CN107032404A - A kind of extra small defect tungsten oxide nanometer grain and its preparation method and application - Google Patents
A kind of extra small defect tungsten oxide nanometer grain and its preparation method and application Download PDFInfo
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- CN107032404A CN107032404A CN201710313210.XA CN201710313210A CN107032404A CN 107032404 A CN107032404 A CN 107032404A CN 201710313210 A CN201710313210 A CN 201710313210A CN 107032404 A CN107032404 A CN 107032404A
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Abstract
The invention discloses a kind of extra small defect tungsten oxide nanometer grain and its preparation method and application, by the use of Dopamine hydrochloride as reducing agent and stabilizer, tungsten hexachloride has synthesized extra small WO as presoma by hydro-thermal method after stirring in organic solvent3‑xQuantum dot, the quantum dot produces heat and singlet oxygen under the irradiation of 808nm laser, can carry out photo-thermal therapy and photodynamic therapy.
Description
Technical field：
The invention belongs to biomedical material preparation field, and in particular to a kind of preparation of extra small defect tungsten oxide nanometer grain
Method, the defect tungsten oxide particle diameter of this method preparation is small to be uniformly dispersed, and good biocompatibility may apply to treatment of cancer side
Face.
Background technology
It is emerging field in nanosecond medical science that nanometer technology is combined the nanometer medical oncology to be formed with medical oncology, is also
The core realm that current various countries frontier science and technology are first developed.Common tumor therapeuticing method mainly includes surgical operation therapy, changed
Treatment, radiotherapy etc. are learned, all tumour cells can be killed on these therapy theories, but these methods are brought to human body
Injury and strong side effect be greater than cancer in itself.Nearest optical therapeutic, which is received much attention, is primarily due to optics
Treatment cost is low, high specificity, Small side effects the features such as.Being usually used in the nano material of photo-thermal therapy has gold nano-material, carbon to receive
Rice material, semi-conducting material etc..
Extra small defect tungsten oxide nanometer grain (WO3-x) be a kind of non-stoichiometric existed with pure form tungsten oxidation
Thing.It has some for example photochromic, near infrared absorptions of unique performance etc., so always one study hotspot.But at present
Prepare WO3-xAlso in the exploratory stage, and most of research is concentrated on and prepared on tungsten oxide nano.And by comparison, nano wire
Quantum dot is small due to its particle diameter, and the features such as being heated evenly is more suitable for applying in biomedical aspect.
Preparing the method for defect tungsten oxide at present mainly has：Chemical vapor infiltration, sputtering method etc. but these methods are to bar
Part has higher requirement, and synthesis is difficult, cost is high.And hydro-thermal method preparation method is simple, relatively low is required to reaction condition, and
The product good dispersion arrived, dynamics than it is more uniform the advantages of.
The content of the invention：
It is an object of the invention to provide the small extra small defect tungsten oxide nanometer grain of a kind of good biocompatibility, particle diameter and its conjunction
Into method and in the application of biomedical aspect.
A kind of preparation method of extra small defect tungsten oxide nanometer grain, stabilizer and reducing agent, chlorination are used as by the use of dopamine
Tungsten is as presoma, and stir laggard water-filling thermal response in organic solution, the extra small defect tungsten oxide being evenly distributed
Nanoparticle.
Described tungsten chloride is selected from WCl6·XH2One or more in O, X=0-6.
The mol ratio of the dopamine and tungsten chloride is 1:1-1:8, further preferred 1:2.
The hydrothermal temperature is 150-250 DEG C, preferably 150-200 DEG C, further preferred 180 DEG C.
The hydro-thermal reaction time is 6-30h, preferably 18-30h；More preferably 24h.
Described organic solvent includes the one or more in triethylene glycol, ethylene glycol, propane diols, preferably three second two
Alcohol.
The product of above-mentioned hydro-thermal reaction is washed at least 3 times with water and ethanol respectively, and 12000rpm centrifugations obtain product.
