CN106478946B - A kind of degradable polyaniline/porous silicon nanocomposite and its preparation method and application - Google Patents
A kind of degradable polyaniline/porous silicon nanocomposite and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of degradable polyaniline/porous silicon nanocomposites and its preparation method and application.Porous silicon nano material prepared by the present invention, is compared to other inorganic nano materials, and there is adjustable aperture, big surface area and surface to be easy to functionalization, can be used for loading different organic molecules, large biological molecule or nano material etc. for porous silicon nano material.In addition, porous silicon nano material has good biocompatibility and biodegradability so that it can have prodigious potentiality in clinical application, this is because porous silicon nanoparticles are excreted after capable of being degraded to orthosilicic acid in vivo by urine.To, we have synthesized degradable polyaniline/porous silicon nanocomposite, the material has obviously stable photo-thermal ability, well water-soluble and outstanding biocompatibility and degradable ability, and adriamycin can be effectively loaded, there can be apparent chemotherapy to combine synergistic therapeutic effect with thermotherapy in vivo or in vitro.
Description
Technical field
The invention belongs to porous silicon nanocomposite technical fields, and in particular to a kind of degradable polyaniline/porous
Silicon nanocomposite and its preparation method and application.
Background technology
Oncotherapy achieves huge progress in the past few decades, from 1991 the death rate caused by tumour under
Drop 20%.But the death toll about 8,200,000 caused by newly-increased tumor patient about 14,100,000 in 2012, tumour, therefore it is current
It needs to develop better oncotherapy technology.Currently, a kind of dependent on the organic or inorganic nano material near infrared absorption
Photo-thermal therapy technology become research hotspot, including：Gold nano structure, palladium nano sheet, lanthanide-doped upper conversion nano
The nanometer polymer of material, copper sulfide nano material, carbon nanomaterial, nir dye package or conjugation.These photo-thermal nanometers
Material can effectively absorb near infrared light and be converted to heat, and near infrared light has good tissue penetration, generation
Heat can lead to the death of tumour cell.In addition to the heating ablation of tumour, photo-thermal therapy, which can also help to induce or improve others, to be controlled
It treats (such as：Chemotherapy or radiotherapy) it is used for the combined therapy of tumour.Currently, it is mostly inorganic nano material to have superior light thermal property material
Material, but these materials can not biodegradable and poor kidney Scavenging activity, this is resulted in can be in long-term existence in life
In object, to bring a potential chronobiological toxicity, and nir dye package or the nanometer polymer of combination can
It is degrading in vivo well.Organic nanometer polymer, the polymer nanocomposite material of conjugation are wrapped up compared to nir dye
Material has pi-electron (such as：Polyaniline, polypyrrole etc.), during multiple photo-thermal these materials present it is very strong and
Stable excessively high thermal energy power.But the polymer of conjugation has the shortcomings that, such as：Poor water-soluble, low anticancer drug
Delivered payload capability, these hinder it and are further used for combined therapy.In order to overcome some above disadvantages, need to develop one kind
There is novelty the degradable photo-thermal nano-carrier of biocompatibility to be used for combined therapy.
Invention content
Goal of the invention：For the deficiencies in the prior art, the object of the present invention is to provide a kind of degradable polyphenyl
Amine/porous silicon nanocomposite meets the application for preparing tumour diagnosis and treatment drug.It is a further object of the present invention to provide in one kind
State the preparation method of degradable polyaniline/porous silicon nanocomposite.Further object of the present invention is to provide above-mentioned drop
The application of the polyaniline of solution/porous silicon nanocomposite.
Technical solution：In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is：
A kind of preparation method of degradable polyaniline/porous silicon nanocomposite, includes the following steps：
1) silicon chip is put into concentrated sulfuric acid hydrogen peroxide solution, impregnates the organic pollution for removing surface, then rinses well,
The mixed liquor for being then placed in hydrofluoric acid and deionized water rinses, and removes the oxide layer on surface；
2) silicon chip is anode, and platinum filament is cathode, and corrosive liquid is the mixed solution of hydrofluoric acid and absolute ethyl alcohol；Substrate is pre- place
The P-type wafer managed, the back side pad one layer of aluminium film, to form good Ohmic contact, in the state of DC voltage-stabilizing, to silicon chip into
Row corrosion, prepares porous silicon；
3) porous silicon made from is positioned in N-Methyl pyrrolidone solution and is ultrasonically treated, then micro- in 4- ethylene aniline
Wave processing, is cleaned with N-Methyl pyrrolidone, and the porous silicon nanoparticles of aniline are made；
4) porous silicon nanoparticles of aniline are added to HCl, aniline and ammonium persulfate as oxidant, ice bath stirring
Reaction is then cleaned with deionized water, N-Methyl pyrrolidone, ethyl alcohol and polyaniline/porous silicon nanocomposite is made；
5) polyaniline/porous silicon nanocomposite is added in Doxorubicin solution, is protected from light processing, then with hypervelocity from
Scheming is washed, both.
