CN103183386B - Preparation method of Nano WO3-X with near infrared photo-thermal converting property - Google Patents
Preparation method of Nano WO3-X with near infrared photo-thermal converting property Download PDFInfo
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Abstract
The invention belongs to the field of near infrared photo-thermal converting nano-composite material, in particular to a nano WO3-X with the near infrared photo-thermal converting property, the preparation method thereof, and the application in a photo-thermal converting reagent. The preparation method comprises the following steps: resolving tungstic acid into an organic solvent, adding oleoyl alcohol under a stirring condition, increasing the temperature of mixed solution to 180 to 300 DEG C and keeping the temperature for 0.5 to 3 hours, so as to obtain lipid solubility WO3-X through centrifugal separation; and adding lipid solubility WO3-X into chloroform solution containing methoxy polyethylene glycol acid, stirring and reacting for 10 to 15 hours, and then carrying out centrifugal separation. The nano WO3-X material adopts a rod-shaped structure, has a uniform appearance, and is 5 to 30 nm in length, the infrared light absorbability and the thermal stability are excellent, the photo-thermal converting efficiency is high, the biocompatibility and the dispersibility are excellent, the nano WO3-X material can effectively kill cancer cells and is an excellent photo-thermal converting reagent in the photo-thermal curing technology.
Description
Technical field
The invention belongs near infrared light thermal transition field of nanometer material technology, particularly a kind of nanometer WO with near infrared light thermal transition character
3-Xand preparation method thereof and preparing the application in photothermal deformation reagent.
Background technology
Photo-thermal therapy technology is a kind of important minimally-invasive treatment technology, and this technology utilizes photothermal deformation reagent to be heat energy by the transform light energy of laser, thus reach the object of killing cell with high temperature.Its feature has accurate location, kills sick cell or tissue, and in numerous technique for hyperthermias, near infrared thermotherapy more receives much concern.At present, study many near infrared light thermal conversion reagent and be mainly divided into noble metal nanometer material, as different-shape nano materials etc. such as gold, palladiums; Carbon material, as carbon nanotube, redox graphene, graphene oxide etc.; Organic compound, as polyaniline etc.; Also have chalcogen copper-based nano material, metal matrix photothermal material etc., kind is many.But for gold, palladium nano structural material, there is a lot of inherent defect, such as, the near infrared absorption of gold, palladium is mainly derived from the surface plasma resonance effect of nanostructure, and surface plasma resonance effect affects very large by the specific inductivity of the pattern of nanostructure, size and surrounding medium, cause result for the treatment of not obvious; Carbon nanomaterial specific absorbance is lower, and preparation condition is comparatively complicated; And for organic compound, anti-light drift ability, long-time easily photodegradation.
Tungsten oxide 99.999, have unique optical property, desirable near infrared absorption performance, high temperature fast ionic conductive performance etc., therefore tool has been widely used.Due to WO
3-Xthe transition of energy interband, makes it have extraordinary absorption near infrared region, therefore can as a kind of desirable optical-thermal conversion material.Have been reported before and gold nano-material is used as photothermal conversion reagent, this reagent has temperature rise effect preferably, but its recycle is poor, and preparation cost is also higher.
Summary of the invention
The object of this invention is to provide a kind of WO
3-Xnano material, this nano material has good absorption near infrared light 980nm place, and produces heat effect, effectively can kill tumour cell, and Heat stability is good, pattern is even, toxic side effect is little, is suitable for biologic applications.
Another object of the present invention is to provide above-mentioned near infrared photothermal converting agent nanometer WO
3-Xpreparation method, this preparation method is raw materials used to be easy to get, low price, technique are simple, reaction controllability is strong.
Object of the present invention can be achieved through the following technical solutions:
A kind of nanometer WO with near infrared light thermal transition character
3-X, it is characterized in that: described WO
3-Xx value in chemical structural formula is 0≤X≤1, this nanometer WO
3-Xfor club shaped structure, mean length is 5-30nm.
Preferably, x=0.1, i.e. described WO
3-Xcoordinate and be divided into WO
2.9.
The above-mentioned nanometer WO with near infrared light thermal transition character
3-Xpreparation method, its step comprises,
(1) wolframic acid is dissolved in phenylate, under agitation condition, adds oleyl alcohol, mixed solution is warming up to 240 DEG C-280 DEG C, keep 0.5-1 hour, after centrifugation, obtain oil soluble WO
3-X;
(2) the oil soluble WO will obtained in step (1)
3-Xin add chloroformic solution containing methoxy poly (ethylene glycol) acid, stirring reaction 10-13 hour, centrifugation.