A kind of extra small defect tungsten oxide nanometer grain, is prepared by above-mentioned method.
Described extra small defect tungsten oxide nanometer grain is used for the preparation for preparing treatment tumour.
The present invention advantage be mainly：(1) WO of this method synthesis3-xParticle diameter is very small；(2) there is obvious photo-thermal to imitate
Should and kinetic effect, can be used for oncotherapy.
Brief description of the drawings
Fig. 1：WO prepared by the present invention3-xTEM figure and EDX power spectrums；
Fig. 2：WO prepared by the present invention3-xXPS figure；
Fig. 3：(A) WO prepared by the present invention of (B) various concentrations3-xSolution 808nm wavelength lights photograph under solution temperature with light
According to the variation diagram of time, WO prepared by (C) present invention3-xThe solar thermochemical cycle figure of solution, WO prepared by (D) present invention3-xSolution is followed
UV-visible spectrum before and after ring；
Fig. 4：Using DPBF as1O2Detection probe, (A) DPBF solution 808nm wavelength lights photograph during ultraviolet-visible inhale
Receive spectrum, WO prepared by (B) present invention3-X+ DPBF solution uv-visible absorption spectra, (C) during 808nm wavelength lights photograph
Under the uv-visible absorption spectra during BP+DPBF solution under leading to Oxygen Condition shines in 808nm wavelength lights, (D) different condition
DPBF (410nm) absorbance change；
Fig. 5：(A) WO prepared by the various concentrations present invention3-xTo 4T under illumination and non-illumination1The toxicity of cell, (B) no
The fluorescence picture dyed with living cells under treatment conditions and apoptotic cell, (C) is intracellular1O2Fluorescence be inverted into picture；
Fig. 6：(A) WO that under the illumination of 808nm wavelength lasers prepared by PBS and the present invention3-xInternal photothermal imaging figure, (B) no
With mouse tumor volume growth chart under the conditions for the treatment of, (C) after 16 days mouse tumor volume vs scheme, mouse in (D) therapeutic process
Changes of weight figure；
Fig. 7：The slice map of mouse major organs and tumor tissues after different therapeutic modalities.
Embodiment
The present invention is intended to further illustrate with reference to embodiment, is not intended to limit the present invention.
Embodiment 1
1、WO3-xPreparation：
Dopamine hydrochloride and WCl6With mol ratio 1:2 are dissolved in triethylene glycol, and mixed liquor is transferred to 20mL polytetrafluoroethyl-ne
In alkene stainless steel autoclave, 24h is heated at 180 DEG C, is cooled to after room temperature, product is washed 3 times with water and ethanol respectively,
12000rpm centrifugations obtain product.
2、WO3-xThe measure of fuel factor and photo and thermal stability：
The WO of 1mL various concentrations is added in suprasil bottle3-xSolution (0,100ppm, 200ppm, 300ppm, 400ppm),
With 808nm wavelength laser light irradiation vial bottom 5min, fixed laser lamp power is 1Wcm-2, every the infrared photo-thermal of 1min
Imager carries out photothermal imaging to solution.The WO of 1mL various concentrations is equally added in quartzy bottle3-xSolution (0,100ppm,
200ppm, 400ppm, 600ppm) solution, with the quartzy bottom of bottle portion 10min of 808nm wavelength lasers light irradiation, the work(of fixed laser lamp
Rate is 1Wcm-2.Every the temperature of 30s recording solutions.Then the concentration of fixed solution be 200ppm, first illumination 10min, it is naturally cold
But 20min is so repeated 5 times to room temperature, equally the change every 30s recording solution temperature.Then determine respectively before 5 circulations
The ultraviolet-visible absorption spectroscopy of solution afterwards.
