CN105600820B - A kind of green titanium dioxide and preparation method thereof, method of modifying and application - Google Patents
A kind of green titanium dioxide and preparation method thereof, method of modifying and application Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 355
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 170
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 61
- 239000003446 ligand Substances 0.000 claims description 41
- 230000004048 modification Effects 0.000 claims description 35
- 238000012986 modification Methods 0.000 claims description 35
- 229920001223 polyethylene glycol Polymers 0.000 claims description 35
- 229940068917 polyethylene glycols Drugs 0.000 claims description 22
- 238000007626 photothermal therapy Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 230000008685 targeting Effects 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 210000003470 mitochondria Anatomy 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 238000002428 photodynamic therapy Methods 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 5
- 230000004941 influx Effects 0.000 abstract description 5
- 230000005945 translocation Effects 0.000 abstract description 5
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 16
- 229910052719 titanium Inorganic materials 0.000 description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- 239000002202 Polyethylene glycol Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 210000005170 neoplastic cell Anatomy 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- 206010028980 Neoplasm Diseases 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000002438 mitochondrial effect Effects 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 241000790917 Dioxys <bee> Species 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000001225 therapeutic effect Effects 0.000 description 4
- 206010020741 Hyperpyrexia Diseases 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 229910003081 TiO2−x Inorganic materials 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 238000010253 intravenous injection Methods 0.000 description 3
- 210000004881 tumor cell Anatomy 0.000 description 3
- -1 wherein Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 208000035269 cancer or benign tumor Diseases 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000030833 cell death Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002626 targeted therapy Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000011419 induction treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000003463 organelle Anatomy 0.000 description 1
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention relates to a kind of green titanium dioxide and preparation method thereof, method of modifying and application, the preparation method includes：Black titanium dioxide is prepared using aluminum reduction method；Black titanium dioxide is dispersed in water, by ultrasonically treated 2~3 hours after, obtain green titanium dioxide.Green titanium dioxide of the invention is obtained by black titanium dioxide by ultrasonically treated, after ultrasonically treated, black titanium dioxide is changed into green titanium dioxide, unformed thickness degree increases to increase with defect causes green titanium dioxide in visible ray and the influx and translocation of near infrared region, and improve stability, the photodynamic therapy agent that can be induced as near infrared light, the preparation method simple and fast that the present invention is taken, it is reproducible, be changed into black titanium dioxide in the stronger green titanium dioxide of near infrared absorption by success, there is provided the new method that a kind of regulation and control titanium dioxide is responded in visible ray and near infrared light.
Description
Technical field
The present invention relates to a kind of green titanium dioxide and preparation method thereof, method of modifying and application, belong to nano material and
Biomedical applications field.
Background technology
Titanium dioxide semiconductor has good photocatalytic activity and chemical stability, and under ultraviolet excitation, can
To produce a large amount of active oxygens, so that inducing cell death.Therefore, it as a kind of inorganic sensitising agent of excellent performance in tumour light
Photodynamic therapy aspect gets most of the attention.But (Anatase is 3.2eV, and Rutile Type is because the energy gap of titanium dioxide is big
3.0eV), it is only capable of exciting lower generation active oxygen, its Photodynamic activity to receive greatly in ultraviolet light (λ=275-390nm)
Limitation.And near infrared light (λ=600-1350nm) is referred to as " biological window ", absorption of the normal structure in this region is minimum,
Ultraviolet light penetration depth can be overcome shallow and the shortcoming of normal structure is damaged.Therefore, the photodynamics/photo-thermal of near-infrared laser induction
Treatment has wider application prospect.
In order to strengthen absorption of the titanium dioxide in visible ray and near infrared light region, scientists have done many trials.Closely
The success of the black titanium dioxide and red titanium dioxide reported over year synthesizes extension titanium dioxide in visible ray and near-infrared
The response in light region provides new strategy.The oxygen for regulating and controlling titanium dioxide by modes such as metal, nonmetallic and auto-dopes is empty
Site concentration and Ti3+Content, so as to reduce the energy gap of titanium dioxide, and then strengthens it in visible ray and near infrared light region
Absorb.
