CN105600820A - Green TiO2 and preparing method, modifying method and application thereof - Google Patents
Green TiO2 and preparing method, modifying method and application thereof 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 349
- 238000000034 method Methods 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 159
- 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 58
- 239000002202 Polyethylene glycol Substances 0.000 claims description 36
- 229920001223 polyethylene glycol Polymers 0.000 claims description 36
- 239000003446 ligand Substances 0.000 claims description 35
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 21
- 238000007626 photothermal therapy Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000002428 photodynamic therapy Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 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 15
- 230000007547 defect Effects 0.000 abstract description 5
- 230000006698 induction Effects 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229940124597 therapeutic agent Drugs 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 20
- 229910052719 titanium Inorganic materials 0.000 description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 18
- 210000004881 tumor cell Anatomy 0.000 description 11
- 206010028980 Neoplasm Diseases 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000002438 mitochondrial effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 230000001939 inductive effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 230000030833 cell death Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010253 intravenous injection Methods 0.000 description 3
- 210000003470 mitochondria Anatomy 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000001225 therapeutic effect Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 229910003081 TiO2−x Inorganic materials 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
- 230000008859 change Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 210000003463 organelle Anatomy 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 238000002626 targeted therapy Methods 0.000 description 2
- 238000012360 testing method 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
- 238000011938 amidation process Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 238000002425 crystallisation Methods 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
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000009093 first-line therapy Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 230000004298 light response Effects 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
- 210000005170 neoplastic cell Anatomy 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 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
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 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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- 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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- 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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- 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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- C—CHEMISTRY; METALLURGY
- 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)
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Abstract
The invention relates to a green TiO2 and preparing method, a modifying method and application thereof. The preparing method comprises: adopting an aluminum reduction method to prepare black TiO2; dispersing the black TiO2 in water, and ultrasonically treating for 2-3h to obtain the green TiO2. The green TiO2 is obtained by ultrasonically treating the black TiO2, after the ultrasonic treatment, the black TiO2 is changed to the green TiO2, due to increase of the thickness of an amorphous form layer and defects, the green TiO2 is enhanced in absorption in the visible light and near infrared regions, the stability is enhanced, the green TiO2 can serve as a photodynamics therapeutic agent of near-infrared light induction, the preparing method is simple and rapid, good in repeatability, the black TiO2 is successfully changed to the green TiO2 with higher absorption in near infrared and a new method regulating the response of TiO2 in visible light and near infrared light is provided.
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 lifeThing field of medical applications.
Background technology
Titanium dioxide semiconductor has good photocatalytic activity and chemical stability, and under ultraviolet excitation, canProduce a large amount of active oxygens, thus inducing cell death. Therefore, it is moving at tumour light as a kind of inorganic sensitising agent of excellent performanceMechanics treatment aspect gets most of the attention. But because the energy gap of titanium dioxide is large, (Anatase is 3.2eV, and Rutile Type is3.0eV), only can excite lower generation active oxygen at ultraviolet light (λ=275 – 390nm), its photodynamics activity has been subject to greatlyRestriction. And near infrared light (λ=600 – 1350nm) is called as " biology window ", normal structure is in the absorption in this regionMinimum, can overcome the shallow shortcoming with damaging normal structure of ultraviolet light penetration depth. Therefore, the photodynamics of near-infrared laser induction/ photo-thermal therapy has application prospect widely.
In order to strengthen the absorption of titanium dioxide in visible ray and near infrared light region, scientists has been done a lot of trials. In recent yearsThe black titanium dioxide of reporting and the success of red titanium dioxide synthesize expansion titanium dioxide in visible ray and near infrared light regionResponse new strategy is provided. By the modes such as metal, nonmetal and auto-dope regulate and control titanium dioxide oxygen vacancy concentration andTi3+Content, thereby the energy gap of minimizing titanium dioxide, and then strengthen its absorption in visible ray and near infrared light region.