3、WO3-xIt is dynamic (dynamical) to determine：
By 3mL WO3-XBlack after the ethanol solution mixing of ethanol solution and 30uL1,3 diphenyl isobenzofuran (DPBF)
2h is stirred under conditions of dark, DBPF absorption and parsing is reached balance, simple DPBF solution is irradiated with 808nm wavelength lasers
60min, UV absorption of the solution at 410nm is determined every 10min；With under 808nm wavelength lasers irradiation air conditionses
DPBF and WO3-xMixed solution 60min is same to determine UV absorption of the solution at 410nm every 10min；1O2Generation
To O2There is dependence, determine and be constantly passed through during being shone with 808nm laser lights under conditions of oxygen equally every 10min measure
WO3-xWith the change of the absorbance at DPBF solution 410nm.
4th, the measure of cytotoxicity：
WO is determined by MTT method (MTT)3-xIn vitro toxicity, collects the 4T1 cell (mouse breast cancers of logarithmic phase
Cell), it is inoculated into Trypsin Induced into single scattered cell in 96 orifice plates, the cell density for making each hole is 1x104/
ML cells, in 5%CO2Overnight incubation in 37 DEG C of incubator.Original fluid is removed after adherent, is changed into containing various concentrations
WO3-x(0,50,100,150,200,250ppm) culture medium be further cultured for 24h.Under the hole dark condition of wherein each concentration half
Continue to cultivate, 10min is shone in the hole of half with 808nm laser lights respectively in addition, and each Kong Lijun adds 10uL concentration after illumination is complete
For 5mg.mL-13- (4,5- dimethyl) -2,5- dimethyl tetrazole bromides (MTT) continue to cultivate 4h, MTT and living cells interior lines
Succinate dehydrogenase in plastochondria can make exogenous MTT be reduced into the bluish violet crystal first a ceremonial jade-ladle, used in libation of water-insoluble, then use centrifugation
Machine centrifuges culture plate, carefully sucks upper strata culture medium, adds the first a ceremonial jade-ladle, used in libation that 200uL DMSO solutions dissolve intracellular formation.Finally
The ultraviolet absorption value at 490nm and 630nm is determined with ELIASA.The activity of cell is calculated according to formula：
Wherein, OD490Nm is absorbance of the solution at 490nm, OD630Nm is absorbance of the solution at 630nm.
5th, life or death negative staining is tested：
We further more visually demonstrate WO with the method for fluorescence imaging3-xTherapeutic effect.Contaminated with green fluorescence
Expect calcein-AM dye living cells, red fluorescence dyestuff PI dye dead cells.Collect logarithmic phase 4T1 cells and be seeded in 96 orifice plates
In, the cell density per hole is 1x104Following several ways processing is carried out after/mL, overnight incubation cell attachment respectively：A, blank
Control group, b, 808nm laser light is shone, c, WO3-xWith d, WO3-x+ 808nm laser lights are shone.A groups are without any processing, and b groups use 808
Laser light shines 10min, and c, d group are with containing WO3-xCell culture fluid culture cell 4h, then shone with 808nm laser opticals
(optical power density is fixed as 1Wcm to 10min–2).Illumination continues to cultivate 24h after terminating.With fluorescent dye Calcein-AM and PI
To all cell dyeing 20min, cell finally is cleaned with PBS solution, is imaged under fluorescence inverted microscope.
6th, it is intracellular1O2Detection：
Take the logarithm the 4T1 cells of phase, the cell digested is seeded in overnight incubation on 96 orifice plates, after after cell attachment points
Into tri- groups of a, b, c, first remove three groups of original culture mediums, to a groups in add new culture medium, b, c group addition contain WO3-x's
Culture medium, continues to cultivate 4h.20uL 0.3mg/mL H is added in every hole2After DCFH-DA cultures 30min, a, c group are used respectively
The laser lamp illumination 10min of 808nm wavelength, removes culture medium above, after brine 2 times, is inverted aobvious with fluorescence
Micro mirror is imaged.
