CN108485644A - Nanocomposite and preparation method thereof with enhancing photodynamic activity - Google Patents
Nanocomposite and preparation method thereof with enhancing photodynamic activity Download PDFInfo
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Abstract
The present invention is a kind of nanocomposite and preparation method thereof with enhancing photodynamic activity.Nanocomposite is upper conversion nano crystalline substance@SiO2@TiO2/ Au is the SiO wrapped up successively brilliant by upper conversion nano, peripheral2And TiO2Shell and it is deposited on TiO2What the Au nanoparticles of shell layer surface were constituted, wherein TiO2For the porous TiO constituted with nanoparticle2Shell.The grain size of nanocomposite is 40~98nm, and Au sizes are 3.0~20.2nm.Preparation method includes the following steps：(1) use control Hydrolyze method for SiO2The upper conversion nano crystalline substance of package wraps up TiO2Shell；(2) use photochemical method in TiO2Area load Au.The preparation process of the present invention is simple, efficient, and the pattern of product is uniform, and the controllability of composition and size is good, and the ability for generating active oxygen species is strong, and photodynamic activity is excellent, good in field of photodynamic application prospect.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, and in particular to a kind of nanometer with enhancing photodynamic activity is multiple
Condensation material and preparation method thereof.
Background technology
In recent years, the cancer that incidence constantly increases seriously threatens human health and life.Conventional cancer treatment means are deposited
In some drawbacks：Operation is difficult to cope with the state of an illness of cancer cell diffusion and can cause more serious body wound, radiation and chemotherapy
It is poor to the therapeutic choice of tumour cell, side effect is big.In contrast, optical dynamic therapy is a kind for the treatment of of cancer of noninvasive
Method is enriched in the photosensitive drug of tumor tissues by incident light irradiation, and photosensitive drug is in a series of optical physics and photochemistry mistake
The active oxygen species (ROS) including singlet oxygen, and then the treatment killed tumour cell, realize cancer are generated in journey.By
The position that nontoxic, optical dynamic therapy occurs over just exciting light irradiation and penetrates in photosensitive drug itself, therefore, therapy tool
There are preferable safety and locality.However, traditional photosensitive drug be mostly excited by visible light (400~760nm) it is organic
The tissue penetration depths of small molecule, exciting light are limited (usually only several millimeters), therefore this method is chiefly used in treating cutaneum carcinoma, the cancer of the esophagus
Equal cancer cells are in the cancer of superficial layer, it is difficult to effective for the treatment in deep tissue or large-sized tumour.
Since rear-earth-doped upper conversion nano crystalline substance has the ability for absorbing near infrared light, emitting ultraviolet light and visible light,
The nano material using the near infrared light of deep tissue penetration as exciting light, with photosensitizer function can be designed using this property.
Document (Nature Communication, 2012,18：It 1580-1585) reports with mesoporous SiO2Wrap up NaYF4:Yb3+/Er3+
54 Nano medication of the structure with photodynamic activity of nanocrystalline load organic photosensitizer ZnPc and step China blueness, it is closely red in 980nm
Under outer light irradiation, NaYF is utilized4:Yb3+/Er3+Up-conversion luminescence excite photosensitizer, generate ROS with kill tumour cell, inhibit
Mouse tumor growth in vivo.Patent (CN104342145A；CN104784692A it) provides and can be used for the organic of optical dynamic therapy
The preparation method of the upper conversion nano crystalline substance of photosensitizer load.However, due to the poor chemical stability of organic photosensitizer, light easily occurs
It bleaches and there is the risk leaked from nanoparticle, the internal optical dynamic therapy of such support type photosensitive drug to answer under environment in vivo
It uses and is restricted.Compared to organic photosensitizer, TiO2That chemical stability is good, ROS generates ability is strong, may be used as inorganic photosensitive
Agent light power killed cells under ultraviolet light.Document (ACS Nano, 2015,9：2584-2599；Biomaterials, 2015,
57：It 93-106) reports TiO2With upper conversion nano is brilliant compound prepares conversion nano crystalline substance-TiO on inorganic photosensitizer2Compound grain
The method of son, the ultraviolet excitation TiO penetrated using upper conversion nano trichite under near infrared light2ROS is generated, can be used for
Inhibit the tumour growth in Mice Body, extend the time-to-live.However, due to upper conversion nano trichite light quantum yield generally compared with
Low while TiO2Photo-generate electron-hole be easy to happen compound, cause the energy conversion efficiency of such inorganic photosensitizer in totality
It is upper very low, show as ROS generate ability is weaker, photodynamic activity have it is to be hoisted.In addition, on the surface modification of functional molecular is
Conversion nano crystalline substance-TiO2The premise of the vivo applications of compound particle, above-mentioned document are used first with silane coupled modified TiO2Table
Face and then the method for being coupled decorating molecule, but the modification of silane coupling agent can consume TiO2Surface portion hydroxyl, closing TiO2
The part photocatalytic activity site on surface, causes the photodynamic activity of drug further to weaken.In this case, in order to maintain
Effective dose needed for optical dynamic therapy, it is necessary to increase the power density of near-infrared excitation light, it is hot that this will increase patient skin
The risk that the significant near infrared light of effect is burnt.Therefore, conversion nano crystalline substance-TiO how is effectively improved2Compound particle upper turn
The ROS generation abilities and photodynamic activity changed light efficiency, improve drug, become such nano material and pacify as inorganic photosensitizer
Primary premise and key technology complete and that be efficiently applied to interior tumor cell inactivation.
