is heated to 50 DEG C -70 DEG C, kept for 5-15 minutes, steam organic solvent, obtain water-soluble BaGdF5Nanometer
Particle；
In step (2), in nano-particle BaGdF5The method of the coating mesoporous silica in surface is as follows：
(2.1) water solubility BaGdF will be contained5For the solution of nano-particle under the conditions of 50-70 DEG C, pH value is adjusted to 8-9, adds successively
Enter tetraethyl orthosilicate and ethyl acetate, then add 3- aminopropyls-triethoxysilane, keeps reacting liquid temperature to 50
It DEG C -70 DEG C, stirs 10-24 hours, makes BaGdF5The coating mesoporous silica of nanoparticle surface；
(2.2) product obtained step (2.1) cools down, and with ethyl alcohol centrifuge washing 6 times, is dispersed in spare in secondary water.
2. a kind of nuclear-shell structured nano-composite material according to claim 1, which is characterized in that the composite material
Grain size is 60-70nm, and the grain size of core is 13-17nm.
3. a kind of nuclear-shell structured nano-composite material according to claim 1, which is characterized in that in step (1.1), oil
Acid, oleyl amine, ethyl alcohol, sodium hydroxide amount ratio be 40mL:3mL:24mL：1.2g；
In step (1.2), the dosage molar ratio of tri- kinds of elements of Gd, Ba, F is 1:1:5；
In step (1.5), BaGdF5Addition proportioning with cetyl trimethylammonium bromide is 1mmol：16-20g.
4. a kind of nuclear-shell structured nano-composite material according to claim 1, which is characterized in that in step (2.1),
BaGdF5, tetraethyl orthosilicate, ethyl acetate and 3- aminopropyls-triethoxysilane addition proportioning be 1mmol：8-
10mL：25-40mL：0.5-3mL；
In step (2.2), BaGdF5Amount ratio with ethyl alcohol is 2mmol：500mL.
5. a kind of nuclear-shell structured nano-composite material according to claim 1, which is characterized in that in step (3), by dihydroxy
Base silicon phthalocyanine is dissolved in n,N-Dimethylformamide, is obtained the n,N-Dimethylformamide solution of silicon phthalocyanine dihydroxide, is dripped dropwise
It is added to the BaGdF that surface is coated with mesoporous silicon oxide5In nano-particle solution, it is protected from light 10-24 hours, centrifuge washing,
Then in the surface modification photosensitizer silicon phthalocyanine dihydroxide of mesoporous silicon oxide；
Wherein, silicon phthalocyanine dihydroxide and the amount ratio of n,N-Dimethylformamide are 15mg：10mL；
Silicon phthalocyanine dihydroxide and BaGdF5Amount ratio be 60mg：1mmol.
6. a kind of nuclear-shell structured nano-composite material according to claim 1, which is characterized in that in step (4), by 1- second
Base-(3- dimethylaminopropyls) phosphinylidyne diimine hydrochloric acid, N- hydroxysuccinimides are dissolved in one water of 2- (N- morpholines) ethanesulfonic acid
It closes in object buffer solution, sequentially adds hyaluronic acid, surface modification has the BaGdF of photosensitizer silicon phthalocyanine dihydroxide5Nano-particle,
It is protected from light 6 hours, solution is dialysed for 24 hours with secondary water after reaction, finally can be obtained target product with Rotary Evaporators concentration
Nuclear-shell structured nano-composite material；
Wherein, a concentration of 0.5M of 2- (N- morpholines) ethanesulfonic acid monohydrate buffer solution,
1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimine hydrochloric acid, N- hydroxysuccinimides, hyaluronic acid and 2- (N-
Morpholine) ethanesulfonic acid monohydrate solution amount ratio be 8-10mg：8-10mg：10mg：5mL；Hyaluronic acid and BaGdF5Plus
It is 50mg to enter proportioning：0.025-0.05mol.
7. a kind of application of nuclear-shell structured nano-composite material as described in claim 1, which is characterized in that the nucleocapsid knot
Application of the structure nanocomposite in preparing mri contrast agent, CT contrast agent, and it is swollen preparing light thermotherapy treatment
The application in the photosensitizer in photothermal reagent, photodynamic therapy treatment tumour in tumor.
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