In step 1), concentrated sulfuric acid hydrogen peroxide solution is：98% concentrated sulfuric acid：Hydrogen peroxide=3：1, volume ratio.
In step 1), silicon chip is put into concentrated sulfuric acid hydrogen peroxide solution, is impregnated 30 minutes under 80 DEG C of heating conditions.
In step 1), the mixed liquor of hydrofluoric acid and deionized water is：A concentration of 40% hydrofluoric acid presses body with deionized water
Product is than being 1：1.
In step 2), corrosive liquid is that hydrofluoric acid and absolute ethyl alcohol press 3：Mixed solution made of 1 volume ratio.
It is 100mA/cm with current density in step 2)2, etching time is that 15 minutes conditions corrode silicon chip.
In step 3), porous silicon obtained is positioned over ultrasound 2 hours in N-Methyl pyrrolidone solution, is then added 3%
The 4- ethylene aniline of volume is cleaned 3 times, the porous silicon that aniline is made is received in 100 DEG C of microwaves 1 hour with N-Methyl pyrrolidone
Rice grain.
In step 4), 1mg/mL benzene VANi-PSiNPs is added to 1mol/L HCl, 10mmol/L aniline and ammonium persulfate
As oxidant, ice bath stirring is reacted 12 hours, is then cleaned with deionized water, N-Methyl pyrrolidone, ethyl alcohol and polyphenyl is made
Amine/porous silicon nanocomposite.
In step 5), 1mg/mL PANi-PSiNPs are added in adriamycin (DOX) solution, are protected from light 12 hours, then
It is washed 3 times with ultracentrifuge, DOX@PANi-PSiNPs is made.
The polyaniline that the preparation method of the degradable polyaniline/porous silicon nanocomposite is obtained/porous
Silicon nanocomposite.
The polyaniline/porous silicon nanocomposite answering in preparing the drug or reagent for tumour diagnosis and treatment
With.
Advantageous effect：Porous silicon nano material prepared by the present invention, is compared to other inorganic nano materials, and porous silicon is received
There is rice material adjustable aperture, big surface area and surface to be easy to functionalization, can be used for loading different organic molecules, life
Object macromolecular or nano material etc..In addition, porous silicon nano material has good biocompatibility and biodegradability, make
Prodigious potentiality can be had in clinical application by obtaining it, this is because porous silicon nanoparticles can be degraded to former silicon in vivo
It is excreted by urine after acid.To which we have synthesized degradable polyaniline/porous silicon nanocomposite, the material
With obviously stable photo-thermal ability, water-soluble and outstanding biocompatibility and degradable ability well, and can be with
It is effective to load adriamycin, there can be apparent chemotherapy to combine synergistic therapeutic effect with thermotherapy in vivo or in vitro.
Description of the drawings
Fig. 1 is XPS figures；
Fig. 2 is the corresponding concentration of element figure of porous silicon-base nanocomposite；
Fig. 3 is FTIR figures；
Fig. 4 is thermograph；
Fig. 5 is (a) molybdenum blue colorimetric method coloration result figure；(b) pass through Si in ICP-OES and UV-vis-NIR volumetric soiutions
Containing spirogram；
Fig. 6 is 4T1 cell viability measurement result figures；
Fig. 7 is mouse thermograph；
Fig. 8 is tumour figure after Different treatments；
Fig. 9 is tumor quality figure after Different treatments.
Specific implementation mode
With reference to specific attached drawing, the present invention is further illustrated.Reagent type used in following embodiment,
Specification and source are as shown in the table.
Embodiment 1
Material preparation：Silicon chip is cut into the square of 2cm × 2cm, is put into the concentrated sulfuric acid (98%)：Hydrogen peroxide=3：1 (volume
Than) solution in, impregnated 30 minutes under 80 DEG C of heating conditions, to remove the organic pollution on surface, then with it is a large amount of go from
Sub- water rinses several times.It is 1 by volume by a concentration of 40% hydrofluoric acid and deionized water：1 mixes in plastic beaker, so
It is put into mixed liquor with the flushed silicon chip of deionized water afterwards, every rinses 30 seconds, removes the oxide layer on surface.