Invention content
The present invention provides a kind of upper conversion nano crystalline substance@SiO with enhancing photodynamic activity2@TiO2The nano combined materials of/Au
Material and preparation method thereof, solves the upper conversion nano crystalline substance-TiO of prior art preparation2The up-conversion luminescence efficiency of class nano material
Lead to the problem of that ability is relatively low, photodynamic activity is weaker with ROS, product has good photodynamic activity.
The purpose of the present invention is achieved through the following technical solutions：
The nanocomposite with enhancing photodynamic activity provided by the invention, is a kind of upper conversion nano crystalline substance@SiO2@
TiO2/ Au nanocomposites are the SiO wrapped up successively brilliant by upper conversion nano, peripheral2And TiO2It shell and is deposited on
TiO2What the Au nanoparticles of shell layer surface were constituted, wherein TiO2For the porous TiO constituted with nanoparticle2Shell.Nanocomposite
Grain size be 40~98nm, Au average-sizes are 3.0~20.2nm.
The nanocomposite is characterized as：
The upper conversion nano crystalline substance is NaYF4:Yb3+/Tm3+、NaYF4:Yb3+/Tm3+@NaGdF4:Yb3+、NaGdF4:Yb3 +/Tm3+In one kind, 980nm near-infrared excitation lights irradiation under can be with emitting ultraviolet light and visible light.
The preparation method with the nanocomposite of enhancing photodynamic activity proposed by the present invention includes two steps：
(1)TiO2The preparation of shell：
By SiO2It is 1 that the upper conversion nano crystalline substance of package, which is dispersed in 20mL volume ratios,:In 1 water/alcohol mixed solvent, then
Diethylenetriamine, solution of tetrabutyl titanate are sequentially added, 8h is stirred to react at 70 DEG C, is disperseed after solid product is eluted with water
In 80mL water, the hydro-thermal reaction 4h at 120 DEG C obtains conversion nano crystalline substance@SiO2@TiO2Compound particle；Wherein SiO2Package
The dosage of upper conversion nano crystalline substance be 1mmol, the dosage of diethylenetriamine is 50mmol, and solution of tetrabutyl titanate is made using ethyl alcohol
Solvent is prepared, a concentration of 1mol/L, and dosage is 1~5mL.
(2) Au loads：
Upper conversion nano crystalline substance@SiO prepared by step (1)2@TiO2Compound particle is dispersed in 20mL water/alcohol mixed solvent
In, carry out photochemical reaction 30min using ultraviolet light dispersion liquid, be added after golden precursor solution continue irradiation reaction 2~
20min obtains conversion nano crystalline substance@SiO2@TiO2/ Au nanocomposites；Wherein upper conversion nano crystalline substance@SiO2@TiO2It is compound
Particle is 0.1mmol, a concentration of 0.1mol/L of golden precursor solution, and dosage is 20~500 μ L.
