CN105126103B - Application of the heteropoly blue near infrared light heat cure - Google Patents
Application of the heteropoly blue near infrared light heat cure Download PDFInfo
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- CN105126103B CN105126103B CN201510611087.0A CN201510611087A CN105126103B CN 105126103 B CN105126103 B CN 105126103B CN 201510611087 A CN201510611087 A CN 201510611087A CN 105126103 B CN105126103 B CN 105126103B
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- heteropoly blue
- photothermal conversion
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Abstract
Application of the heteropoly blue of the present invention near infrared light heat cure, the chemical formula of the heteropoly blue is [N (CH3)4]5[PMo2W10O40]·4H2O, for preparing the photothermal conversion reagent of near infrared light heat cure cancer cell；When the photothermal conversion reagent is used near infrared light heat cure cancer cell, concrete operation step is：Photothermal conversion reagent is added in 1640 culture mediums, is incubated 4 6h of cancer cell, using the laser light of 808nm according to 10 20min, then the survival rate by MTT colorimetric determination cancer cells.Compared with prior art, heteropoly blue [N (CH of the present invention3)4]5[PMo2W10O40]·4H2O has preferable absorption in near-infrared region, and with preferable photothermal conversion ability, for preparing the photothermal conversion reagent of near infrared light heat cure cancer cell, photothermal conversion efficiency is high, photo and thermal stability is good.
Description
Technical field
The invention belongs near infrared light thermal transition field of material technology, are related to heteropoly blue answering near infrared light heat cure
With.
Background technology
Heteropoly blue is the reduzate of heteropoly acid and its salt, is that the transition metal such as molybdenum, the tungsten of a major class lower valency are miscellaneous more
The general name of hydrochlorate is mostly mixed valence compound, and composition is complicated, and water and air is stablized, have variable oxidation state, electric conductivity,
Diversity of light sensitivity and different oxidation state colors etc..After being reduced due to heteropoly acid and its salt, although a small number of be presented other
Color, but it is most of navy blue is all presented, so being traditionally known as " heteropoly blue " (Heteropoly Blue).Heteropoly blue is
A kind of complex of mixed valence.According to the heterogeneity of various heteropolyanions, one or more electricity can be introduced after reduction
Son, and the properties such as electron delocalization, localization and anti-ferromagnetic coupling interaction are presented, make it have different magnetic properties.At present, for
The research of heteropoly blue substantially concentrates on the property Quality Research such as the optics to it, magnetics, electricity and catalytic chemistry.
Photo-thermal therapy technology is a kind of important minimally-invasive treatment technology, and the technology is using photothermal conversion reagent by laser
Luminous energy is converted to thermal energy, so as to achieve the purpose that kill cell with high temperature.Its main feature is that can be accurately positioned, kill sick cell or
Tissue.And in numerous technique for hyperthermia, near-infrared thermotherapy is more concerned.At present, more near-infrared photo-thermal is studied to turn
It changes reagent and is broadly divided into noble metal nanometer material, carbon material, also organic compound, chalcogen copper-based nano material, Metal Substrate light
Hot material etc., species are relatively more.And it is current, related heteropoly blue is rarely reported as photothermal conversion reagent.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide heteropoly blues near infrared light
Application in heat cure is mainly used as photothermal conversion reagent, and near infrared light thermotherapy.
The purpose of the present invention can be achieved through the following technical solutions：
Application of the heteropoly blue near infrared light heat cure, the chemical formula of the heteropoly blue is [N (CH3)4]5
[PMo2W10O40]·4H2O, for preparing the photothermal conversion reagent of near infrared light heat cure cancer cell.
When the photothermal conversion reagent is used near infrared light heat cure cancer cell, concrete operation step is：With 1640 trainings
Foster basigamy photothermal conversion reagent is incubated cancer cell 4-6h, using the laser light of 808nm according to 10-20min, then passes through MTT colorimetrics
Method detects the survival rate of cancer cell.
The photothermal conversion reagent is formed by heteropoly blue and redistilled water mixed preparing, and the photothermal conversion
The mass concentration of heteropoly blue is 10-400 μ g/mL in reagent.
The mass concentration of heteropoly blue is 200-400 μ g/mL in the photothermal conversion reagent.
The mass concentration of heteropoly blue is 200 μ g/mL in the photothermal conversion reagent.
The cancer cell is one kind in breast cancer cell or cervical cancer cell.
