CN104030360A - Controllable synthesis and synchronous surface modifying method of MoS2 nanosheet - Google Patents
Controllable synthesis and synchronous surface modifying method of MoS2 nanosheet Download PDFInfo
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Abstract
The invention relates to a controllable synthesis and synchronous surface modifying method of an MoS2 nanosheet. The method comprises the steps that ammonium tetrathiomolybdate serves as an Mo source and an S source, or the ammonium molybdate serves as the Mo source, the thiourea serves as the S source, the ammonium tetrathiomolybdate or the ammonium molybdate and the thiourea are dissolved in water or the mixed solvent of water and polyethylene glycol, thermal treatment is carried out for 12-18 hours under the temperature ranging from 200 DEG C to 220 DEG C, separating and washing are carried out to obtain the MoS2 nanosheet, and the type and concentration of the Mo source and the S source and/or the adopted solvent are/or controlled so that the size of the MoS2 nanosheet can be controlled.
Description
Technical field
The invention belongs to Bio-Nano-Materials field, be specifically related to the MoS that a kind of controlledly synthesis and synchronous surface are modified
2the preparation method of nanometer sheet.
Background technology
Cancer is one of the most dangerous disease of current threat human health.The Chinese tumour registration of < < 2012 annual report > > according to the issue of national tumour Register shows, China resident, because the probability of cancer mortality is 13%, has 1 people because of cancer death in average every 7-8 people.Over nearly 20 years, China's cancer presents rejuvenation and the high trend of M & M " three lines ".Operation, radiation and chemotherapy are several important means of current cancer therapy.Operative treatment is taked local excision's tumor tissues, conventionally can bring huge wound to patient's body and mind.Chemotherapy and radiation method is two kinds of Main Means for the treatment of at present cancer, but these two kinds of method treatment cancers all exist a series of deficiency.Chemotherapy easily causes the toxic side effect of each organ of whole body, and can make tumour produce multidrug resistance, affects result for the treatment of.Radiotherapy also has very large toxic side effect to biological organs, and range of application has significant limitation.People, day by day pursue today of high-quality life, develop new cancer treatment method, improve patient's quality of life, extend the lifetime of tumour patient, there is undoubtedly important research and Practical significance.
Photo-thermal ablation technology, it is photo-thermal therapy, be rising in recent years a kind of novelty micro-/without wound tumor therapeuticing method, it utilizes optothermal material to absorb and near-infrared laser is converted to heat, makes tumor tissues local heating and causes tumour ablation dead and then kill targetedly tumour cell.Near infrared light (wavelength region: 700-1100nm) there is good biological tissue's penetrance, penetrate process photoabsorption decay little and almost to normal biological tissue not damaged, thus biomedical sector particularly therapeutic field of tumor represented good application prospect.The prerequisite that near infrared light is brought into play diagnosis and treatment effect is in vivo to have the nano material that absorbs and near infrared light is converted into heat.
At present, the optical-thermal conversion material of research report is divided into organic compound/polymkeric substance (as Indocyanine Green, polypyrrole nano particle), tungsten oxide nano, nano copper sulfate particle, carbon nanomaterial (as Graphene) and noble metal nanometer material (as gold nanorods, the nanometer sheet of palladium) etc.For noble metal nanometer material, can there is obvious morphology change in it under near-infrared laser radiation condition, finally causes the skew of absorption peak and significantly affect the light thermal property of material.The shortcomings such as the uptake factor of carbon material is relatively low, photo-thermal transformation efficiency is low, have limited it and have further applied.Transient metal sulfide is (as MoS
2, MoSe
2, WS
2and WSe
2) because thering is the advantages such as low cost, low toxicity, become the important research direction in optothermal material field.This class transient metal sulfide has stratiform " class sandwich " structure more, between each atoms metal in same layer, by covalent bonds, between layer-layer, with weak Van der Waals force, combines.The constructional feature of this uniqueness makes them in the application in the fields such as environmental protection, the energy, get the attention.Yet, metallic sulfide in the research of biomedical sector also in the starting stage.