The present invention makes tetrabutyl titanate hydrolysis generate TiO using control Hydrolyze method first2, make it in SiO2Package upper turn
Nanocrystalline periphery is changed to form nanoparticle and combine porous TiO2Shell promotes TiO using hydro-thermal reaction2Crystallization.Herein, SiO2Shell
On the one hand layer has the upper conversion nano of connection brilliant and TiO2Effect, avoid because lattice mismatch lead to TiO2It is difficult in upper conversion
The compound problem of nanocrystal surface；On the other hand, since existing synthetic technology can easily control SiO2The thickness of shell, and Au
Enhancing Au the degree of up-conversion luminescence with the spacing of upper conversion nano trichite light influences significantly, to use SiO2Shell can facilitate
Ground adjusts conversion nano crystalline substance@SiO on product of the present invention2@TiO2The spacing of Au and upper conversion nano crystalline substance in/Au, to be converted in enhancing
The photodynamic activity of nanocrystalline luminous intensity, optimized product is provided convenience.Then, in alcohol/aqueous systems, ultraviolet luminous energy light
The golden predecessor of solution generates Au simple substance, meanwhile, TiO under ultraviolet light2Light induced electron can also restore golden predecessor, in turn
Make Au in TiO2Surface in situ nucleation and growth.Therefore, using photochemical method in upper conversion nano crystalline substance@SiO2@TiO2Surface is heavy
Product Au has following technical advantage：First, Au sizes can be regulated and controled by controlling photochemical reaction process, it is especially suitable
For obtaining small size Jenner's grain of rice, is conducive to optimization and prepares the high upper conversion nano crystalline substance SiO of ROS generations ability2@TiO2/Au；
Second, entire photochemistry is without adding stabilizer or surfactant, thus Au surface cleaning, without stabilizer or table
Face activating agent, avoid by product adsorb or combine stabilizer or surfactant biosystem application in there may be poison
The negative effect of side effect.In two stages, the first stage turns the photochemical reaction that the present invention uses using in ultraviolet light
Change nanocrystalline@SiO2@TiO2Compound particle, its role is to activate TiO2Photocatalysis performance；Golden predecessor is added in second stage
Solution continues the step of photochemical reaction, and its role is to make golden predecessor in TiO2The dual work of photocatalysis and ultraviolet light photodissociation
With the lower Au simple substance for quickly being restored, being generated in TiO2Surface in situ is nucleated and growth.Compared to the upper conversion nano of irradiation in advance
Brilliant@SiO2@TiO2Compound particle, only direct irradiation contain golden predecessor and upper conversion nano crystalline substance@SiO2@TiO2Compound particle mixes
The advantages of single stage photochemical reaction of conjunction solution, two benches photochemical reaction proposed by the present invention, is：It can accelerate Au
In TiO2The formation speed and distributing homogeneity on surface, the deposition efficiency for improving Au in product.By changing SiO2That wraps up is upper
It the size of conversion nano crystalline substance, the dosage of solution of tetrabutyl titanate and golden precursor solution and photochemical reaction time, can adjust
Conversion nano crystalline substance@SiO in control2@TiO2The size of/Au, contained Au of size and number.
SiO in step (1)2The upper conversion nano crystalline substance of package is selected from NaYF4:Yb3+/Tm3+@SiO2、NaYF4:Yb3+/Tm3 +@NaGdF4:Yb3+@SiO2、NaGdF4:Yb3+/Tm3+@SiO2In one kind, with NaYF4:Yb3+/Tm3+、NaYF4:Yb3+/Tm3+@
NaGdF4:Yb3+Or NaGdF4:Yb3+/Tm3+As upper conversion nano crystalline substance, by document (Advanced Materials, 2008,
20：4765–4769；Biomaterials, 2012,33：1079-1089) prepared by the method reported, by changing reactant silicic acid
The dosage of tetra-ethyl ester can regulate and control SiO2The thickness of shell, and then obtain various sizes of SiO2The upper conversion nano of package is brilliant.Compared with
Good, SiO2The size of the upper conversion nano crystalline substance of package is 34~82nm, wherein SiO2The thickness of shell is 5~20nm.
Water/alcohol mixed solvent in step (2) is prepared by water and ethyl alcohol or isopropanol, preferably, the volume of water and alcohol
Than being 1:(0.1~5).
The HAuCl that golden precursor solution in step (2) is concentration 0.1mol/L4Or AuCl3Aqueous solution, preferably, dosage
For 20~500 μ L.Golden predecessor is HAuCl4Or AuCl3。
The photochemical reaction of step (2) uses ultraviolet light as reaction energy, and light source used should have emitting ultraviolet light
Function, preferably, light source be xenon lamp.
The photochemical reaction of step (2) includes two stages：First stage is only to irradiate upper conversion nano crystalline substance@SiO2@TiO2
The dispersion liquid of compound particle, for activating TiO2Photocatalysis performance, when a length of 30min；Second stage is that golden predecessor is added
Continue irradiation reaction after solution, for making golden predecessor in TiO2It is quickly gone back under the double action of photocatalysis and ultraviolet light photodissociation
Former, generation Au simple substance is in TiO2Surface in situ is nucleated and growth, preferably, second stage light application time is 2~20min.
The nanocomposite with enhancing photodynamic activity proposed by the present invention, in light power killing tumor cells
Application prospect it is good, the nanocomposite under 980nm near infrared lights have good ROS generate ability, have light
The ability of power killing tumor cells.