Mitochondria is the center of energy of cell, and it is extensively distributed in cytoplasm. And mitochondria is to thermo-responsive, Neng GoutongCross the active oxygen inducing cell death producing in organelle. Therefore, in recent years, Mitochondrially targeted photodynamics and photo-thermal therapyBecome a kind of new mode that improves oncotherapy efficiency and security. In order further to reduce laser power density and material veinID, needs the photodynamics/photo-thermal Synergistic treatment nanometer system that designs and build a kind of target tumor cell mitochondrial badly.
Summary of the invention
For above demand, the object of the present invention is to provide a kind of green titanium dioxide, and build based on green titanium dioxidePhotodynamics/photo-thermal Synergistic treatment nanometer system of the target tumor cell mitochondrial of titanium.
At this, the invention provides a kind of green titanium dioxide and preparation method thereof, described preparation method comprises: also adopt aluminiumFormer legal system is for black titanium dioxide; Then black titanium dioxide is dispersed in water,, after 2～3 hours, obtains by ultrasonic processingTo green titanium dioxide.
Green titanium dioxide of the present invention is obtained by ultrasonic processing by black titanium dioxide, after ultrasonic processing, and black dioxyChange titanium and become green titanium dioxide, unformed layer thickness increases and defect increases and causes green titanium dioxide at visible ray and near-infraredThe absorption in region strengthens, and has improved stability, can be used as the photoinduced photodynamic therapy agent of near-infrared, and the present invention adoptsPreparation method's simple and fast of getting, reproducible, successfully changes black titanium dioxide into the green two stronger near infrared absorptionTitanium oxide, provide a kind of regulate and control titanium dioxide in the new method of visible ray and near infrared light response.
The present invention also provides a kind of method of modifying of green titanium dioxide, comprise by green titanium dioxide first after through polyethylene glycolModification and Mitochondrially targeted ligand modified process and prepare Mitochondrially targeted ligand modified green titanium dioxide, whereinMitochondrially targeted ligand modified process is used 1-ethyl-phosphinylidyne diimmonium salt hydrochlorate EDC and triphenylphosphine TPP.
On green titanium dioxide basis, in order further to improve therapeutic efficiency and security, by Mitochondrially targeted partModify, obtain Mitochondrially targeted ligand modified green titanium dioxide, built based on this Mitochondrially targeted ligand modified greenPhotodynamics/photo-thermal therapy nanometer system of the target tumor cell mitochondrial of titanium dioxide. This is Mitochondrially targeted ligand modifiedGreen titanium dioxide has good Mitochondrially targeted effect, and under Same Wavelength near-infrared laser excites, Mitochondrially targetedLigand modified green titanium dioxide can produce active oxygen and Gao Re simultaneously, thus center of energy-line grain of destroyed tumor cellBody, and then inducing death of neoplastic cells. Be somebody's turn to do the target tumor cell line based on Mitochondrially targeted ligand modified green titanium dioxidePhotodynamics/photo-thermal therapy nanometer system of plastochondria can be at lower laser power density (980nm, 0.72Wcm-2) andLow material intravenous injection dosage (8mgkg-1, permouse) under realize good photodynamic tumor/photo-thermal therapy effect.The present invention not only provides a kind of new method for strengthening titanium dioxide in the absorption in visible ray and near infrared light region, and for buildingPhotodynamics/photo-thermal therapy nanometer system of target tumor organelle provides a kind of New Policy, to promoting titanium dioxide at biologyThe application in field is significant.
In the present invention, described polyethyleneglycol modified process comprises: the aqueous solution that polyethylene glycol is distributed to green titanium dioxideIn, ultrasonic processing obtains polyethyleneglycol modified green titanium dioxide, wherein, and the mass ratio of green titanium dioxide and polyethylene glycolFor 1:1～1:2. Preferably 0.5～1 hour ultrasonic processing time.