7th, zoopery：
The foundation of tumor model：The 4T1 cells of logarithmic phase are collected, once remove remnants' with brine after centrifugation
Nutrient solution.Contain the physiological saline of 4T1 cells in the dorsal sc injection 100uL of the male BALB/c mouse of 6 weeks, after a week
The back of mouse has tumour to grow, and the size of gross tumor volume can pass through vernier caliper measurement, v=ab2/ 2 treat gross tumor volume about
For 120mm3When, mouse is randomly divided into 4 groups every group 3：A, blank control group；B, 808nm wavelength laser irradiation group；c、WO3-x
Group；d、WO3-x+ 808nm wavelength laser irradiation groups.A and b groups inject 20uL physiological saline, c and d components in inside tumor respectively
Carry out not intratumor injection 20uLWO3-x(WO3-xConcentration is 0.5mg.kg–1).Inject and 808nm wavelength laser light irradiation d groups are used after 2h
Tumor locus 5min, the power of laser lamp is 1W.cm-2.In During Illumination tumor locus is recorded near infrared imaging instrument
Temperature.Every the body weight of the big small records mouse of 1 day measurement tumour, mouse is put to death by way of cervical vertebra disconnects after 16 days.
Dissection taking-up major organs (heart, liver, spleen, lung, kidney and tumour) progress histotomy is carried out to mouse and HE dyeing is fallen with fluorescence
Put the change of microscope tissues observed.The inhibiting rate of tumour is calculated by formula below.
VCRepresent blank control group mouse tumor volume VTRepresent experimental mice gross tumor volume.
The result of the test of the present invention：
1st, transmission electron microscope is characterized：
In order to characterize WO3-xThe pattern of nanoparticle, tem study is carried out to it.As shown in figure 1, probably 1-
2nm nanoparticle is evenly distributed in carbon and supported on film, is schemed by EDX it can be seen that the main component of the nanoparticle is O and W.
2nd, x-ray photoelectron power spectrum is characterized：
By Fig. 2 it can be seen that in 35.82eV (W6+4f7/2) and 38.05eV (W6+4f5/2) there are two strong peaks at place,
34.72eV(W5+4f7/2) and 36.82eV (W5+4f5/2) there are two weak peaks at place, it may be said that the bright product is main by W5+to W6+Composition
And atomic ratio is 89:11.Uv-visible absorption spectra.
3rd, thermomechanical effect：
WO3-xThere is stronger absorption under 808nm wavelength, and as the lift-off value of the increase temperature of concentration gradually increases.For
More visually illustrate WO3-xWith good photo-thermal effect, with WO of the infrared thermography to various concentrations3-xSolution exists
808nm wavelength lights carry out photothermal imaging during shining 5min.It is apparent that with WO3-xThe increase photothermal imaging of concentration
Photo it is brighter, Fig. 3 A.600ppm WO is irradiated with 808nm wavelength lasers3-xAfter dispersion liquid 10min, 29 DEG C by of temperature
91 DEG C have been increased to, and after similarity condition processing water, temperature is increased to 39 DEG C or so by 29 DEG C.It is possible thereby to illustrate WO3-xHave
Good photothermy such as Fig. 3 B.Every time with solution elevated temperature during the circulation irradiation of 808nm wavelength lasers lamp in circulation experiment
Degree is essentially identical, and the time being cooled to every time used in room temperature is essentially identical, and the WO after 5 times circulate3-xThe ultraviolet of solution can
See absworption peak and overlapping before circulation, this explanation WO3-xWith good photo and thermal stability.See Fig. 3 C, D
4th, kinetic effect：
1,3 diphenyl isobenzofuran (DPBF) is most widely used active oxygen capturing agent, and it can be with1O2Reaction generation
1,2- dibenzoyl benzene (DBB), can be by determining the decreasing value indirect reaction of UV absorptions of the DPBF at 410nm1O2Production
Raw amount.Absworption peak after simple DPBF solution illumination 60min at 410nm does not change substantially, you can to exclude light
Blanching effect Fig. 4 A.And as addition WO3-xAfterwards, it can be found that with the extension of light application time, absworption peaks of the DPBF at 410nm
Gradually weaken, illustrate under the irradiation of 808nm laser, WO3-xIt can produce1O2Fig. 4 B.And carry out it under logical Oxygen Condition,