The present invention has the advantages that as a result of above technical scheme compared with existing invention：
(1) the enhancing amplitude of the Au luminous intensities to upper conversion nano crystalline substance is up to 1.2 times, while can enhance TiO2Light
Catalytic activity, under the premise of not improving the power density of near-infrared excitation light, the dual humidification of Au makes conversion nano
Brilliant@SiO2@TiO2The relatively upper conversion nano crystalline substance@SiO of/Au2@TiO2ROS generate ability and be remarkably reinforced, the oxidative stress of ROS improves
It is 0.6~4.1 times, apparent to the photodynamic activity of tumour cell inactivation.
(2) upper conversion nano crystalline substance@SiO prepared by the present invention2@TiO2The chemical property of/Au nanocomposites is stablized, shape
Looks are uniform, and size is less than 100nm, Au dimension adjustables and surface is without stabilizer or surfactant, avoid stabilizer
Or the potential negative effect that material occurs in biosystem application in surfactant.
(3) preparation is simple, the period is short, efficient by the present invention.
Description of the drawings
Fig. 1 is upper conversion nano crystalline substance@SiO2@TiO2The structural schematic diagram of/Au nanocomposites.In figure：1. conversion is received on
Meter Jing；2.SiO2Shell；3.TiO2Shell；4.Au nanoparticles.
Fig. 2 is the transmission electron microscope picture of 1 product of embodiment.
Fig. 3 is the transmission electron microscope picture of 2 product of embodiment.
Fig. 4 is the transmission electron microscope picture of 3 product of embodiment.
Fig. 5 is the transmission electron microscope picture of 6 product of embodiment.
Fig. 6 is the X-ray powder diffraction figure of 6 product of embodiment.
Fig. 7 is the energy spectrum diagram of 6 product of embodiment.
Fig. 8 is the up-conversion luminescence spectrogram of 6 product of embodiment 1 and embodiment.
Fig. 9 is the transmission electron microscope picture of 7 product of embodiment.
Figure 10 is the transmission electron microscope picture of 8 product of embodiment.
Figure 11 is the effect of embodiment 1 and 6~8 product of embodiment the oxidative degradation rhodamine B under 980nm near infrared lights photograph
Figure.
Figure 12 is the transmission electron microscope picture of 9 product of embodiment.
Figure 13 is the transmission electron microscope picture of 10 product of embodiment.
Figure 14 is the transmission electron microscope picture of 11 product of embodiment.
Figure 15 is the transmission electron microscope picture of 12 product of embodiment.
Figure 16 is the transmission electron microscope picture of 13 product of embodiment.
Figure 17 is the transmission electron microscope picture of 14 product of embodiment.
Figure 18 is the transmission electron microscope picture of 15 product of embodiment.
Figure 19 is the transmission electron microscope picture of 16 product of embodiment.
Figure 20 is that 16 product of embodiment is degraded 1,3 diphenyl isobenzofuran solution under 980nm near infrared lights
Abosrption spectrogram.
Figure 21 is the transmission electron microscope picture of 17 product of embodiment.
Figure 22 is comparison diagram of 6 product of embodiment to the dark toxicity and illumination toxicity of human cervical carcinoma cell HeLa.
Specific implementation mode
In the present invention, it is prepared and is turned by control hydrolysis of tetrabutyl titanate, photoreduction gold predecessor two-step reaction
Change nanocrystalline@SiO2@TiO2/ Au nanocomposites, with SiO2The upper conversion nano crystalline substance of package passes through change as reactant
The type and size of reactant, dosage and light application time regulate and control the size and composition of product, the upper conversion nano crystalline substance@of gained
SiO2@TiO2The ROS of/Au nanocomposites generates ability and is improved, the superior activity of light power killing tumor cells.
Following embodiment and attached drawing are to the content that the present invention is furture elucidated, but present disclosure is not limited solely to
Embodiment below.
Embodiment 1：
The present embodiment prepares conversion nano crystalline substance@SiO as follows2@TiO2Nano-complex particle：
Take SiO2Superscribe conversion nano crystalline substance (NaYF4:Yb3+/Tm3+@SiO2, SiO2Shell thickness is 11nm) 1mmol, surpass
It is 1 that sound, which is scattered in 20mL volume ratios,:In 1 water/alcohol mixed solvent, diethylenetriamine 50mmol is added, under stiring dropwise
The solution of tetrabutyl titanate (using ethanol as solvent) of a concentration of 1mol/L of 3mL is added, then heats to 70 DEG C, is stirred to react
8h.Centrifugation removal reaction clear liquid, is dispersed in after solid product 3 times is washed with water in 80mL water, the hydro-thermal reaction 4h at 120 DEG C,
Obtain conversion nano crystalline substance@SiO2@TiO2Compound particle (NaYF4:Yb3+/Tm3+@TiO2)。
The upper conversion nano crystalline substance@SiO observed under transmission electron microscope shown in Fig. 22@TiO2The pattern of compound particle, determines TiO2
Shell is by TiO2Nano-particle forms, and has porous structure, the average grain diameter of product is 55nm.