In the present invention, described Mitochondrially targeted ligand modified process comprises: according to mass ratio 1:1～3:1 by 1-ethyl-phosphinylidyneDiimmonium salt hydrochlorate and Mitochondrially targeted part are dissolved in organic solution, add polyethyleneglycol modified green titanium dioxide, chamberCentrifugal collection after temperature lucifuge stirs, obtains Mitochondrially targeted ligand modified green titanium dioxide, wherein, polyethyleneglycol modifiedThe mass ratio of green titanium dioxide and Mitochondrially targeted part is 1:1～5:1. Described organic solution particular methanol.
Preferably, described polyethylene glycol is amino polyethylene glycol.
Preferably, described Mitochondrially targeted part is triphenylphosphine (TPP).
The present invention also provides a kind of Mitochondrially targeted ligand modified green titanium dioxide being obtained by above-mentioned method of modifying, instituteState Mitochondrially targeted ligand modified green titanium dioxide by green titanium dioxide through polyethyleneglycol modified process and Mitochondrially targeted joiningBody modification prepares.
Preferably, the particle diameter of described Mitochondrially targeted ligand modified green titanium dioxide is 15～35 nanometers.
The present invention also provide a kind of above-mentioned green titanium dioxide prepare in the photoinduced photodynamic therapy agent of near-infrared shouldWith, this green titanium dioxide refers to the green titanium dioxide being obtained by ultrasonic processing by black titanium dioxide.
The present invention also provides a kind of above-mentioned Mitochondrially targeted ligand modified green titanium dioxide to apply in biological field, outstandingIts application in the agent of preparation photodynamics/photo-thermal therapy.
The present invention also provides a kind of above-mentioned Mitochondrially targeted ligand modified green titanium dioxide at cancer target and light treatment neckThe application in territory.
The present invention also provides a kind of above-mentioned Mitochondrially targeted ligand modified green titanium dioxide at the light of preparing near-infrared inductionApplication in dynamics and photo-thermal therapy agent.
The present invention also provides a kind of above-mentioned Mitochondrially targeted ligand modified green titanium dioxide at the light of preparing near-infrared inductionApplication in the agent of dynamics/photo-thermal Synergistic treatment.
The present invention also provides a kind of above-mentioned Mitochondrially targeted ligand modified green titanium dioxide thin for the preparation of target tumorApplication in the novel inorganic nanometer sensitising agent of born of the same parents' photo-thermal/photodynamics Synergistic treatment of mitochondrial while.
Brief description of the drawings
Fig. 1 is that black titanium dioxide (a, b) and the green titanium dioxide (c, d) that embodiment 1 makes is dispersed in water respectivelyHigh resolution transmission electron microscopy photo and corresponding digital photograph;
Fig. 2 is that the EDS of the green titanium dioxide that makes of embodiment 1 can spectrogram;
Fig. 3 is the Raman collection of illustrative plates of the embodiment 1 original white titanium dioxide, black titanium dioxide and the green titanium dioxide that make;
Fig. 4 is black titanium dioxide and the UV-Vis collection of illustrative plates of the green titanium dioxide aqueous solution under same concentrations that embodiment 1 makes;
Fig. 5 is that at 980nm laser, (power density is 0.72Wcm to the green titanium dioxide prepared of embodiment 1-2) the lower generation of irradiationActive oxygen aptitude tests curve;
Fig. 6 is the DLS of green titanium dioxide after amino polyethylene glycol and the ligand modified modification of TPP target that embodiment 1 makesParticle diameter and Zeta potential figure. Wherein, a is particle diameter distribution map, and b is Zeta bit map/bitmap;
Fig. 7 is the FTIR of green titanium dioxide after amino polyethylene glycol and the ligand modified modification of TPP target that embodiment 1 makesCollection of illustrative plates;
Fig. 8 is the intensification song of the green titanium dioxide aqueous solution that makes of embodiment 1 under 980nm laser different capacity density is irradiatedLine.
Detailed description of the invention
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, only should be understood that accompanying drawing and following embodimentBe used for illustrating the present invention, and unrestricted the present invention.