In described step (1), the amount ratio of wolframic acid, phenylate and oleyl alcohol is 1mg:0.06-0.3mL:0.03-0.2mL.
In described step (2), the add-on of methoxy poly (ethylene glycol) acid and chloroform is than being 4-9mg/mL.
In described step (2), W elements and methoxy poly (ethylene glycol) acid add proportioning 1 × 10
-6-1 × 10
-2mmol:1mg.Preferably, in described step (2), W elements and methoxy poly (ethylene glycol) acid add proportioning 5 × 10
-4-1 × 10
-3mmol:1mg.
The above-mentioned nanometer WO with near infrared light thermal transition character
3-Xpreparing the application in photothermal deformation reagent.
Compared with prior art, beneficial effect of the present invention is:
1, the nanometer WO for preparing of the present invention
3-Xmaterial is club shaped structure, and pattern is even, and length is 5-30nm, and this nano material has good infrared Absorption performance, well 980nm near infrared light can be converted into heat energy, Heat stability is good.And this nano material biocompatibility and dispersiveness very good, toxic side effect is little, can be used for biologic applications.
2, preparation technology of the present invention is simple, and raw material is cheap, be easy to get.
3, described nanometer WO
3-Xmaterial photothermal conversion efficiency is high, and when sample concentration reaches 1.2mg/mL, under the exciting of 980nm laser, in 5 minutes, temperature can rise to 55 DEG C, effectively can kill cancer cells, is a kind of splendid photothermal deformation reagent in photo-thermal therapy technology.
Accompanying drawing explanation
Fig. 1 is oil soluble WO obtained in embodiment 5
3-XtEM figure, wherein Fig. 1 (A) schemes for low resolution TEM, and Fig. 1 (B) schemes for high resolution TEM.
Fig. 2 is oil soluble WO obtained in embodiment 5
3-XxRD figure spectrum.
Fig. 3 is oil soluble WO obtained in embodiment 5
3-XxPS figure.
Fig. 4 is the dispersed comparison diagram of sample obtained in embodiment 5.
Fig. 5 is the near-infrared absorption spectrum figure of sample obtained in embodiment 5.
Fig. 6 is the photothermal deformation stability test figure of sample obtained in embodiment 5.
Fig. 7 is the photo-thermal intensification efficiency diagram of sample obtained in embodiment 5.
Fig. 8 is the MTT cytotoxicity test pattern of the different concns of sample obtained in embodiment 5.
Fig. 9 is that sample obtained in embodiment 5 is to the photo-thermal effect figure of Hela cell (cervical cancer cell).
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
(1) oil soluble WO
3-Xpreparation
Get wolframic acid 124.92mg (0.5mmol) in round vase, be scattered in 20mL phenylate, under agitation condition, add the oleyl alcohol of 5mL.After being added dropwise to complete, to device air-discharging, then heated up by mixed solution, temperature is elevated to 240 DEG C, keeps 0.5 hour.After reaction terminates, centrifugation, can obtain oil soluble WO
3-X, and this product is stored in the chloroform of 40mL.
(2) WO
3-Xmodification
Get the methoxy poly (ethylene glycol) acid dissolve of 100mg in the chloroform of 13mL, and then add oil soluble WO obtained in 5mL step (1)
3-X(0.0625mmol), stirring reaction 12 hours, after reaction terminates, centrifugation, obtains sample.By the oil soluble WO obtained in the present embodiment
3-Xcarry out XRD figure spectrum to detect, the result characterized from XRD figure illustrates, synthesized WO
3-Xcoordinate and be divided into WO
2.9.
Embodiment 2
(1) oil soluble WO
3-Xpreparation
Get wolframic acid 249.84mg (1mmol) in round-bottomed flask, be scattered in 20mL phenylate, under agitation condition, add the oleyl alcohol of 10mL.After being added dropwise to complete, to device air-discharging, then heated up by mixed solution, temperature is elevated to 240 DEG C, keeps 0.5 hour.After reaction terminates, centrifugation, can obtain oil soluble WO
3-X, and this product is stored in the chloroform of 40mL.