Embodiment 2：
With the step of embodiment 1 and technique is identical, but SiO is used2Superscribe conversion nano crystalline substance (NaYF4:Yb3+/Tm3+@
SiO2, SiO2Shell thickness is 5nm) 1mmol, the dosage of solution of tetrabutyl titanate is 1mL, and products therefrom is seen under transmission electron microscope
The pattern that measures is as shown in figure 3, the pattern of visible product is with embodiment 1, but average grain diameter is 38nm.
Embodiment 3：
With the step of embodiment 1 and technique is identical, but SiO is used2Superscribe conversion nano crystalline substance (NaYF4:Yb3+/Tm3+@
SiO2, SiO2Shell thickness is 11nm) 1mmol, the dosage of solution of tetrabutyl titanate is 5mL, and products therefrom is seen under transmission electron microscope
The pattern that measures is as shown in figure 4, the pattern of visible product is with embodiment 1, but average grain diameter is 61nm.
Embodiment 4：
With the step of embodiment 1 and technique is identical, but SiO is used2Superscribe conversion nano crystalline substance (NaYF4:Yb3+/Tm3+@
NaGdF4:Yb3+@SiO2) 1mmol, the dosage of solution of tetrabutyl titanate is 5mL, what products therefrom observed under transmission electron microscope
Pattern is with embodiment 1, but average grain diameter is 90nm.
Embodiment 5：
With the step of embodiment 1 and technique is identical, but SiO is used2Superscribe conversion nano crystalline substance (NaGdF4:Yb3+/Tm3+@
SiO2) 1mmol, the dosage of solution of tetrabutyl titanate is 1mL, the same embodiment of pattern that products therefrom observes under transmission electron microscope
1, but average grain diameter is 38nm.
Embodiment 6：
The present embodiment prepares conversion nano crystalline substance@SiO as follows2@TiO2/ Au nanocomposites：
1 product 0.1mmol of Example, ultrasonic disperse are 1 in 20mL volume ratios:In 0.1 water/alcohol mixed solvent,
Dispersion liquid is loaded on 50mL single port quartz round-bottomed flasks, the ultraviolet light dispersion liquid 30min emitted with xenon lamp is rapidly joined dense
Degree is the HAuCl of 0.1mol/L4100 μ L of solution, continue irradiation reaction 10min after stirring evenly, centrifugation removal reaction clear liquid is used
Water washing solid product 3 times obtains conversion nano crystalline substance@SiO2@TiO2/ Au nanocomposites.
Transmission electron microscope picture shown in fig. 5 shows that Au are dispersed in coarse TiO in product2Shell layer surface, product are averaged
Grain size is 64nm, and contained Au of average-size is 6.1nm, and Au pars are 4.7/product particles.
X-ray powder diffraction figure shown in fig. 6 proves that product includes β phases NaYF4, Anatase TiO2With face-centered cubic knot
Tri- kinds of amorphous materials of structure Au.
Energy spectrum diagram shown in Fig. 7 confirms that product includes Na, F, Y, Yb, Tm, Si, Ti, O, Au and C element.
The up-conversion luminescence spectrum of 6 product of embodiment 1 and embodiment shown in Fig. 8, the luminous intensity of 6 product of embodiment are
2.2 times of 1 product of embodiment, it was demonstrated that the Au luminous intensities for enhancing conversion nano crystalline substance, enhancing amplitude are 1.2 times.
To sum up, the testing result of transmission electron microscope, X-ray powder diffraction, element power spectrum and up-conversion luminescence spectrum proves real
Apply 6 product of example in pattern, phase structure, elemental composition with the present invention target product it is consistent, and Au have improve on turn
The effect of changing light efficiency.
Embodiment 7：
With the step of embodiment 6 and technique is identical, but HAuCl4The dosage of solution is 20 μ L, and products therefrom is in transmission electron microscope
Under the pattern that observes as shown in figure 9, the pattern of visible product is with embodiment 6, but Au average-sizes are 3.8nm, Au
Par be 3.1/product particles.