The present invention passes through black titanium dioxide (blacktitania, B-TiO2-x) carrying out ultrasonic processing, black oxidation titanium changesA kind of novel green titanium dioxide (greentitania, G-TiO are become2-x), this green titanium dioxide is at visible ray and near-infraredThe absorption in light region obviously strengthens. On this basis, green titanium dioxide is carried out to further finishing, through polyethylene glycolAfter modification and Mitochondrially targeted ligand modified process, obtain Mitochondrially targeted ligand modified green titanium dioxide, mitochondriaThe ligand modified green titanium dioxide of target presents good dispersiveness and stability in the aqueous solution, and has good biofaciesCapacitive, good Mitochondrially targeted specificity.
Preparation method from black titanium dioxide to green titanium dioxide provided by the invention, is dispersed in black titanium dioxideIn water, after ultrasonic processing a period of time, obtain stable, absorb stronger green titanium dioxide near infrared region and (seeFig. 4, under same concentrations, green titanium dioxide absorbance is larger), particle diameter 15～35 nanometers of this green titanium dioxide; Meanwhile,Corresponding aqueous solution color has become green from black, in its ultrasonic processing procedure, introduces without any allogenic material, and this systemStandby process is irreversible, and black titanium dioxide can obtain stable green titanium dioxide after by ultrasonic processing a period of time, andGreen titanium dioxide can not be reduced to black titanium dioxide again after ultrasonic processing. This green titanium dioxide is near infrared light regionAbsorb obviously and strengthen, and present a maximum absorption band at 920nm place. As a kind of preferred version, described black dioxyThe ultrasonic processing time that change titanium changes green titanium dioxide into is 2-3h. Described black titanium dioxide can reduce by high temperature aluminumMethod makes, particle diameter 15～35 nanometers of described black titanium dioxide (black titanium dioxide preparation process bibliography:[1]Wang,Zhou，Yang,Chongyin，Lin,Tianquan，Yin,Hao，Chen,Ping，Wan,Dongyun，Xu,Fangfang，Huang,Fuqiang，Lin,Jianhua，Xie,Xiaoming，andJiang,Mianheng.Visible-lightphotocatalytic,solarthermalandphotoelectrochemicalpropertiesofaluminium-reducedblackTitania.EnergyEnviron.Sci., 2013,6,3007-3014.; [2] Chinese patent: two warm area reducing process are prepared black titanium dioxideThe method of titanium, number of patent application: 2013101536488).
Black titanium dioxide becomes green titanium dioxide, and unformed layer thickness increases and defect increases and causes green titanium dioxideAbsorption at visible ray and near infrared region strengthens. Therefore, this green titanium dioxide can be used as the photoinduced photodynamics of near-infraredTherapeutic agent.
In order further to improve therapeutic efficiency and security, the present invention carries out further surface to green titanium dioxide again and repaiiesDecorations. Comprise amino polyethylene glycol functionalization and the modification process that is connected Mitochondrially targeted part TPP. For TPP is connectedReceive green titanium dioxide surface, first-selection need be connected to amido functional group green titanium dioxide surface, and this process is called amino poly-Ethylene glycol functionalization, as an example, for example, comprises the following steps: by appropriate two ends all with amino polyethylene glycol as(H2N-PEG5000-NH2) be distributed in the aqueous solution of green oxidation titanium, ultrasonic a period of time (for example 0.5～1h), obtainAmino polyethyleneglycol modified green oxidation titanium solution. Centrifugal collection, freeze-dried back. Described green titanium dioxide and ammoniaThe preferred 1:1-1:2 of mass ratio of base polyethylene glycol.
Then appropriate 1-ethyl-phosphinylidyne diimmonium salt hydrochlorate and TPP are dissolved in methanol solution, then add amino poly-second twoGreen titanium dioxide after alcohol is modified, room temperature lucifuge stirs rear centrifugal collection of a period of time (for example 24h), obtains TPPThe green titanium dioxide of modifying. Wherein, described 1-ethyl-phosphinylidyne diimmonium salt hydrochlorate is 1-ethyl-(3-dimethylaminopropyl)Phosphinylidyne diimmonium salt hydrochlorate (EDC). The preferred 1:1-3:1 of mass ratio of described EDC and TPP, described amino polyethylene glycol is repaiiedGreen titanium dioxide after decorations and the quality optimization 1:1-5:1 of TPP.