As a member of metallic sulfide, MoS
2nano material has been widely used in the research work of the energy and field of environment protection.As a kind of nano material that near infrared light is had to strong absorption, MoS
2the research that nanometer sheet is used for oncotherapy as optothermal material but rarely has report.The people such as Chou have studied chemical stripping MoS first
2sheet (ceMoS
2) preparation, the absorption characteristic near infrared light, and evaluated ceMoS under the irradiation near infrared light at cell levels
2to the fragmentation effect of cancer cells (Angewandte Chemie, 2013,125:4254-4258.).Yet, this ceMoS
2sheet footpath in about 1um, cannot meet intravenous needs, so uncomfortable fit in melting tumor tissues.At present, the hot method of hydrothermal/solvent is synthetic MoS
2the main method of nano material.Conventional Mo source mainly comprises ammonium molybdate, Sodium orthomolybdate, ammonium thiomolybdate, acetic acid molybdenum dimer etc., and S source mainly comprises elemental sulfur, dithiocarbonic anhydride, hydrogen sulfide, thiocarbamide etc., the MoS obtaining
2pattern mostly be sheet or tubulose.The MoS of the Hydrothermal Synthesis of current bibliographical information
2sheet footpath many more than 200nm, its colloidal stability also needs to be investigated.The people such as Liu have reported that (Adv.Mater.2014, DOI:10.1002/adma.201305256) prepares sheet footpath at the MoS of 200nm left and right by the method for chemical stripping recently
2nanometer sheet, and by further PEG, modify to reduce the MoS of chemical stripping
2sheet footpath, finally obtained diameter at the MoS of 50nm left and right
2-PEG nanometer sheet.Due to MoS
2nanometer sheet itself cannot be as Graphene class carbon material the organism carbochain such as mode by " π-pi-conjugated " and PEG be connected and realize finishing, therefore the technique synthetic and that surface PEG is modified having been reported is very complicated, and cannot realize MoS
2effective control of nanometer sheet pattern.Up to now, a kind of can synchronously realization MoS not yet developed in this area
2the method that the controlledly synthesis of nanometer sheet and surface PEG are modified.
Summary of the invention
The present invention is intended to fill up and cannot synchronously realizes MoS
2the blank that the controlledly synthesis of nanometer sheet and surface PEG are modified, the invention provides the MoS that a kind of controlledly synthesis and synchronous surface are modified
2nanometer sheet and preparation method thereof.
The invention provides a kind of MoS
2the preparation method of nanometer sheet, described method comprises:
Take four thio ammonium molybdate as Mo source and S source, or take ammonium molybdate as Mo source and take thiocarbamide as S source, in the mixed solvent of it is water-soluble or water and polyoxyethylene glycol, 200-220 ℃ of thermal treatments, after 12-18 hours, through separated, washing, obtain MoS
2nanometer sheet, wherein controls kind, concentration and/or the solvent for use in Mo source and S source to control described MoS
2the size of nanometer sheet.
Preferably, take four thio ammonium molybdate as Mo source and S source, the concentration of controlling four thio ammonium molybdate is that 1-6mg/mL be take and made the MoS that sheet footpath is 40-125nm
2nanometer sheet.
Preferably, take water as solvent, take four thio ammonium molybdate as Mo source and S source, the concentration of controlling four thio ammonium molybdate is that 4-6mg/mL be take and made the MoS that sheet footpath is 50 ± 10nm
2nanometer sheet.
Preferably, take the mixed solvent of water and polyoxyethylene glycol as solvent, take four thio ammonium molybdate as Mo source and S source, the concentration of controlling four thio ammonium molybdate is that 4-6mg/mL be take and made the MoS that sheet footpath is 79 ± 15nm
2nanometer sheet.
Preferably, take the mixed solvent of water and polyoxyethylene glycol as solvent, take four thio ammonium molybdate as Mo source and S source, the concentration of controlling four thio ammonium molybdate is that 1-3mg/mL be take and made the MoS that sheet footpath is 79 ± 15nm
2nanometer sheet.