Mitochondria is the center of energy of cell, and it is widely distributed in cytoplasm.And mitochondria is to thermo-responsive, Neng Goutong
Cross the active oxygen inducing cell death produced in organelle.Therefore, in recent years, Mitochondrially targeted photodynamics and photo-thermal therapy
Become a kind of new paragon for improving tumor treatment efficiency and security.It is quiet in order to further reduce laser power density and material
Arteries and veins injection dosage, needs design badly and builds a kind of mitochondrial photodynamics of targets neoplastic cells/photo-thermal Synergistic treatment nanometer body
System.
The content of the invention
For above demand, it is an object of the invention to provide a kind of green titanium dioxide, and build based on green dioxy
Change the mitochondrial photodynamics of the targets neoplastic cells/photo-thermal Synergistic treatment nanometer system of titanium.
Here, the present invention provides a kind of green titanium dioxide and preparation method thereof, the preparation method includes：Using aluminium also
Former method prepares black titanium dioxide；Then black titanium dioxide is dispersed in water, by ultrasonically treated 2~3 hours after, obtain
Green titanium dioxide.
Green titanium dioxide of the invention is obtained by ultrasonically treated by black titanium dioxide, it is ultrasonically treated after, black two
Titanium oxide is changed into green titanium dioxide, and unformed thickness degree increases and defect increases and causes green titanium dioxide in visible ray and near
The influx and translocation of region of ultra-red, and stability is improve, the photodynamic therapy agent that can be induced as near infrared light, the present invention
It is the preparation method simple and fast taken, reproducible, successfully black titanium dioxide is changed into stronger near infrared absorption
A kind of green titanium dioxide, there is provided the new method that regulation and control titanium dioxide is responded in visible ray and near infrared light.
The present invention also provides a kind of method of modifying of green titanium dioxide, including by after green titanium dioxide elder generation through poly- second two
Alcohol modification and Mitochondrially targeted ligand modified process and prepare Mitochondrially targeted ligand modified green titanium dioxide,
Wherein Mitochondrially targeted ligand modified process uses 1- ethyls-phosphinylidyne diimmonium salt hydrochlorate EDC and triphenylphosphine TPP.
On green titanium dioxide basis, in order to further improve therapeutic efficiency and security, matched somebody with somebody by Mitochondrially targeted
Body is modified, and obtains Mitochondrially targeted ligand modified green titanium dioxide, is constructed Mitochondrially targeted ligand modified based on this
The mitochondrial photodynamics of the targets neoplastic cells/photo-thermal therapy nanometer system of green titanium dioxide.The Mitochondrially targeted part
The green titanium dioxide of modification has good Mitochondrially targeted effect, and in the case where Same Wavelength near-infrared laser is excited, line
The green titanium dioxide of plastochondria targeting ligand modification can simultaneously produce active oxygen and hyperpyrexia, so that the energy of destroyed tumor cell
Center-mitochondria, and then inducing death of neoplastic cells.This is based on the targeting of Mitochondrially targeted ligand modified green titanium dioxide
The mitochondrial photodynamics of tumour cell/photo-thermal therapy nanometer system can be in relatively low laser power density (980nm, 0.72W
cm-2) and relatively low material intravenous injection dosage (8mg kg-1, per mouse) under realize preferable tumor photodynamic/photo-thermal
Therapeutic effect.The present invention is not only that absorption of the enhancing titanium dioxide in visible ray and near infrared light region provides a kind of new side
Method, and a kind of new strategy is provided to build the photodynamics/photo-thermal therapy nanometer system of targets neoplastic cells device, to promoting
Titanium dioxide is significant in the application of biological field.
In the present invention, the polyethyleneglycol modified process includes：Polyethylene glycol is distributed to the water-soluble of green titanium dioxide
It is ultrasonically treated to obtain polyethyleneglycol modified green titanium dioxide in liquid, wherein, the quality of green titanium dioxide and polyethylene glycol
Than being 1:1~1:2.Sonication treatment time preferably 0.5~1 hour.