(2) WO
3-Xmodification
Get the methoxy poly (ethylene glycol) acid dissolve of 100mg in the chloroform of 15mL, and then add oil soluble WO obtained in 5mL step (1)
3-X(0.125mmol), stirring reaction 12 hours, after reaction terminates, centrifugation, obtains sample.By the oil soluble WO obtained in the present embodiment
3-Xcarry out XRD figure spectrum to detect, the result characterized from XRD figure illustrates, synthesized WO
3-Xcoordinate and be divided into WO
2.9.
Embodiment 3
(1) oil soluble WO
3-Xpreparation
Get wolframic acid 124.92mg (0.5mmol) in round-bottomed flask, be dispersed in 30mL phenylate, under agitation condition, add the oleyl alcohol of 10mL.After being added dropwise to complete, to device air-discharging, then heated up by mixed solution, temperature is elevated to 280 DEG C, keeps 0.5 hour.After reaction terminates, centrifugation, can obtain oil soluble WO
3-X, and this product is stored in the chloroform of 40mL.
(2) WO
3-Xmodification
Get the methoxy poly (ethylene glycol) acid dissolve of 100mg in the chloroform of 15mL, and then add oil soluble WO obtained in 5mL step (1)
3-X(0.0625mmol), stirring reaction 10 hours, after reaction terminates, centrifugation, obtains sample.By the oil soluble WO obtained in the present embodiment
3-Xcarry out XRD figure spectrum to detect, the result characterized from XRD figure illustrates, synthesized WO
3-Xcoordinate and be divided into WO
2.9.
Embodiment 4
(1) oil soluble WO
3-Xpreparation
Get wolframic acid 187.38mg (0.75mmol) in round-bottomed flask, be dispersed in 30mL phenylate, under agitation condition, add the oleyl alcohol of 20mL.After being added dropwise to complete, to device air-discharging, then heated up by mixed solution, temperature is elevated to 280 DEG C, keeps 0.5 hour.After reaction terminates, centrifugation, can obtain oil soluble WO
3-X, and this product is stored in the chloroform of 40mL.
(2) WO
3-Xmodification
Get the methoxy poly (ethylene glycol) acid dissolve of 100mg in the chloroform of 20mL, and then add oil soluble WO obtained in 5mL step (1)
3-X(0.094mmol), stirring reaction 13 hours, after reaction terminates, centrifugation, obtains sample.By the oil soluble WO obtained in the present embodiment
3-Xcarry out XRD figure spectrum to detect, the result characterized from XRD figure illustrates, synthesized WO
3-Xcoordinate and be divided into WO
2.9.
Embodiment 5
(1) oil soluble WO
3-Xpreparation
Get wolframic acid 187.38mg (0.75mmol) in round-bottomed flask, be dispersed in 30mL phenylate, under agitation condition, add the oleyl alcohol of 20mL.After being added dropwise to complete, to device air-discharging, then heated up by mixed solution, temperature is elevated to 280 DEG C, keeps 1 hour.After reaction terminates, centrifugation, can obtain oil soluble WO
3-X, and this product is stored in the chloroform of 40mL.
(2) WO
3-Xmodification
Get the methoxy poly (ethylene glycol) acid dissolve of 100mg in the chloroform of 15mL, and then add oil soluble WO obtained in 5mL step (1)
3-X(0.094mmol), stirring reaction 12 hours, after reaction terminates, centrifugation, obtains sample.
Fig. 1 is oil soluble WO obtained in the present embodiment
3-XtEM figure, wherein Fig. 1 (A) schemes for low resolution TEM, and Fig. 1 (B) schemes for high resolution TEM, the WO synthesized as we can see from the figure
3-Xfor club shaped structure, pattern is even, and length is 5-30nm.
Fig. 2 is oil soluble WO obtained in the present embodiment
3-XxRD figure spectrum, the result characterized from XRD figure illustrates, synthesized WO
3-Xcoordinate and be divided into WO
2.9.
Fig. 3 is oil soluble WO obtained in the present embodiment
3-XxPS figure, show from the results of elemental analyses figure, there is the tungsten that appraises at the current rate in synthesized material, the characterization result of the XRD figure of its structure and Fig. 2 matches.
Fig. 4 is the dispersed comparison diagram of sample obtained in the present embodiment, Fig. 4 (A) is the solvability picture before sample modification, Fig. 4 (B) is the solvability picture after sample modification, as can be seen from Figure, sample is dissolved in chloroform before modified, is insoluble to phosphate buffer solution, and modified sample is dissolved in phosphate buffer solution, and be insoluble to chloroform, WO is described
3-Xmodification success.