DPBF is more obvious compared under air conditionses in 410nm absorbance reduction degree after illumination, that is, increases oxygen in solution
Content can make WO3-xProduce1O2Efficiency strengthen Fig. 4 C.The decreasing value of Fig. 4 D DPBF absorbances at 410nm is intuitively compared
Compared with absorbance does not change substantially after simple DPBF illumination；Contain WO under air conditionses3-xDPBF solution illumination 60min
Absorbance reduces 20% afterwards, and explanation has1O2Produce.Contain WO under Oxygen Condition3-xDPBF solution illumination 60min after extinction
Angle value reduces 33%, that is, being passed through oxygen can improve1O2Yield.It is possible thereby to illustrate WO3-xThe energy under 808nm wavelength lights photograph
It is enough to produce1O2。
5th, MTT toxicity tests
Using MTT methods to WO3-xExternal antitumous effect is investigated.It can be seen that in the condition without illumination
Under, WO3-xAt concentrations up to 250ppm when 4T1 cells survival rate still remain in 80% WO described above3-xThe toxicity of itself
Relatively low good biocompatibility.In light application time under the same conditions, with WO3-xThe survival rate of the increase cell of concentration gradually drops
Low, when concentration is 250ppm, the survival rate of cell only has 30%.See Fig. 5 A, illustrate the WO under dark condition3-xIt is basic to cell
There is no toxicity, and under the irradiation of 808nm laser WO3-xMake cancer cell death that there is certain toxic side effect.
6th, life or death negative staining is tested
In order to more visually verify WO3-xCancer cell death can be made, we are contaminated with Green fluorescent dye calcein-AM
Living cells, red fluorescence dyestuff PI dye dead cells.It can be seen from Fig. 5 B when without any processing, the cell in the visual field is equal
The fluorescence of green is sent, illustrates that cell state is fine.Only use 808nm laser light irradiation or WO3-xHandle cell constantly, the visual field
In only fragmentary several cells send red fluorescence, illustrate that the active of laser irradiating cell does not influence and WO substantially3-xIt is biological
The good small toxicity of compatibility, and with containing WO3-xMedium culture carry out after laser light photograph, largely display is red for cell in the visual field
Color, illustrates that most cells are dead, i.e. WO3-xProduced under the irradiation of laser lamp1O2Make cell death with heat, its result and
The result of MTT experiment is consistent.
7th, intracellular ROS detection：
Using H2DCFH-DA as ROS fluorescence probes, WO is investigated3-xROS ability is produced in the cell.As shown in Figure 5 C, a groups
During with 808nm laser process cells, the intracellular fluorescence that is substantially not visible illustrates that ROS probes can not be produced under the conditions of simple light photograph
It is raw1O2；B groups only use WO3-xIt is intracellular during processing cell also not send green fluorescence, and WO3-xCell is handled with 808nm simultaneously
When can be seen that it is intracellular send green and fluorescence, illustrate WO3-xHave under the irradiation of 808nm lasers1O2Produce,1O2With
Probe combines and sends green fluorescence.
8th, using BALB/c mouse as zoopery object, subcutaneous in mouse sets up tumor model.Noted in mouse tumor
Penetrate WO3-x808nm wavelength laser light irradiation mouse tumor position 5min are used afterwards, at the same time record tumor locus with thermal imaging system
The change of temperature.As seen from Figure 6, WO is not injected3-xMouse 808nm laser light irradiations 5min after temperature only rise to
41℃.And injected WO3-xMouse, tumor locus temperature is increased to 69 DEG C after illumination 5min, it can be seen that WO3-xHave
Good photothermy.Gross tumor volume reaches 120mm3When, mouse is randomly divided into 4 groups：A, blank control group b, 808nm laser
Irradiation group, WO3-xGroup d, WO3-x+ 808nm laser irradiation groups, as shown in fig. 6, the volume of a, b, c group mouse tumor do not occur it is bright
Aobvious reduction, d group mouse intratumor injections WO3-xThe growth of tumour is by obvious after solution 808nm wavelength laser light irradiations 5min
Suppress.Illustrate the WO under conditions of illumination3-xPhotodynamic therapy and thermodynamic therapy can effectively suppress the growth of tumour.