In the present invention, the specific preparation method of photothermal conversion reagent is：5mg heteropoly blue solid particles are weighed, measure 5mL bis- times
Distilled water, ultrasonic disperse obtain the heteropoly blue aqueous solution of 1mg/mL, are then once diluted with redistilled water again to being completely dissolved
Into required mass concentration, i.e. 10-400 μ g/mL.
In the present invention, the heteropoly blue [N (CH3)4]5[PMo2W10O40]·4H2O is black-and-blue solid powder, with reference to existing
There is technology to be prepared, for example, with reference to Northeast Normal University master thesis (Liu Zhengxi：Based on mono-/bis-omission Keggin-type
Synthesis, crystal structure and the magnetic research of the HPAs complex of anion), it mainly includes the following steps that：
(1) with reference to Inorganic Synthesis this this book chapters page 100 of volume 27 the 3rd, presoma needed for synthesis
Na9PW9O34；
(2) with the presoma Na of synthesis9PW9O34For raw material, N is added in2H4·H2[the Mo of O reduction gained2O4]2+, adjust molten
Liquid pH, and under hydrothermal condition, stir to get final material [N (CH3)4]5[PMo2W10O40]·4H2O。
It weighs and prepares the heteropoly blue of gained and be dissolved in redistilled water, be made into the solution of 1mg/mL, after ultrasonic disperse, sampling
The quartz colorimetric utensil of two sides light transmission is placed in, absorption of the heteropoly blue in 400-1000nm wave bands is monitored with nucleic acid/protein analyzer
Situation.UV absorption shows heteropoly blue of the present invention [N (CH3)4]5[PMo2W10O40]·4H2O has preferable in near-infrared region
It absorbs.
It weighs the heteropoly blue obtained by preparing to be dissolved in redistilled water, wiring solution-forming, bis- water samples of 1mL is taken after ultrasonic disperse
Product are placed in fluorescence cuvette.Cuvette is placed in camera bellows, is irradiated with the laser of 808nm, until solution heating reach platform with
Stop laser light afterwards to shine.It while illumination, is monitored in real time with thermal infrared imager, passes through near infrared light thermal imaging software systems
Receive the temperature variations of sample solution.
By near infrared light Thermal test, heteropoly blue [N (CH of the present invention are further proved3)4]5[PMo2W10O40]·4H2O has
There is higher photothermal conversion efficiency.
Based on above-mentioned characteristic, heteropoly blue [N (CH produced by the present invention3)4]5[PMo2W10O40]·4H2O can be used as photo-thermal and turn
Reagent is changed, and in near-infrared photo-thermal physical therapy.
Compared with prior art, heteropoly blue [N (CH of the present invention3)4]5[PMo2W10O40]·4H2O has in near-infrared region
It is preferable to absorb, and with preferable photothermal conversion ability, available for the photothermal conversion for preparing near infrared light heat cure cancer cell
Reagent, meanwhile, material preparation process is simple, reaction controllability is strong, it is raw materials used be easy to get, be cheap, the photo-thermal of resulting materials
High conversion efficiency, photo and thermal stability are good.