Embodiment 8：
With the step of embodiment 6 and technique is identical, but HAuCl4The dosage of solution is 500 μ L, and products therefrom is in transmission electricity
The pattern observed under mirror is as shown in Figure 10, it is seen that the pattern of product is with embodiment 6, but Au average-sizes are 8.5nm, Au
The par of grain is 5.9/product particles.
Each 5mg of product for weighing embodiment 1, embodiment 6~8 respectively is dispersed in a concentration of 1mg/L rhodamine Bs of 4 parts of 10mL
It in solution, is protected from light stirring 1h and reaches adsorption equilibrium, it is 1.5W/cm that mixed liquor, which is placed at power density,2980nm near infrared lights
Lower irradiation reaction, the ROS oxidative degradation rhodamine Bs generated using sample, the rhodamine B degradation rate for reacting 7h are as shown in figure 11.
As a result show that the degradation rate of rhodamine B in the presence of 6~8 product of embodiment is respectively 1.6,3.2 and in the presence of 1 product of embodiment
5.1 times, it was demonstrated that compare 1 product of embodiment, the presence of Au improves TiO2Photocatalysis performance, make 6~8 product of embodiment
ROS generates ability enhancing, and the oxidative stress of ROS improves 0.6~4.1 times.
Above-mentioned photocatalysis is experiments have shown that conversion nano crystalline substance@SiO on 6~8 product of embodiment2@TiO2/ Au is compared with 1 product of embodiment
Upper conversion nano crystalline substance@SiO2@TiO2ROS generate ability enhancing, the oxidative stress of ROS improves 0.6~4.1 times.
Embodiment 9：
With the step of embodiment 8 and technique is identical, but HAuCl is added4Continue illumination reaction 2min after solution.Products therefrom
The pattern observed under transmission electron microscope is as shown in figure 12, it is seen that the pattern of product is with embodiment 8, but Au average-sizes are
4.1nm, Au pars are 3.4/product particles.
Embodiment 10：
With the step of embodiment 8 and technique is identical, but HAuCl is added4Continue illumination reaction 5min after solution.Products therefrom
The pattern observed under transmission electron microscope is as shown in figure 13, it is seen that the pattern of product is with embodiment 8, but Au average-sizes are
4.8nm, Au pars are 3.4/product particles.
Embodiment 11：
With the step of embodiment 8 and technique is identical, but HAuCl is added4Continue illumination reaction 8min after solution.Products therefrom
The pattern observed under transmission electron microscope is as shown in figure 14, it is seen that the pattern of product is with embodiment 8, but Au average-sizes are
6.3nm, Au pars are 5.6/product particles.
Embodiment 12：
With the step of embodiment 8 and technique is identical, but HAuCl is added4Continue illumination reaction 20min after solution.Gained produces
The pattern that object observes under transmission electron microscope is as shown in figure 15, it is seen that the pattern of product is with embodiment 8, but Au average-sizes
For 8.8nm, Au pars are 9.0/product particles.
Embodiment 13：
With the step of embodiment 12 and the volume ratio of water/alcohol mixed solvent that technique is identical but used is 1:1.Gained
The pattern that product observes under transmission electron microscope is as shown in figure 16, it is seen that the pattern of product is with embodiment 12, but Au are averaged
Size is 10.3nm, and Au pars are 5.9/product particles.
Embodiment 14：
With the step of embodiment 12 and the volume ratio of water/alcohol mixed solvent that technique is identical but used is 1:5.Gained
The pattern that product observes under transmission electron microscope is as shown in figure 17, it is seen that the pattern of product is with embodiment 12, but Au are averaged
Size is 20.2nm, and Au pars are 4.4/product particles.
Embodiment 15：
With the step of embodiment 6 and technique is identical, but use the product of 0.1mmol embodiments 2 as raw material, products therefrom
The pattern observed under transmission electron microscope is as shown in figure 18, it is seen that the pattern of product is with embodiment 6, but the average grain diameter of product is
43nm, contained Au of average-size are 4.8nm, and Au pars are 4.2/product particles.
Embodiment 16：
With the step of embodiment 6 and technique is identical, but it is a concentration of using 4 product of 0.1mmol embodiments and 500 μ L
The AuCl of 0.1mol/L3For solution as reactant, the pattern that products therefrom observes under transmission electron microscope is as shown in figure 19, it is seen that
The pattern of product is with embodiment 6, but the average grain diameter of product is 98nm, and the average-size of contained Au grains is 3.4nm, Au
Par is 12.4/products.