Fig. 5 is the near-infrared absorption spectrum figure of sample obtained in the present embodiment, and show from figure, the material of synthesis has good absorption at 980nm place, ensure that material possesses and absorbs 980nm laser, the ability of release of heat.
Fig. 6 is the photothermal deformation stability test figure of sample obtained in the present embodiment, as can be seen from Figure, sample is under 5 reciprocal illumination (980nm laser illumination), and each effect heated up almost there is not difference, and the photo and thermal stability of the sample prepared by explanation is good.
Fig. 7 is the photo-thermal intensification efficiency diagram of sample obtained in the present embodiment, as can be seen from Figure, the temperature rise effect of sample changes with the change of sample concentration, sample concentration is high, temperature rise effect is good, when sample concentration reaches 1.2mg/mL, under the exciting of 980nm laser, in 5 minutes, temperature can rise to 55 DEG C.
Fig. 8 is the MTT cytotoxicity test pattern of the different concns of sample obtained in the present embodiment, and as can be seen from Figure, when sample concentration is within the scope of 0.75mg/mL, the toxicity of sample is all less, may be used for biologic applications.
Fig. 9 be sample obtained in the present embodiment to the photo-thermal effect figure of Hela cell (cervical cancer cell), be 0.35W/cm at 980nm wavelength, laser intensity
2, the survival rate of Hela cell with material solubility and light application time change and change, illumination is longer, and material solubility is larger, and cancer cell death number is higher.
Embodiment 6
(1) oil soluble WO
3-Xpreparation
Get wolframic acid 187.38mg (0.75mmol), put into round-bottomed flask, add 30mL phenylate, it is disperseed as far as possible, under agitation condition, add the oleyl alcohol of 15mL.After being added dropwise to complete, to device air-discharging, then heated up by mixed solution, temperature is elevated to 280 DEG C, keeps 1 hour.After reaction terminates, centrifugation, can obtain oil soluble WO
3-X, and this product is stored in the chloroform of 40mL.
(2) WO
3-Xmodification
Get the methoxy poly (ethylene glycol) acid dissolve of 100mg in the chloroform of 15mL, and then add oil soluble WO obtained in 5mL step (1)
3-X(0.094mmol), stirring reaction 10 hours, after reaction terminates, centrifugation, obtains sample.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the content disclosed in this embodiment.The equivalence completed under not departing from spirit disclosed in this invention so every or amendment, all fall into the scope of protection of the invention.
Claims (4)
1. one kind has the nanometer WO of near infrared light thermal transition character
3-Xpreparation method, it is characterized in that: described WO
3-Xx value in chemical structural formula is 0≤X≤1, this nanometer WO
3-Xfor club shaped structure, mean length is 5-30nm, and its step comprises,
(1) wolframic acid is dissolved in phenylate, under agitation condition, adds oleyl alcohol, mixed solution is warming up to 240 DEG C-280 DEG C, keep 0.5-1 hour, after centrifugation, obtain oil soluble WO
3-X; The amount ratio of described wolframic acid, phenylate and oleyl alcohol is 1mg:0.06-0.3mL:0.03-0.2mL;
(2) the oil soluble WO will obtained in step (1)
3-Xin add chloroformic solution containing methoxy poly (ethylene glycol) acid, stirring reaction 10-13 hour, centrifugation; Described W elements and methoxy poly (ethylene glycol) acid add proportioning 1 × 10
-6-1 × 10
-2mmol:1mg.
2. the nanometer WO with near infrared light thermal transition character according to claim 1
3-Xpreparation method, it is characterized in that: in described step (2), methoxy poly (ethylene glycol) acid and chloroform add-on than be 4-9mg/mL.
3. the nanometer WO with near infrared light thermal transition character according to claim 1
3-Xpreparation method, it is characterized in that: in described step (2), W elements and methoxy poly (ethylene glycol) acid add proportioning 5 × 10
-4-1 × 10
-3mmol:1mg.
4. the nanometer WO with near infrared light thermal transition character according to claim 1
3-Xpreparation method, it is characterized in that: described WO
3-Xx=0.1 in chemical structural formula.
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| CN109987633B (en) * | 2017-12-29 | 2022-03-29 | 天津大学 | Oxygen vacancy-rich tungsten trioxide porous nanorod, catalytic system, preparation method and application thereof |
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| Synthesis if W18O49 Nanorod via Ammonium Tungsten Oxide and Its Interesting Optical Properties;Chongshen Guo et al.;《Langmuir》;20110829;第27卷;12172-12178 * |
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