Description of the drawings
Fig. 1 is heteropoly blue of the present invention [N (CH3)4]5[PMo2W10O40]·4H2The XRD spectrum of O；
Fig. 2 is heteropoly blue of the present invention [N (CH3)4]5[PMo2W10O40]·4H2The XPS collection of illustrative plates of O；
Fig. 3 is heteropoly blue of the present invention [N (CH3)4]5[PMo2W10O40]·4H2The UV-vis collection of illustrative plates of O；
Fig. 4 is heteropoly blue of the present invention [N (CH3)4]5[PMo2W10O40]·4H2The photo-thermal heating curve of O various concentration solution；
Fig. 5 is heteropoly blue of the present invention [N (CH3)4]5[PMo2W10O40]·4H2The photo and thermal stability curve of O；
Fig. 6 is heteropoly blue of the present invention [N (CH3)4]5[PMo2W10O40]·4H2O acts on the toxotest figure of 4T1 cells；
Fig. 7 is heteropoly blue of the present invention [N (CH3)4]5[PMo2W10O40]·4H2O acts on the toxotest figure of Hela cells；
Fig. 8 is heteropoly blue of the present invention [N (CH3)4]5[PMo2W10O40]·4H2O acts on the photo-thermal effect test of 4T1 cells
Figure.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Heteropoly blue [N (CH in following embodiments3)4]5[PMo2W10O40]·4H2O be black-and-blue solid powder, preparation side
Method refers to Northeast Normal University master thesis (Liu Zhengxi：HPAs complex based on mono-/bis-omission Keggin-type anion
Synthesis, crystal structure and magnetic research), mainly include the following steps that：
(1) with reference to Inorganic Synthesis this this book chapters page 100 of volume 27 the 3rd, presoma needed for synthesis
Na9PW9O34；
(2) with the presoma Na of synthesis9PW9O34For raw material, N is added in2H4·H2[the Mo of O reduction gained2O4]2+, adjust molten
Liquid pH, and under hydrothermal condition, stir to get final material [N (CH3)4]5[PMo2W10O40]·4H2O。
Embodiment 1：
It weighs preparation gained heteropoly blue solid 4mg and is dissolved in 10mL secondary waters, the solution of 400 μ g/mL is made into, after ultrasonic disperse
The 1mL samples is taken to be placed in fluorescence cuvette.Cuvette is placed in camera bellows to be irradiated with the laser of 808nm, until solution heating reaches
Stop laser light after to platform to shine.It is monitored in real time while illumination with thermal infrared imager, passes through near infrared light thermal imaging
Software systems receive the temperature variations of sample solution.As a result as shown in Fig. 4 curves, under the irradiation of 808nm laser, 5min
Interior, temperature raises about 9 DEG C.
Fig. 1 show the XRD spectrum of the present embodiment heteropoly blue, wherein the peak of 15 ° -30 ° corresponding anionicsites, 7.86 °,
8.84 °, 9.36 ° it is corresponding be cationic moiety strong peak, with provide in document by monocrystalline simulate come diffracting spectrum
It is corresponding, and the position consistency of main peak, while also illustrate that the purity of compound products is higher；Fig. 2 is miscellaneous more for the present embodiment
Blue XPS collection of illustrative plates, elemental analysis in figure the result shows that, there is the molybdenums of low price in the heteropoly blue of the present embodiment；Fig. 3 is this reality
The UV-vis collection of illustrative plates of a heteropoly blue is applied, as shown in the figure：Material between 600-800nm (wave crest is located at 720nm) there are one compared with
Strong wider absorption, mostlys come from Mo among heteropoly blueⅤTo MoⅥElectron transition；Fig. 5 show the present embodiment heteropoly blue light
Thermal stability curve, it is seen that the present embodiment heteropoly blue sample passes through 8 reciprocal illumination (808nm laser illuminations),
The difference on effect very little to heat up every time illustrates the light and heat stability of the present embodiment heteropoly blue sample.
Embodiment 2：
The heteropoly blue solution 2mL of the 400 μ g/mL configured in embodiment 1 is measured, 2mL secondary waters is added to be configured to 200 μ g/mL
Solution, the 1mL samples is taken to be placed in fluorescence cuvette.Cuvette is placed in camera bellows to be irradiated with the laser of 808nm, until solution
Heating stops laser light photograph after reaching platform.It is monitored in real time while illumination with thermal infrared imager, passes through near infrared light
Thermal imaging software systems receive the temperature variations of sample solution.As a result as shown in Fig. 4 curves, in the irradiation of 808nm laser
Under, in 5min, temperature raises about 6 DEG C.
Embodiment 3：
The heteropoly blue solution 2mL of the 200 μ g/mL configured in embodiment 2 is measured, 2mL secondary waters is added to be configured to 100 μ g/mL
Solution, the 1mL samples is taken to be placed in fluorescence cuvette.Cuvette is placed in camera bellows to be irradiated with the laser of 808nm, until solution
Heating stops laser light photograph after reaching platform.It is monitored in real time while illumination with thermal infrared imager, passes through near infrared light
Thermal imaging software systems receive the temperature variations of sample solution.As a result as shown in Fig. 4 curves, in the irradiation of 808nm laser
Under, in 5min, temperature raises about 3 DEG C.
Embodiment 4：
The heteropoly blue solid being prepared is weighed, the light that heteropoly blue mass concentration is 50 μ g/mL is made into 1640 culture mediums
Hot-cast socket reagent is incubated cancer cell 6h, using the laser light of 808nm according to 10min, then passes through MTT colorimetric determination cancer cells
Survival rate.