The product 2mg for weighing embodiment 16 is dispersed in 1, the 3- diphenyl isobenzofurans of a concentration of 20mg/L of 8mL
In (DPBF, singlet oxygen detection probe) solution, it is protected from light stirring 1h and reaches adsorption equilibrium, place reaction liquid into and be in power density
2.5W/cm2980nm near infrared lights under irradiate reaction, the intervals 10min sampling, centrifuge solid, draw reaction clear liquid test
As a result absorption spectrum is shown in Figure 20.The absorption peak of DPBF quickly reduces in 60min in reaction clear liquid, the absorbance at 411nm
The range of decrease is 74%, illustrates ROS (singlet oxygen) degradations that most of DPBF has been generated by product.
DPBF degradation experiments demonstrate conversion nano crystalline substance@TiO2/ Au nanocomposites are in 980nm near infrared lights
The lower ability with quickly generation ROS species (singlet oxygen).
Embodiment 17：
With the step of embodiment 16 and the volume ratio of water/isopropyl alcohol mixed solvent that technique is identical but used is 1:0.1,
The pattern that products therefrom observes under transmission electron microscope is with embodiment 16, but Au average-sizes are 3.0nm, and Au are averaged
Quantity is 10.8/products.
Embodiment 18：
It with the step of embodiment 6 and technique is identical, but uses 5 product of 0.1mmol embodiments as reactant, is being added
HAuCl4Continue illumination reaction 2min after solution, the pattern that products therefrom observes under transmission electron microscope is as shown in figure 21, it is seen that
The pattern of product is with embodiment 6, but the average grain diameter of product is 40nm, contained Au of average-size is 3.2nm, and Au are put down
Equal quantity is 3.1/product particles.
Embodiment 19：
The present embodiment tests upper conversion nano crystalline substance@SiO using mtt assay2@TiO2/ Au nanocomposites are to human cervical carcinoma
The cytotoxicity and photodynamic activity of HeLa cells, specifically take following steps：
A. cytotoxicity test：Configuration 5 × 104The HeLa cell suspending liquids of/mL add 100 μ L cells to suspend according to every hole
The dosage of liquid plants HeLa cells in 96 orifice plates, in 37 DEG C, 5%CO2It is cultivated for 24 hours in the incubator of atmosphere.With DMEM culture solutions
Disperse 6 product of embodiment, prepares the dispersion liquid (the μ g/mL of a concentration of 0,50,100,200,400 and 600) of various concentration.It respectively takes point
100 μ L of dispersion liquid are separately added into different holes, each concentration sets 5 parallel holes, are protected from light culture for 24 hours.20 μ L are added into each hole
The tetrazolium bromide solution (MTT) of a concentration of 5mg/mL continues to be protected from light culture 4h, sucks the culture solution in hole, be added into each hole
100 μ L dimethyl sulfoxides shake 10min and dissolve MTT, measure absorbance value of the well at 570nm with microplate reader, deduct blank
The absorbance value in hole calculates the survival rate of cell, and using 5 parallel holes, results are averaged.Calculation formula is：The survival of cell
Absorbance value × 100%. of absorbance value/control sample of rate=experimental group sample
B. photodynamic activity is tested：Configuration 5 × 104The HeLa cell suspending liquids of/mL add 100 μ L cells outstanding according to every hole
The dosage of supernatant liquid plants HeLa cells in 96 orifice plates, in 37 DEG C, 5%CO2It is cultivated for 24 hours in the incubator of atmosphere.It is cultivated with DMEM
Liquid disperses 6 product of embodiment, prepares various concentration dispersion liquid (the μ g/mL of a concentration of 0,50,100,200,400 and 600).It respectively takes point
100 μ L of dispersion liquid are separately added into different holes, and each concentration sets 5 parallel holes, wash away unbonded product after being protected from light culture 6h, weight
Isometric culture solution is newly added, is 1.2W/cm in power density2980nm near infrared lights under irradiation 5min, interval 5min after
5min is irradiated again, is then put back to incubator and is continued to be protected from light culture 18h.The MTT of 20 a concentration of 5mg/mL of μ L is added into each hole
Solution continues to be protected from light culture 4h, sucks the culture solution in hole, 100 μ L dimethyl sulfoxides are added into each hole, it is molten to shake 10min
MTT is solved, absorbance value of the well at 570nm is measured with microplate reader, deducts the absorbance value of blank well, calculate depositing for cell
Motility rate, using 5 parallel holes, results are averaged.Calculation formula is：The absorbance value of survival rate=experimental group sample of cell/
Absorbance value × 100%. of control sample
Figure 22 is comparison diagram of 6 product of embodiment to the dark toxicity and illumination toxicity of HeLa cells.Under dark surrounds,
When the concentration of product increases to 600 μ g/mL, the survival rate of HeLa cells is 78%, shows that the cytotoxicity of product is relatively low；But
Under 980nm near infrared lights, the survival rates of HeLa cells is significantly reduced with the increase of production concentration, product it is a concentration of
The survival rate of HeLa cells is down to 48% when 600 μ g/mL, it was demonstrated that product lives to killing tumor cells with significant light power
Property.