Silicon chip is anode, and platinum filament is cathode, and corrosive liquid is that hydrofluoric acid and absolute ethyl alcohol press 3：It is mixed made of 1 volume ratio
Solution.Substrate is pretreated P-type wafer, and one layer of aluminium film is padded at the back side, to form good Ohmic contact, in DC voltage-stabilizing
It is 100mA/cm with current density under state2, etching time is that 15 minutes conditions corrode silicon chip, is prepared porous
Silicon (PSiNPs).Porous silicon obtained is positioned over ultrasound 2 hours in N-Methyl pyrrolidone solution, and 3% volume is then added
4- ethylene aniline is cleaned 3 times with N-Methyl pyrrolidone in 100 DEG C of microwaves 1 hour, the porous silicon nanoparticles of aniline is made
(VANi-PSiNPs)。
1mg/mL VANi-PSiNPs are added to the ammonium persulfate of 1mol/L HCl, 10mmol/L aniline and 10mmol/L
As oxidant, ice bath stirring is reacted 12 hours, is then cleaned with deionized water, N-Methyl pyrrolidone, ethyl alcohol and polyphenyl is made
Amine/porous silicon nanocomposite (PANi-PSiNPs).
1mg/mL PANi-PSiNPs are added in 250ug/mL adriamycins (DOX) solution, is protected from light 12 hours, then uses
Ultracentrifuge is washed 3 times, and DOX@PANi-PSiNPs are made.
X-ray electron spectrum (XPS) is nano combined for characterizing porous silicon-base with Fourier transform infrared spectroscopy (FTIR)
Atomic concentration, element composition and the functional group of object.(1) XPS spectrum of PSiNPs, (2) VANi-PSiNPs, (3) PANi-PSiNPs
Figure such as Fig. 1, corresponding atomic concentration calculate such as Fig. 2.C 1s, N 1s, O 1s, Si 2p, Si 2s and F 1s correspond to
Element in PSiNPs, 4- ethylene aniline and polyaniline, wherein N element can be used in the 4- Ethenylbenzenes of the upper PSiNPs of detection grafting
The concentration variation of amine and aniline molecule, N element is (1) (0.00%) → (2) (1.7%) → (3) (2.8%), because of 4- ethylene
Atom containing N in aniline and aniline molecule, so the constant increase of N 1s signals.In addition, in the surface grafting polymerization object of porous silicon
Thickness is continuously increased, and to which the XPS thickness for detecting Si is reduced, the concentration variation of Si elements is (1) (29.2%) → (2)
(6.5%) → (3) (4.5%).The infrared spectrum of porous silicon-base nano-complex such as Fig. 3, compared to PSiNPs and VANi-
PSiNPs, PANi-PSiNPs are in 1584cm-1With 1504cm-1There are 2 new peaks and corresponds to C=N and C=C on polyaniline
The stretching vibration of quinoid and benzenoid form, 2983cm-1With 803cm-1The constantly enhancing of this 2 peaks is because continuously in graft polymerization 4-
Ethylene aniline and aniline, 1302cm-1Corresponding to the C-N stretching vibrations of second aromatic amine.In addition, 1645cm-1With 1080cm-1
Corresponding to the stretching vibration of SiO-H, the stretching vibration of the bending vibration space Si-O-Si of Si-OH, 962cm-1With 874cm-12
Peak corresponds to Si-OH stretching vibrations, 2100cm-1、908cm-1、670cm-1With 616cm-1Corresponding to Si-HxStretching vibration with it is curved
The disappearance of Qu Zhendong.XPS illustrates to polymerize in PSi surface oxidations with FTIR has gone up polyaniline.
Thermal Imaging Camera is used to detect the temperature change of PANi-PSiNPs solution.Such as Fig. 4, by the PANi- of 400 μ g/mL
PSiNPs is exposed to 1.6W/cm2Irradiated 20 minutes under NIR laser, it can be seen that solution temperature gradually get higher (blue be low temperature,
Red is high temperature), 39.1 DEG C are increased to from 20.6 DEG C, and PBS only increases 2.2 DEG C and 5.4 DEG C with PSiNPs temperature, as a result illustrates
PANi, which is grafted on, can effectively absorb near infrared light and be converted into heat on PSiNPs, and PANi-PSiNPs is in irradiation 4 times
It remains to keep good photo-thermal effect after NIR laser, illustrates that PANi-PSiNPs has good photo and thermal stability.