Embodiment 5：
The heteropoly blue solid being prepared is weighed, the light that heteropoly blue mass concentration is 20 μ g/mL is made into 1640 culture mediums
Hot-cast socket reagent is incubated cancer cell 5h, using the laser light of 808nm according to 10min, then passes through MTT colorimetric determination cancer cells
Survival rate.
Embodiment 6：
The heteropoly blue solid being prepared is weighed, the light that heteropoly blue mass concentration is 10 μ g/mL is made into 1640 culture mediums
Hot-cast socket reagent is incubated cancer cell 4h, using the laser light of 808nm according to 10min, then passes through MTT colorimetric determination cancer cells
Survival rate.
Fig. 6 is the design sketch that the corresponding heteropoly blue solution of embodiment 2-6 is incubated 4T1 (mouse breast cancer) cell, works as material
When concentration reaches 200 μ g/mL, cell survival rate illustrates the another fixed toxicity of this material, but toxicity is very more than 75%
It is small.
Fig. 7 is the design sketch that the corresponding heteropoly blue solution of embodiment 2-6 is incubated Hela (cervical carcinoma of people) cell, works as material
When concentration reaches 200 μ g/mL, cell survival rate illustrates the another fixed toxicity of this material, but toxicity is very more than 70%
It is small.
After Fig. 8 is incubated 4T1 (mouse breast cancer) cell for the corresponding heteropoly blue solution of embodiment 2-6, swashed with near-infrared
Light illumination (808nm, 0.4W/cm2, illumination 10min) design sketch, when material concentration reaches 200 μ g/mL, cell survival rate
For more than 64%, for light control group, the photo-thermal that embodiment 2-6 heteropoly blues show to increase and enhance with concentration is imitated
Fruit, this illustrates its photothermal conversion efficiency height, has good photo-thermal therapy prospect.
Embodiment 7：
The heteropoly blue solid being prepared is weighed, the light that heteropoly blue mass concentration is 320 μ g/mL is made into 1640 culture mediums
Hot-cast socket reagent is incubated cancer cell 6h, using the laser light of 808nm according to 15min, then passes through MTT colorimetric determination cancer cells
Survival rate.
Embodiment 8：
The heteropoly blue solid being prepared is weighed, the light that heteropoly blue mass concentration is 320 μ g/mL is made into 1640 culture mediums
Hot-cast socket reagent is incubated cancer cell 6h, using the laser light of 808nm according to 20min, then passes through MTT colorimetric determination cancer cells
Survival rate.
Claims (4)
1. application of the heteropoly blue in photothermal conversion reagent is prepared, which is characterized in that the chemical formula of the heteropoly blue is [N
(CH3)4]5[PMo2W10O40]·4H2O, for preparing the photothermal conversion reagent of near infrared light heat cure cancer cell.
2. application of the heteropoly blue according to claim 1 in photothermal conversion reagent is prepared, which is characterized in that the light
Hot-cast socket reagent is formed by heteropoly blue and redistilled water mixed preparing, and in the photothermal conversion reagent heteropoly blue matter
Amount concentration is 10-400 μ g/mL.
3. application of the heteropoly blue according to claim 2 in photothermal conversion reagent is prepared, which is characterized in that the light
The mass concentration of heteropoly blue is 200-400 μ g/mL in hot-cast socket reagent.
4. application of the heteropoly blue according to claim 3 in photothermal conversion reagent is prepared, which is characterized in that the light
The mass concentration of heteropoly blue is 200 μ g/mL in hot-cast socket reagent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050074551A1 (en) * | 2002-08-01 | 2005-04-07 | Xueying Huang | Ethylene glycol monolayer protected nanoparticles |
| CN103736106A (en) * | 2013-11-26 | 2014-04-23 | 上海师范大学 | Graphene oxide/bismuth selenide/PVP nanometer composite material, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050074551A1 (en) * | 2002-08-01 | 2005-04-07 | Xueying Huang | Ethylene glycol monolayer protected nanoparticles |
| CN103736106A (en) * | 2013-11-26 | 2014-04-23 | 上海师范大学 | Graphene oxide/bismuth selenide/PVP nanometer composite material, preparation method and application thereof |
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| Title |
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| MoO3–x-Based Hybrids with Tunable Localized Surface Plasmon Resonances:Chemical Oxidation Driving Transformation from Ultrathin Nanosheets to Nanotubes;Qingquan Huang,et al;《chemistry》;20121105;第18卷;第15283-15287页 * |
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