Under near-infrared laser (980nm) irradiates, the green oxidation titanium that this TPP modifies can produce a large amount of active oxygen (examplesAs hydroxyl radical free radical, peroxy radical, hydrogen peroxide etc.) (reactiveoxygenspecies, ROS), can be used as a kind of near-infraredThe photodynamic therapy agent exciting. The green oxidation titanium that this TPP modifies simultaneously can also be heat by near-infrared laser light energy conversionCan, thereby can be used as a kind of photo-thermal therapy agent. In addition, because mitochondria is to thermo-responsive, can be in the effect of Gao Re and active oxygenLower inducing cell death. The present invention, by Mitochondrially targeted part triphenylphosphine (TPP) in amidation process grafting, has builtPhotodynamics/photo-thermal therapy nanometer system (G-TiO of the target tumor cell mitochondrial based on green oxidation titanium2-x-TPP), visitRope its application at biomedical sector. Therefore, the present invention not only provides a kind of preparation side of novel green oxidation titaniumMethod, and further it is carried out Mitochondrially targetedly ligand modifiedly having explored it in the application aspect neoplasm targeted therapy afterwards.
The invention has the beneficial effects as follows: green titanium dioxide prepared by the present invention has good dispersiveness and stable in waterProperty, and there is good biological safety. After Mitochondrially targeted ligand modified modification, there is Mitochondrially targeted specificity. ?Safe laser power density (980nm, 0.72Wcm-2) and lower material intravenous injection dosage (8mgkg-1,perMouse), under, obtained significant photodynamic tumor/photo-thermal therapy effect. Preparation technology's simple and fast of the present invention, pollutionLittle, reproducible; Strengthen the absorption of titanium dioxide in visible ray and near infrared light region; Explored green titanium dioxide simultaneouslyApplication aspect neoplasm targeted therapy. The Mitochondrially targeted ligand modified green titanium dioxide that the present invention obtains can be used as onePhotodynamics/photo-thermal therapy agent of excellent performance can realize the especially efficient and safe treatment of cancer of various diseases simultaneously,In materialogy and medical domain, have very important significance.
Further exemplify embodiment below to describe the present invention in detail. Should be understood that equally following examples are only for to thisBright being further described, can not be interpreted as limiting the scope of the invention, and those skilled in the art is according to of the present inventionSome nonessential improvement that foregoing is made and adjustment all belong to protection scope of the present invention. Proportioning that following example is concrete,The technological parameter such as time, temperature is only also an example in OK range, and those skilled in the art can saying by this paperBright doing in suitable scope selected, and do not really want to be defined in the below concrete numerical value of example.
Embodiment 1.
One, the preparation of green titanium dioxide:
Original black titanium dioxide prepared by 100mg aluminum reduction method is dispersed in 20mL water, ultrasonic processing 2-3h. After reactingSolution centrifugal collect, freeze-dried back.
Fig. 1 a is the high-resolution-ration transmission electric-lens photo of the original black titanium dioxide prepared of the present embodiment, black titanium dioxide in figureTitanium presents special nucleocapsid structure, with the titanium dioxide TiO of crystallization2For core, the unformed titanium dioxide of coated outside one deck TiO2-xShell, particle diameter is about 20-30nm..
Fig. 1 b is the digital photograph that black titanium dioxide prepared by the present embodiment is dispersed in water. In figure, black titanium dioxide existsBad dispersibility in water, reunites serious, is deposited in cuvette bottom, and supernatant is water.
Fig. 1 c is the high-resolution-ration transmission electric-lens photo of the green titanium dioxide prepared of the present embodiment, figure Green titanium dioxide grainBlack titanium dioxide is compared without significant change with pattern in footpath, but unformed layer thickness obviously increases. This green titanium dioxide is describedThe defect of unformed layer increases, and oxygen vacancy concentration increases.