In the present invention, the Mitochondrially targeted ligand modified process includes：According to mass ratio 1:1~3:1 by 1- ethyls-carbon
Acyl diimmonium salt hydrochlorate and Mitochondrially targeted part are dissolved in organic solution, add polyethyleneglycol modified green titanium dioxide
Titanium, is collected by centrifugation after the stirring of room temperature lucifuge, obtains Mitochondrially targeted ligand modified green titanium dioxide, wherein, polyethylene glycol
The green titanium dioxide of modification and the mass ratio of Mitochondrially targeted part are 1:1~5:1.The preferred methyl alcohol of organic solution.
It is preferred that the polyethylene glycol is amino-polyethyleneglycols.
It is preferred that the Mitochondrially targeted part is triphenylphosphine (TPP).
The present invention also provides a kind of Mitochondrially targeted ligand modified green titanium dioxide obtained by above-mentioned method of modifying,
The Mitochondrially targeted ligand modified green titanium dioxide is by green titanium dioxide through polyethyleneglycol modified process and mitochondria
Targeting ligand modification is prepared.
It is preferred that the particle diameter of the Mitochondrially targeted ligand modified green titanium dioxide is 15~35 nanometers.
The present invention also provides a kind of above-mentioned green titanium dioxide in the photodynamic therapy agent for preparing near infrared light induction
Application, the green titanium dioxide refer to by black titanium dioxide pass through the ultrasonically treated green titanium dioxide for obtaining.
The present invention also provides a kind of above-mentioned Mitochondrially targeted ligand modified green titanium dioxide and is applied in biological field,
Application especially in photodynamics/photo-thermal therapy agent is prepared.
The present invention also provides a kind of above-mentioned Mitochondrially targeted ligand modified green titanium dioxide and is controlled in cancer target and light
The application in treatment field.
The present invention also provides a kind of above-mentioned Mitochondrially targeted ligand modified green titanium dioxide and is preparing near-infrared induction
Photodynamics and photo-thermal therapy agent in application.
The present invention also provides a kind of above-mentioned Mitochondrially targeted ligand modified green titanium dioxide and is preparing near-infrared induction
Photodynamics/photo-thermal Synergistic treatment agent in application.
It is swollen for targetting in preparation that the present invention also provides a kind of above-mentioned Mitochondrially targeted ligand modified green titanium dioxide
Oncocyte is mitochondrial while application in the novel inorganic nanometric photosensitizer of photo-thermal/photodynamics Synergistic treatment.
Brief description of the drawings
Fig. 1 is that black titanium dioxide (a, b) obtained in embodiment 1 and green titanium dioxide (c, d) are dispersed in water respectively
High resolution transmission electron microscopy photo and corresponding digital photograph；
Fig. 2 is the EDS energy spectrum diagrams of green titanium dioxide obtained in embodiment 1；
Fig. 3 is the Raman of original white titania, black titanium dioxide and green titanium dioxide obtained in embodiment 1
Collection of illustrative plates；
Fig. 4 is the UV- of black titanium dioxide obtained in embodiment 1 and the green titanium dioxide aqueous solution under same concentrations
Vis collection of illustrative plates；
Fig. 5 be embodiment 1 prepare green titanium dioxide 980nm laser (power density be 0.72W cm-2) under irradiation
Produce active oxygen aptitude tests curve；
Fig. 6 is embodiment 1 obtained by green titanium dioxide after amino-polyethyleneglycols and TPP targeting ligand modifications
DLS particle diameters and Zeta potential figure.Wherein, a is grain size distribution, and b is Zeta bit map/bitmaps；
Fig. 7 is embodiment 1 obtained by green titanium dioxide after amino-polyethyleneglycols and TPP targeting ligand modifications
FTIR collection of illustrative plates；
Fig. 8 is liter of the green titanium dioxide aqueous solution under 980nm laser different capacity density irradiations obtained in embodiment 1
Warm curve.
Specific embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following implementation methods, it should be appreciated that accompanying drawing and following implementation methods
The present invention is merely to illustrate, is not intended to limit the present invention.