The experimental result that mtt assay tests HeLa cell survival rates confirms upper conversion nano crystalline substance@SiO2@TiO2/ Au is nano combined
Material photodynamic activity with killing tumor cells under 980nm near infrared lights.
Claims (10)
1. a kind of nanocomposite with enhancing photodynamic activity, it is characterised in that, periphery brilliant by upper conversion nano is successively
The SiO of package2And TiO2Shell, and it is deposited on TiO2The Au nanoparticles of shell layer surface are configured to upper conversion nano crystalline substance@SiO2@
TiO2/ Au composite materials, wherein TiO2For the porous TiO constituted with nanoparticle2Shell.
2. nanocomposite according to claim 1, it is characterised in that：The upper conversion nano crystalline substance uses NaYF4:Yb3 +/Tm3+、NaYF4:Yb3+/Tm3+@NaGdF4:Yb3+、NaGdF4:Yb3+/Tm3+In one kind.
3. nanocomposite according to claim 1, it is characterised in that：The average grain diameter of the nanocomposite is 40
~98nm, Au average-sizes are 3.0~20.2nm.
4. a kind of preparation method with the nanocomposite for enhancing photodynamic activity, it is characterised in that include the following steps：
(1)TiO2The preparation of shell：
By SiO2It is 1 that the upper conversion nano crystalline substance of package, which is dispersed in 20mL volume ratios,:In 1 water/alcohol mixed solvent, then successively
Diethylenetriamine, solution of tetrabutyl titanate is added, is stirred to react 8h at 70 DEG C, is dispersed in after solid product is eluted with water
In 80mL water, the hydro-thermal reaction 4h at 120 DEG C obtains conversion nano crystalline substance@SiO2@TiO2Compound particle；Wherein SiO2Package
The dosage of upper conversion nano crystalline substance is 1mmol, and the dosage of diethylenetriamine is 50mmol, and solution of tetrabutyl titanate is made molten using ethyl alcohol
Agent is prepared, a concentration of 1mol/L, and dosage is 1~5mL；
(2) Au loads：
Upper conversion nano crystalline substance@SiO prepared by step (1)2@TiO2Compound particle is dispersed in 20mL water/alcohol in the mixed solvent, makes
Photochemical reaction 30min is carried out with ultraviolet light dispersion liquid, continues irradiation 2~20min of reaction after golden precursor solution is added,
Obtain conversion nano crystalline substance@SiO2@TiO2/ Au nanocomposites；Wherein upper conversion nano crystalline substance@SiO2@TiO2Compound particle is
0.1mmol, a concentration of 0.1mol/L of golden precursor solution, dosage are 20~500 μ L.
5. the preparation method of nanocomposite according to claim 4, it is characterised in that：Light described in step (2)
Chemical reaction uses ultraviolet light as reaction energy, and light source used is xenon lamp.
6. the preparation method of nanocomposite according to claim 4, it is characterised in that：Light described in step (2)
Chemical reaction includes 2 stages：First stage is only to irradiate upper conversion nano crystalline substance@SiO2@TiO2The dispersion liquid of compound particle, the
Two-stage is to continue irradiation reaction after golden precursor solution is added；Golden predecessor is HAuCl4Or AuCl3。
7. the preparation method of nanocomposite according to claim 4, it is characterised in that：Gold described in step (2)
Precursor solution is HAuCl4Or AuCl3Aqueous solution.
8. the preparation method of nanocomposite according to claim 4, it is characterised in that：Water/alcohol described in step (2)
Mixed solvent is prepared by water and ethyl alcohol or isopropanol, and wherein the volume ratio of water and alcohol is 1:(0.1~5).
9. the preparation method of nanocomposite according to claim 4, it is characterised in that：SiO described in step (1)2
The upper conversion nano crystalline substance of package uses NaYF4:Yb3+/Tm3+@SiO2、NaYF4:Yb3+/Tm3+@NaGdF4:Yb3+@SiO2、
NaGdF4:Yb3+/Tm3+@SiO2In one kind.
10. the upper conversion nano crystalline substance@SiO that in claim 4 to 9 prepared by any the method2@TiO2/ Au nanocomposites,
Its application in light power killing tumor cells.
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