Obvious reduction does not occur for the body weight of mouse over the course for the treatment of, and histotomy result is shown, major organs (the heart spleen of mouse
Lung kidney) obvious exception does not occur, illustrate that therapeutic process does not produce obvious toxicity to mouse (see Fig. 7).
Claims (9)
1. a kind of preparation method of extra small defect tungsten oxide nanometer grain, it is characterised in that by the use of dopamine as stabilizer and also
Former agent, tungsten chloride is as presoma, and stir laggard water-filling thermal response in organic solution, and what is be evenly distributed is extra small scarce
Fall into tungsten oxide nanometer grain.
2. preparation method according to claim 1, it is characterised in that described tungsten chloride is selected from WCl6·XH2O, X=0-6
In one or more.
3. preparation method according to claim 1, it is characterised in that the mol ratio of the tungsten chloride and dopamine is 1:1-
1:8, more preferably 1:2.
4. preparation method according to claim 1, it is characterised in that the hydrothermal temperature is 150-250 DEG C, preferably
150-200 DEG C, further preferred 180 DEG C.
5. preparation method according to claim 1, it is characterised in that the hydro-thermal reaction time is 6-30h, preferably 18-
30h；More preferably 24h.
6. preparation method according to claim 1, it is characterised in that described organic solvent includes triethylene glycol, second two
One or more in alcohol, propane diols, preferably triethylene glycol.
7. preparation method according to claim 1, it is characterised in that the product of hydro-thermal reaction is washed with water and ethanol respectively
At least 3 times, 12000rpm centrifugations obtain product.
8. a kind of extra small defect tungsten oxide nanometer grain, it is characterised in that prepared as the method described in claim any one of 1-7
Obtain.
9. the application of the extra small defect tungsten oxide nanometer grain described in claim 8, it is characterised in that for preparing treatment tumour
Preparation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133191A (en) * | 2018-09-17 | 2019-01-04 | 陕西科技大学 | A kind of three-dimensional pure phase cobalt sulfide nanosphere anode material of lithium-ion battery and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936075A (en) * | 2014-04-18 | 2014-07-23 | 中南大学 | Preparation method of tungsten trioxide film with high photoelectric performance |
| CN105001436A (en) * | 2015-06-25 | 2015-10-28 | 东华大学 | Preparation method of high-flexible light W18O49 electrochromic film |
| CN105680021A (en) * | 2016-03-26 | 2016-06-15 | 上海大学 | Poly-dopamine coated nano-micro powder and preparation method thereof |
-
2017
- 2017-05-05 CN CN201710313210.XA patent/CN107032404B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936075A (en) * | 2014-04-18 | 2014-07-23 | 中南大学 | Preparation method of tungsten trioxide film with high photoelectric performance |
| CN105001436A (en) * | 2015-06-25 | 2015-10-28 | 东华大学 | Preparation method of high-flexible light W18O49 electrochromic film |
| CN105680021A (en) * | 2016-03-26 | 2016-06-15 | 上海大学 | Poly-dopamine coated nano-micro powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HUAPING PENG ET AL.: "Fabrication and multifunctional properties of ultrasmall water-soluble tungsten oxide quantum dots", 《CHEM.COMMUN》 * |
| 霍达: "金属及金属氧化物诊疗体系的医学应用研究", 《中国博士学位论文全文数据库 医药卫生科技辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133191A (en) * | 2018-09-17 | 2019-01-04 | 陕西科技大学 | A kind of three-dimensional pure phase cobalt sulfide nanosphere anode material of lithium-ion battery and preparation method thereof |
| CN109133191B (en) * | 2018-09-17 | 2020-09-29 | 陕西科技大学 | Three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material and preparation method thereof |
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