Preferably, take ammonium molybdate as Mo source and take thiocarbamide as S source, the concentration of controlling ammonium molybdate is 20-50mg/mL, and the concentration of thiocarbamide is that 50～80g/mL be take and made the MoS that sheet footpath is 160-345nm
2nanometer sheet.
Preferably, take water as solvent, take ammonium molybdate as Mo source and take thiocarbamide as S source, make the MoS that sheet footpath is 195 ± 34nm
2nanometer sheet.
Preferably, take the mixed solvent of water and polyoxyethylene glycol as solvent, take ammonium molybdate as Mo source and take thiocarbamide as S source, make the MoS that sheet footpath is 296 ± 47nm
2nanometer sheet.
Preferably, while being added with PEG in the solvent of selecting, described MoS
2nanometer sheet is connected with PEG molecule.
Preferably, in described mixed solvent, the volume ratio of water and polyoxyethylene glycol is 1:(0.5-2.5).
Beneficial effect of the present invention:
Technique of the present invention is simple, and product is easy to get; The MoS in the different sheets footpath preparing
2(MoS
2-PEG) nanometer sheet has good blood compatibility and biocompatibility.Synthetic MoS
2-PEG nanometer sheet can absorb near infrared light and it is converted into heat energy and makes radiation position local heating, kills tumour cell; At nano grain surface grafting PEG, can strengthen the colloidal stability of nano material, improve the biocompatibility of material, reduce body reticuloendothelial system the non-specific of nano material engulfed, make nano material be enriched in more tumor region, improve the result for the treatment of to tumour;
The present invention is by add a certain proportion of PEG400 (preferably, the distilled water adopting in the present invention and the volume ratio of PEG400 are 1:0.5-1:1.5) in hydrothermal/solvent thermal response system, at synthetic MoS
2in the time of nanometer sheet, a step realizes MoS
2the structure regulating of nanometer sheet and surface PEG are modified.The a small amount of H producing in reaction process
2s gas can be removed effectively by the mode of follow-up thanomin aqueous cleaning.Therefore, preparation method of the present invention is simple, output is high, is applicable to large-scale industrial and produces;
In one embodiment, the MoS that is 79 ± 15nm by of the present invention footpath
2-PEG nanometer sheet is scattered in 0.9% NaCl injection liquid, and 200uL is injected into lotus by tail vein injection mode to be had in the Balb/C nude mouse of 4T1 breast cancer tumour model, after 24 hours, by power density, is 1W/cm
2, wavelength is 808nm near-infrared laser irradiates tumour 5 minutes.Experimental result is found, the MoS that injection sheet footpath is 79 ± 15nm
2the growth of-PEG nanometer sheet group mouse tumor volume is subject to obvious inhibition.And under equal conditions, only inject the MoS that sheet footpath is 79 ± 15nm
2-PEG nanometer sheet not irradiating laser, injection 0.9% NaCl injection liquid parallel laser is irradiated, and it is obvious only to inject three groups of small mouse tumor propagations of NaCl injection liquid of 0.9%.This experimental result shows the MoS that of the present invention footpath is 79 ± 15nm
2-PEG nanometer sheet has good anti-tumor in vivo effect, in fields such as oncotherapies, has potential application prospect.