The present invention is by black titanium dioxide (black titania, B-TiO2-x) carry out ultrasonically treated, black oxidation
Titanium is transformed to a kind of new green titanium dioxide (green titania, G-TiO2-x), the green titanium dioxide is visible
The absorption of light and near infrared light region is remarkably reinforced.On this basis, further surface modification is carried out to green titanium dioxide,
After through polyethyleneglycol modified process and Mitochondrially targeted ligand modified process, Mitochondrially targeted ligand modified green dioxy is obtained
Change titanium, Mitochondrially targeted ligand modified green titanium dioxide is presented good dispersiveness and stability, and tool in aqueous
There are preferable biocompatibility, good Mitochondrially targeted specificity.
The present invention provide from black titanium dioxide to the preparation method of green titanium dioxide, black titanium dioxide is disperseed
It is being stablized, absorb stronger green titanium dioxide near infrared region by after ultrasonically treated a period of time in water
(see Fig. 4, green titanium dioxide absorbance is bigger under same concentrations), 15~35 nanometers of the particle diameter of the green titanium dioxide；Meanwhile,
Corresponding aqueous solution color becomes green from black, does not have any allogenic material to introduce in its ultrasonication, and should
Preparation process is irreversible, i.e., black titanium dioxide is by the green titanium dioxide that can be stablized after ultrasonically treated a period of time
Titanium, and green titanium dioxide can not be reduced to black titanium dioxide after ultrasonically treated again.The green titanium dioxide is near red
Outer smooth region absorbs and is remarkably reinforced, and a maximum absorption band is presented at 920nm.It is described black as a kind of preferred scheme
The sonication treatment time that color titanium dioxide is changed into green titanium dioxide is 2-3h.The black titanium dioxide can be by high temperature
Aluminum reduction method is obtained, 15~35 nanometers of particle diameter (the black titanium dioxide preparation process bibliography of the black titanium dioxide：
[1] Wang, Zhou, Yang, Chongyin, Lin, Tianquan, Yin, Hao, Chen, Ping, Wan, Dongyun, Xu,
Fangfang, Huang, Fuqiang, Lin, Jianhua, Xie, Xiaoming, and Jiang, Mianheng.Visible-
light photocatalytic,solar thermal and photoelectrochemical properties of
aluminium-reduced black titania.Energy Environ.Sci.,2013,6,3007-3014.；[2] China
Patent：Method for preparing black titanium dioxide by using dual-temperature area reducing, number of patent application：2013101536488).
Black titanium dioxide is changed into green titanium dioxide, and unformed thickness degree increases to increase with defect causes green titanium dioxide
Titanium is in visible ray and the influx and translocation of near infrared region.Therefore, the light that the green titanium dioxide can be induced as near infrared light is moved
Mechanics therapeutic agent.
In order to further improve therapeutic efficiency and security, the present invention carries out further surface to green titanium dioxide again
Modification.Modification process including amino-polyethyleneglycols functionalization and connection mitochondria targeting ligand TPP.In order to TPP is connected
Green titanium dioxide surface is connected to, amido functional group need to be connected to green titanium dioxide surface by first-selection, and the process is referred to as amino
Polyethylene glycol functionalization, as an example, for example, comprises the following steps：By appropriate two ends all polyethylene glycol with amino such as
(H2N-PEG5000-NH2) be distributed in the aqueous solution of green oxidation titanium, ultrasound a period of time (such as 0.5~1h) obtains amino
Polyethyleneglycol modified green oxidation titanium solution.It is collected by centrifugation, freeze-dried back.The green titanium dioxide and amino are poly-
The mass ratio of ethylene glycol preferably 1:1-1:2.
Then appropriate 1- ethyls-phosphinylidyne diimmonium salt hydrochlorate and TPP are dissolved in methanol solution, add the poly- second of amino
Green titanium dioxide after glycol modification, is collected by centrifugation after room temperature lucifuge stirring a period of time (such as 24h), that is, obtain TPP and repair
The green titanium dioxide of decorations.Wherein, the 1- ethyls-phosphinylidyne diimmonium salt hydrochlorate is 1- ethyls-(3- dimethylaminopropyl)
Phosphinylidyne diimmonium salt hydrochlorate (EDC).The mass ratio of the EDC and TPP preferably 1:1-3:1, after the amino-polyethyleneglycols modification
Green titanium dioxide and TPP quality preferably 1:1-5:1.