Molybdenum blue colorimetric method is for detecting the degradation of PANi-PSiNPs and PSiNPs in 37 DEG C of PBS, porous silicon-base nanometer material
Material is degraded to soluble SiO2Blue molybdenum compound can be changed into rapidly, as shown in Fig. 5 (a), Si elements is dense in solution
Degree can be by ultraviolet-visible-near-infrared spectrophotometry (UV-vis-NIR) in 815nm semiquantitative determinations, under Fig. 5 (b)
It is shown.In addition, the concentration of Si can also be determined by inductively coupled plasma emission spectrography (ICP-OES) in solution
Amount, as shown on Fig. 5 (b).The result shows that PANi-PSiNPs and PSiNPs in preceding 1 hour obvious degradation, then slowly drop
Solution, and PANi-PSiNPs is low compared to PSiNPs degradation efficiencies, this is because the PANi in PANi-PSiNPs has delayed drop
Solution, but PANi-PSiNPs and PSiNPs can in physiological environment sustaining degradation.
2 cell application of embodiment
MTT experiment be used to assess the survival ability of 4T1 cells, use DOX, PANi-PSiNPs, DOX@PANi- respectively
Then PSiNPs incubated cells carry out laser irradiation 20 minutes (carrying out control experiment, material illumination has with not illumination), irradiate
Complete incubation different time (2,4,10 or 20 hours).Such as Fig. 6, after being incubated, DOX@PANi-PSiNPs combinations laser compared to
Other groups present highest cell toxicant rationality, as a result illustrate compared with the control group, in the same circumstances, only carry out the thin of chemotherapy
Born of the same parents' survival rate is 37.1%, and the cell survival rate for only carrying out photo-thermal therapy is 62.2%, and chemotherapy is when photo-thermal therapy is combined
Cell survival rate be 23.1%.
3 vivo applications of embodiment
By 106A mouse mastopathy cell (4T1) is injected into the right leg outer side of Balb/C mouse, when the size of tumour reaches
50-70mm3When, intratumor injection material：(1) phosphate buffered saline solution (PBS)+NIR (near-infrared laser) (control), (2) Ah mould
Element (DOX)+NIR, (3) PANi-PSiNPs+NIR, (4) DOX@PANi-PSiNPs, (5) DOX@PANi-PSiNPs+NIR, injection
Dosage is that 1mg/kg DOX, 10mg/kg PANi-PSiNPs or 10mg/kg DOX@PANi-PSiNPs, NIR laser powers are
1.4W/cm2, irradiation time is 10 minutes, and mouse tumor temperature change, thermal imaging camera testing number are detected with Thermal Imaging Camera
According to seeing Fig. 7, NIR laser irradiations after ten minutes, the tumor region temperature of PANi-PSiNPs and DOX@PANi-PSiNPs injections
45 DEG C or so are increased to, and the tumor region temperature of other groups is 30 DEG C or so, the results showed that PANi-PSiNPs is injected in vivo
It still is able to show outstanding photo-thermal effect with DOX@PANi-PSiNPs.In 14 days after drug and laser treatment of mouse, 2 days
A gross tumor volume is measured, is euthanized to mouse after 14 days and takes out tumour and taken pictures and weighed, Fig. 8 and figure are recorded in
In 9, the results showed that DOX@PANi-PSiNPs+NIR present maximum inhibition rate of tumor growth, explanation compared to other 3 groups
Treatment is combined the growth that can inhibit tumour to greatest extent with photo-thermal therapy.
As it can be seen that porous silicon nano material prepared by the present invention has prodigious potentiality in tumour diagnosis and treatment.It is compared to it
There is adjustable aperture, big surface area and surface to be easy to functionalization, can use for his inorganic nano material, porous silicon nano material
In loading different organic molecule, large biological molecule or nano material etc..In addition, porous silicon nano material has biology well
Compatibility and biodegradability so that it can have prodigious potentiality in clinical application, this is because porous silicon nanoparticles
It is excreted by urine after orthosilicic acid capable of being degraded in vivo.To which we have synthesized degradable polyaniline/more
Hole silicon nanocomposite, the material have obviously stable photo-thermal ability, well water-soluble and outstanding bio-compatible
Property and degradable ability, and adriamycin can be effectively loaded, can have apparent chemotherapy and thermotherapy in vivo or in vitro
Combine synergistic therapeutic effect.