Fig. 1 d is the digital photograph that green titanium dioxide prepared by the present embodiment is dispersed in water. Figure Green titanium dioxide waterSolution presents macroscopic green, and is dispersed in the aqueous solution, occurs obvious Tyndall effect when laser beam irradiation.
Fig. 2 is that the EDS of the green titanium dioxide prepared of the present embodiment can spectrogram, proves the existence of Ti and O.
Fig. 3 is the Raman of the present embodiment original white titanium dioxide, black titanium dioxide and the green titanium dioxide preparedCollection of illustrative plates, three is all shown as Anatase, and main Raman peak generation blue shift, reconfirms that green titanium dioxide titanyl room is denseDegree increases.
Fig. 4 is the black titanium dioxide prepared of the present embodiment and the UV-Vis collection of illustrative plates of green titanium dioxide. Identical described in figureThe green titanium dioxide of concentration is compared black titanium dioxide and is strengthened in the absorption in visible ray and near infrared light region, and has occurred oneSignificantly maximum absorption wavelength, is 920nm.
Fig. 5 is green titanium dioxide prepared by the present embodiment, and at 980nm laser, (power density is 0.72Wcm-2) shinePenetrate down, produce active oxygen aptitude tests curve. Green titanium dioxide described in figure is compared simple irradiation laser, the work of generationProperty oxygen content showed increased.
Two, the preparation that Mitochondrially targeted part TPP modifies green titanium dioxide:
1) amino polyethyleneglycol modified green titanium dioxide
By 100mg two ends all with amino polyethylene glycol as (H2N-PEG5000-NH2) be distributed to the aqueous solution of green oxidation titaniumIn, ultrasonic a period of time, obtain amino polyethyleneglycol modified green oxidation titanium solution. Centrifugal collection, freeze drying standbyWith;
2) Mitochondrially targeted ligand modified green titanium dioxide
50mg1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDC) and 20mgTPP are dissolved in to 20mLIn methanol solution, then add the amino green titanium dioxide after polyethyleneglycol modified of 100mg, room temperature lucifuge stir after 24h fromThe heart is collected, and obtains the green titanium dioxide that TPP modifies.
Fig. 6 a is the DLS particle diameter of green titanium dioxide after amino polyethylene glycol and TPP modify prepared by the present embodimentDistribution map. Amino polyethylene glycol described in figure and TPP be green titanium dioxide particle diameter increase after modifying, and distribution broadens, distribution of peaksParticle diameter is for to increase to 135 again to 196nm from 59nm, and this is attributed to respectively the successful modification of amino polyethylene glycol and TPP.
Fig. 6 b is the Zeta potential of green titanium dioxide after amino polyethylene glycol and TPP modify prepared by the present embodimentFigure. After amino polyethylene glycol described in figure and TPP modify, green titanium dioxide current potential moves to positive direction, has confirmed amino poly-The successful modification of ethylene glycol and TPP target part.
Fig. 7 is the FTIR collection of illustrative plates of green titanium dioxide after amino polyethylene glycol and TPP modify prepared by the present embodiment.In figure, there is the characteristic absorption peak of Ti-N-O and P-O functional group, illustrated that amino polyethylene glycol and TPP target part are to greenThe success of titanium dioxide modification.
Fig. 8 is the green titanium dioxide aqueous solution of Mitochondrially targeted modification prepared by the present embodiment, in the different merits of 980nm laserHeating curve under the irradiation of rate density. Green titanium dioxide aqueous solution ascending temperature described in figure is along with laser power density increaseIncrease gradually.