Under near-infrared laser (980nm) irradiation, the green oxidation titanium of TPP modifications can produce a large amount of active oxygens (for example
Hydroxyl radical free radical, peroxy radical, hydrogen peroxide etc.) (reactive oxygen species, ROS), can be used as a kind of near-infrared
The photodynamic therapy agent for exciting.Near-infrared laser luminous energy can also be converted into heat energy by the green oxidation titanium of TPP modifications simultaneously,
So that can be used as a kind of photo-thermal therapy agent.Further, since mitochondria can be lured thermo-responsive in the presence of hyperpyrexia and active oxygen
Guided cell is dead.The present invention is grafted upper mitochondria targeting ligand triphenylphosphine (TPP) by amidation process, constructs based on green
The mitochondrial photodynamics of the targets neoplastic cells/photo-thermal therapy nanometer system (G-TiO of color titanium oxide2-x- TPP), explore it
In the application of biomedical sector.Therefore, the present invention provide not only a kind of preparation method of new green oxidation titanium, and
Further it is carried out it is Mitochondrially targeted it is ligand modified after explore its application in terms of neoplasm targeted therapy.
The beneficial effects of the invention are as follows：Green titanium dioxide prepared by the present invention has good dispersiveness and steady in water
It is qualitative, and with good biological safety.By Mitochondrially targeted ligand modified modified with Mitochondrially targeted specificity.
In safe laser power density (980nm, 0.72W cm-2) and relatively low material intravenous injection dosage (8mg kg-1,per
Mouse under), significant tumor photodynamic/photo-thermal therapy effect is achieved.Preparation process is simple of the present invention is quick, it is small to pollute,
It is reproducible；Enhance absorption of the titanium dioxide in visible ray and near infrared light region；Simultaneously green titanium dioxide is explored to exist
Application in terms of neoplasm targeted therapy.The Mitochondrially targeted ligand modified green titanium dioxide that the present invention is obtained can be used as one kind
Photodynamics/the photo-thermal therapy agent of excellent performance, can simultaneously realize the efficient and safe treatment of various diseases especially cancer,
Had very important significance in materialogy and medical domain.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
The technological parameters such as proportioning, time, temperature are also only that an example in OK range, i.e. those skilled in the art can be by these
Selection in suitable scope is done in the explanation of text, and does not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1.
First, the preparation of green titanium dioxide：
Original black titanium dioxide prepared by 100mg aluminum reduction methods is dispersed in 20mL water, ultrasonically treated 2-3h.Will be anti-
Solution centrifugal after answering is collected, freeze-dried back.
Fig. 1 a are the high-resolution-ration transmission electric-lens photo of original black titanium dioxide manufactured in the present embodiment, black dioxy in figure
Change titanium and special core shell structure, i.e. the titanium dioxide TiO to crystallize is presented2It is core, one layer of unformed titanium dioxide is wrapped up in outside
Titanium TiO2-xShell, particle diameter is about 20-30nm..
Fig. 1 b are the digital photograph that black titanium dioxide manufactured in the present embodiment is dispersed in water.Black titanium dioxide in figure
The bad dispersibility in water, reunites serious, is deposited in cuvette bottom, and supernatant is water.
Fig. 1 c are the high-resolution-ration transmission electric-lens photo of green titanium dioxide manufactured in the present embodiment, figure Green titanium dioxide
Particle diameter compares black titanium dioxide with pattern without significant change, but unformed thickness degree substantially increases.Illustrate the green dioxy
The defect for changing the unformed layer of titanium increases, oxygen vacancy concentration increase.
Fig. 1 d are the digital photograph that green titanium dioxide manufactured in the present embodiment is dispersed in water.Figure Green titanium dioxide
The aqueous solution is presented macroscopic green, and it is dispersed in aqueous, there is obvious dindar effect in laser beam when irradiating
Should.
Fig. 2 is the EDS energy spectrum diagrams of green titanium dioxide manufactured in the present embodiment, it was demonstrated that have the presence of Ti and O.
Fig. 3 is the Raman of original white titania manufactured in the present embodiment, black titanium dioxide and green titanium dioxide
Collection of illustrative plates, three is illustrated as Anatase, and main Raman peaks occur blue shift, reconfirm green titanium dioxide oxygen vacancy concentration
Increase.