Claims (10)
1. a kind of preparation method of degradable polyaniline/porous silicon nanocomposite, which is characterized in that including following step
Suddenly：
1) silicon chip is put into concentrated sulfuric acid hydrogen peroxide solution, impregnates the organic pollution for removing surface, then rinses well, then
The mixed liquor for being put into hydrofluoric acid and deionized water rinses, and removes the oxide layer on surface；
2) silicon chip is anode, and platinum filament is cathode, and corrosive liquid is the mixed solution of hydrofluoric acid and absolute ethyl alcohol；Substrate is pretreated
P-type wafer, one layer of aluminium film is padded at the back side, to form good Ohmic contact, in the state of DC voltage-stabilizing, is carried out to silicon chip rotten
Erosion, prepares porous silicon；
3) porous silicon made from is positioned in N-Methyl pyrrolidone solution and is ultrasonically treated, and 4- ethylene aniline is added, then microwave
Processing, is cleaned with N-Methyl pyrrolidone, and the porous silicon nanoparticles of aniline are made；
4) porous silicon nanoparticles of aniline are added to HCl, aniline and as the ammonium persulfate of oxidant, ice bath stirring is anti-
It answers, is then cleaned with deionized water, N-Methyl pyrrolidone, ethyl alcohol and polyaniline/porous silicon nanocomposite is made；
5) polyaniline/porous silicon nanocomposite is added in Doxorubicin solution, is protected from light processing, then uses ultracentrifuge
Washing, both.
2. the preparation method of degradable polyaniline/porous silicon nanocomposite according to claim 1, feature exist
In in step 1), concentrated sulfuric acid hydrogen peroxide solution is that 98% concentrated sulfuric acid presses 3 with hydrogen peroxide：Solution made of 1 volume ratio；Silicon chip is put
Enter in concentrated sulfuric acid hydrogen peroxide solution, is impregnated 30 minutes under 80 DEG C of heating conditions.
3. the preparation method of degradable polyaniline/porous silicon nanocomposite according to claim 1, feature exist
In in step 1), the mixed liquor of hydrofluoric acid and deionized water is：A concentration of 40% hydrofluoric acid is by volume with deionized water
1：1.
4. the preparation method of degradable polyaniline/porous silicon nanocomposite according to claim 1, feature exist
In in step 2), corrosive liquid is that hydrofluoric acid and absolute ethyl alcohol press 3：Mixed solution made of 1 volume ratio.
5. the preparation method of degradable polyaniline/porous silicon nanocomposite according to claim 1, feature exist
In being 100mA/cm with current density in step 2)2, etching time is that 15 minutes conditions corrode silicon chip.
6. the preparation method of degradable polyaniline/porous silicon nanocomposite according to claim 1, feature exist
In in step 3), porous silicon obtained is positioned over ultrasound 2 hours in N-Methyl pyrrolidone solution, and 3% volume is then added
4- ethylene aniline is cleaned 3 times with N-Methyl pyrrolidone in 100 DEG C of microwaves 1 hour, the porous silicon nanometer of aniline is made
Grain.
7. the preparation method of degradable polyaniline/porous silicon nanocomposite according to claim 1, feature exist
In, in step 4), by the porous silicon nanoparticles of 1mg/mL aniline be added to 1mol/L HCl, 10mmol/L aniline and
Ammonium persulfates of the 10mmol/L as oxidant, ice bath stirring are reacted 12 hours, and deionized water, N- crassitudes are then used
Polyaniline/porous silicon nanocomposite is made in ketone, ethyl alcohol cleaning.
8. the preparation method of degradable polyaniline/porous silicon nanocomposite according to claim 1, feature exist
In in step 5), 1mg/mL polyanilines/porous silicon nanocomposite is added in Doxorubicin solution, is protected from light 12 hours, so
It is washed 3 times with ultracentrifuge afterwards, degradable polyaniline/porous silicon nanocomposite is made.
9. the preparation method of the degradable polyaniline of claim 1-8 any one of them/porous silicon nanocomposite is obtained
Polyaniline/porous silicon the nanocomposite obtained.
10. polyaniline/porous silicon nanocomposite described in claim 9 is preparing drug or reagent for tumour diagnosis and treatment
In application.
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| Electroluminescence from porous silicon using a conducting polyaniline contact;D.P. Halliday等;《Thin Solid Films》;19961231;第276卷;299-302页 * |
| Hybrid nanostructures based on the conducting;L Monastyrskyi等;《J. Phys.: Conf. Ser.》;20111231;第289卷;1-6页 * |
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