In sum, the invention provides one simply, efficiently green titanium dioxide process and build based on greenTarget tumor cell mitochondrial photodynamics/photo-thermal Synergistic treatment nanometer system of titanium dioxide. After ultrasonic processing, blackTitanium dioxide becomes green titanium dioxide, and unformed layer thickness increases and defect increases and causes green titanium dioxide at visible ray and closelyThe absorption of region of ultra-red strengthens. Therefore, this green titanium dioxide can be used as the photoinduced photodynamic therapy agent of near-infrared. WithAfter, in order further to improve therapeutic efficiency and security, we modify by Mitochondrially targeted part TPP, built based onPhotodynamics/photo-thermal therapy nanometer system of the target tumor cell mitochondrial of this green titanium dioxide. The green that this TPP modifiesTitanium dioxide has good Mitochondrially targeted effect, and under Same Wavelength near-infrared laser excites, this green oxidation titanium energyEnough produce active oxygen and Gao Re simultaneously, thus the center of energy-mitochondria of destroyed tumor cell, and then induced tumor cell is deadDie. Photodynamics/photo-thermal therapy the nanometer system that is somebody's turn to do the target tumor cell mitochondrial based on green titanium dioxide can be lowerUnder laser power density and lower material intravenous injection dosage, realize good photodynamic tumor/photo-thermal therapy effect. ThisBright not only for enhancing titanium dioxide provides a kind of new method in the absorption in visible ray and near infrared light region, and for building targetPhotodynamics/photo-thermal therapy nanometer system of tumour cell device provides a kind of New Policy. This leads at biology promoting titanium dioxideThe application in territory is significant.
Claims (11)
1. a preparation method for green titanium dioxide, is characterized in that, described preparation method comprises: adopt aluminum reduction method to prepare black titanium dioxide; Black titanium dioxide is dispersed in water, after 2～3 hours, obtains green titanium dioxide by ultrasonic processing.
2. the green titanium dioxide being made by preparation method claimed in claim 1.
3. the method for modifying of green titanium dioxide described in a claim 2, it is characterized in that, green titanium dioxide is prepared to Mitochondrially targeted ligand modified green titanium dioxide through polyethyleneglycol modified process and Mitochondrially targeted ligand modified process first, and wherein Mitochondrially targeted ligand modified process is used 1-ethyl-phosphinylidyne diimmonium salt hydrochlorate EDC and triphenylphosphine TPP.
4. method of modifying according to claim 3, it is characterized in that, described polyethyleneglycol modified process comprises: polyethylene glycol is distributed in the aqueous solution of green titanium dioxide, ultrasonic processing obtains polyethyleneglycol modified green titanium dioxide, wherein, the mass ratio of green titanium dioxide and polyethylene glycol is 1:1～1:2.
5. according to the method for modifying described in claim 3 or 4, it is characterized in that, described Mitochondrially targeted ligand modified process comprises: according to mass ratio 1:1～3:1 by 1-ethyl-phosphinylidyne diimmonium salt hydrochlorate and Mitochondrially targeted part triphenylphosphine dissolved in organic solution, add polyethyleneglycol modified green titanium dioxide, centrifugal collection after room temperature lucifuge stirs, obtain Mitochondrially targeted ligand modified green titanium dioxide, wherein, the mass ratio of polyethyleneglycol modified green titanium dioxide and Mitochondrially targeted part is 1:1～5:1.
6. according to the method for modifying described in any one in claim 3 to 5, it is characterized in that, described polyethylene glycol is amino polyethylene glycol.
7. according to the method for modifying described in any one in claim 3 to 6, it is characterized in that, described organic solution is methyl alcohol.
8. the Mitochondrially targeted ligand modified green titanium dioxide being obtained by the method for modifying described in any one in claim 3 to 7.
9. Mitochondrially targeted ligand modified green titanium dioxide according to claim 8, is characterized in that, the particle diameter of described Mitochondrially targeted ligand modified green titanium dioxide is 15～35 nanometers.
10. a green titanium dioxide claimed in claim 2 is in the application of preparing in the photoinduced photodynamic therapy agent of near-infrared.
11. 1 kinds of Mitochondrially targeted ligand modified green titanium dioxide claimed in claim 8 are applied in biological field, especially preparation as the application in the agent of photodynamics/photo-thermal therapy.
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