Fig. 4 is the UV-Vis collection of illustrative plates of black titanium dioxide manufactured in the present embodiment and green titanium dioxide.Phase described in figure
Black titanium dioxide and is occurred in that in the influx and translocation in visible ray and near infrared light region compared with concentration green titanium dioxide
One obvious maximum absorption wavelength, is 920nm.
Fig. 5 is green titanium dioxide manufactured in the present embodiment, and in 980nm laser, (power density is 0.72Wcm-2) irradiation
Under, produce active oxygen aptitude tests curve.For green titanium dioxide described in figure is compared to simple irradiation laser, the activity of generation
Oxygen content showed increased.
2nd, the preparation of the Mitochondrially targeted green titanium dioxide of part TPP modifications：
1) the green titanium dioxide of amino-polyethyleneglycols modification
By 100mg two ends all polyethylene glycol such as (H with amino2N-PEG5000-NH2) it is distributed to the water of green oxidation titanium
In solution, ultrasound a period of time, the green oxidation titanium solution of amino-polyethyleneglycols modification is obtained.It is collected by centrifugation, after freeze-drying
It is standby；
2) Mitochondrially targeted ligand modified green titanium dioxide
50mg 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDC) and 20mg TPP are dissolved in
In 20mL methanol solutions, the green titanium dioxide after the modification of 100mg amino-polyethyleneglycols is added, after room temperature lucifuge stirring 24h
It is collected by centrifugation, that is, obtains the green titanium dioxide of TPP modifications.
Fig. 6 a are the DLS particle diameters by green titanium dioxide after amino-polyethyleneglycols and TPP modifications manufactured in the present embodiment
Distribution map.Green titanium dioxide particle diameter increase after amino-polyethyleneglycols described in figure and TPP modifications, distribution broadens, distribution of peaks grain
Footpath is to increase to 135 again to 196nm from 59nm, and this is attributed to the successful modification of amino-polyethyleneglycols and TPP respectively.
Fig. 6 b are the Zeta potential by green titanium dioxide after amino-polyethyleneglycols and TPP modifications manufactured in the present embodiment
Figure.Green titanium dioxide current potential is moved to positive direction after amino-polyethyleneglycols described in figure and TPP modifications, it was confirmed that the poly- second of amino
The successful modification of glycol and TPP targeting ligands.
Fig. 7 is the FTIR collection of illustrative plates by green titanium dioxide after amino-polyethyleneglycols and TPP modifications manufactured in the present embodiment.
The characteristic absorption peak of Ti-N-O and P-O functional groups is occurred in that in figure, illustrates amino-polyethyleneglycols and TPP targeting ligands to green two
Modified titanium dioxide is modified successfully.
Fig. 8 is the Mitochondrially targeted green titanium dioxide aqueous solution of modification manufactured in the present embodiment, in 980nm laser difference work(
Heating curve under rate density irradiation.Green titanium dioxide aqueous solution ascending temperature described in figure increases with laser power density
And gradually increase.
In sum, the invention provides it is a kind of simple, efficiently green titanium dioxide process and building be based on it is green
The targets neoplastic cells mitochondria photodynamics of color titanium dioxide/photo-thermal Synergistic treatment nanometer system.It is black after ultrasonically treated
Color titanium dioxide is changed into green titanium dioxide, and unformed thickness degree increases to increase with defect causes green titanium dioxide in visible ray
With the influx and translocation of near infrared region.Therefore, the photodynamic therapy agent that the green titanium dioxide can be induced as near infrared light.
Then, in order to further improve therapeutic efficiency and security, we are modified by Mitochondrially targeted part TPP, are constructed and are based on
The mitochondrial photodynamics of the targets neoplastic cells/photo-thermal therapy nanometer system of the green titanium dioxide.The green of TPP modifications
Titanium dioxide has good Mitochondrially targeted effect, and in the case where Same Wavelength near-infrared laser is excited, the green oxidation titanium
Active oxygen and hyperpyrexia can be simultaneously produced, so that the center of energy-mitochondria of destroyed tumor cell, and then induced tumor cell is dead
Die.This be based on green titanium dioxide the mitochondrial photodynamics of targets neoplastic cells/photo-thermal therapy nanometer system can be relatively low
Laser power density and relatively low material intravenous injection dosage under realize preferable tumor photodynamic/photo-thermal therapy effect.
The present invention is not only that absorption of the enhancing titanium dioxide in visible ray and near infrared light region provides a kind of new method, and is structure
Photodynamics/photo-thermal therapy the nanometer system for building targets neoplastic cells device provides a kind of new strategy.This is to promoting titanium dioxide
It is significant in the application of biological field.
Claims (8)
1. a kind of method of modifying of green titanium dioxide, it is characterised in that black titanium dioxide is prepared using aluminum reduction method；Will be black
Color titanium dioxide is dispersed in water, by ultrasonically treated 2~3 hours after, obtain green titanium dioxide；By green titanium dioxide elder generation
Prepared Mitochondrially targeted ligand modified by amino-polyethyleneglycols modification and Mitochondrially targeted ligand modified process
Green titanium dioxide, wherein Mitochondrially targeted ligand modified process use 1- ethyls-phosphinylidyne diimmonium salt hydrochlorate EDC and triphen
Base phosphine TPP.
2. method of modifying according to claim 1, it is characterised in that the amino-polyethyleneglycols modification includes：Will
Amino-polyethyleneglycols are distributed in the aqueous solution of green titanium dioxide, the ultrasonically treated green two for obtaining amino-polyethyleneglycols modification
Titanium oxide, wherein, the mass ratio of green titanium dioxide and amino-polyethyleneglycols is 1:1~1:2.
3. method of modifying according to claim 1, it is characterised in that the Mitochondrially targeted ligand modified process includes：
According to mass ratio 1:1~3:1 1- ethyls-phosphinylidyne diimmonium salt hydrochlorate and Mitochondrially targeted ligand triphenylphosphine are dissolved in it is organic
In solution, the green titanium dioxide of amino-polyethyleneglycols modification is added, be collected by centrifugation after the stirring of room temperature lucifuge, obtain mitochondria target
To ligand modified green titanium dioxide, wherein, the green titanium dioxide and Mitochondrially targeted part of amino-polyethyleneglycols modification
Mass ratio be 1:1~5:1.
4. method of modifying according to claim 3, it is characterised in that the organic solution is methyl alcohol.
5. the Mitochondrially targeted ligand modified green that a kind of method of modifying as any one of Claims 1-4 is obtained
Titanium dioxide.
6. Mitochondrially targeted ligand modified green titanium dioxide according to claim 5, it is characterised in that the line grain
The particle diameter of the green titanium dioxide of body targeting ligand modification is 15~35 nanometers.
7. the Mitochondrially targeted ligand modified green titanium dioxide described in a kind of claim 5 is applied in biological field.
8. application according to claim 7, it is characterised in that prepared as in photodynamics and photo-thermal therapy agent
Using.
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| CN106745222A (en) * | 2017-03-14 | 2017-05-31 | 上海友兰科技有限公司 | A kind of method that black titanium dioxide is largely uniformly prepared |
| CN108514636B (en) * | 2018-03-30 | 2021-04-20 | 张晗 | Nano titanium photo-thermal preparation based on titanium quantum dots and preparation method thereof |
| CN108993514A (en) * | 2018-07-25 | 2018-12-14 | 金华职业技术学院 | A kind of black TiO2Foamed nickel catalyst agent and its preparation method and application |
| CN111762811B (en) * | 2019-04-02 | 2021-06-15 | 中国科学院上海硅酸盐研究所 | Method for preparing black titanium oxide loaded conductive TiO with specific proportion by disproportionating and decomposing titanium suboxide |
| CN111056567B (en) * | 2019-12-25 | 2022-02-11 | 苏州机数芯微科技有限公司 | Preparation method of black rutile phase titanium dioxide |
| CN114031112B (en) * | 2021-09-15 | 2023-06-16 | 中国科学技术大学 | Titanium oxide photo-thermal material, preparation method thereof and application thereof in photo-thermal tumor treatment under second biological infrared window |
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