Accompanying drawing explanation
Fig. 1 shows and in embodiments of the present invention, prepares the MoS that sheet footpath is respectively 50 ± 10nm
2the MoS of nanometer sheet (a), 79 ± 15nm
2the MoS of-PEG nanometer sheet (b), 103 ± 22nm
2the MoS of-PEG nanometer sheet (c), 195 ± 34nm
2the MoS of nanometer sheet (d) and 296 ± 47nm
2tEM figure and the flake diameter distribution figure thereof of-PEG nanometer sheet (e);
Fig. 2 shows the MoS in the different sheets footpath of preparing in embodiments of the present invention
2or MoS
2the Fourier transform infrared spectroscopy figure of-PEG nanometer sheet;
Fig. 3 shows the MoS in the different sheets footpath of preparing in embodiments of the present invention
2or MoS
2ultraviolet-visible-the near-infrared absorption spectrum of-PEG nanometer sheet;
It is the MoS of 79 ± 15nm (a), 103 ± 22nm (b) and 296 ± 47nm (c) that Fig. 4 shows sheet footpath in embodiments of the present invention
2the hydration kinetics diameter of-PEG nanometer sheet in physiological saline;
Fig. 5 shows the MoS in the different sheets footpath of preparing in embodiment of the present invention
2or MoS
2the x-ray photoelectron spectroscopy spectrogram (b) of the X ray diffracting spectrum of-PEG nanometer sheet (a) and Mo and S;
Fig. 6 a shows the MoS that adopts the different sheets footpath of preparing in embodiment of the present invention
2or MoS
2the concentration of Mo prepared by-PEG nanometer sheet is that suspension or the distilled water of 100ppm is 0.6W/cm at power
2808nm laser radiation under water temperature with the variation schematic diagram of radiated time;
Fig. 6 b shows and adopts the MoS that the sheet footpath of preparing in embodiment of the present invention is 79 ± 15nm
2the concentration of Mo prepared by-PEG nanometer sheet is that the suspension of 100ppm is 0.6W/cm at power
2808nm laser radiation under water temperature change and the relation of radiation number of times;
Fig. 7 a shows the MoS that the sheet footpath of preparing in the embodiments of the present invention that contain different concns is 79 ± 15nm
2ultraviolet-visible-near-infrared absorption spectrum figure of the suspension of-PEG nanometer sheet;
It is 0.6W/cm that Fig. 7 b shows in density
2near-infrared laser irradiate under, contain the MoS preparing in embodiment of the present invention
2the concentration of-PEG nanometer sheet (sheet footpath is 79 ± 15nm) is respectively the changing conditions figure of the suspension water temperature of 100ppm and 200ppm;
Fig. 7 c shows the MoS preparing in the embodiment of the present invention that contains (concentration of Mo is 100ppm) under same concentration
2the suspension water temperature of-PEG nanometer sheet (sheet footpath is 79 ± 15nm) is with the changing conditions of laser intensity;
Fig. 8 shows the MoS that in embodiments of the present invention, sheet footpath is 79 ± 15nm
2the hemolysis rate of-PEG nanometer sheet and the relation of concentration (a), and the MoS that contains different concns
2the fresh plasma of-PEG nanometer sheet (sheet footpath 79 ± 15nm) is hatched prothrombin time (PT), fibrinogen content (FIB) and activated partial thrombin time (APTT) value (b) of measuring after 5min;
Fig. 9 shows and the MoS that contains different concns Mo
2-PEG nanometer sheet (sheet footpath is 79 ± 15nm) suspension is hatched the surviving rate of mouse mastopathy cell (4T1 cell) after 24h and photo-thermal therapy effect altogether, and (cell is 1.0W/cm through power
2808nm laser radiation 5min) the Trypan Blue result figure (dead cell can be dyed for blueness by trypan blue) of cell (a) and after laser treatment.
Embodiment
Below in conjunction with accompanying drawing and following embodiment, further illustrate the present invention, should be understood that accompanying drawing and following embodiment are only for the present invention is described, and unrestricted the present invention.
The present invention relates to a kind of MoS
2the controlledly synthesis of nanometer sheet and synchronous surface modifying method, method can for following one of them:
(1) four thio ammonium molybdate is dissolved in distilled water, after stirring, gained solution is transferred to sealed reaction for some time in the stainless steel cauldron of contraposition polyphenyl liner of 100mL volume, products therefrom is cleaned for several times with the thanomin aqueous solution and distilled water respectively, obtain the MoS that sheet footpath is 50 ± 10nm
2nanometer sheet;
(2) four thio ammonium molybdate is dissolved in the mixing solutions of distilled water and polyoxyethylene glycol, after stirring, gained solution is transferred to sealed reaction for some time in the stainless steel cauldron of contraposition polyphenyl liner of 100mL volume, products therefrom is cleaned for several times with the thanomin aqueous solution and distilled water respectively, obtain the MoS that sheet footpath is 79 ± 15nm
2-PEG nanometer sheet;
(3) other conditions are constant, only change the concentration of four thio ammonium molybdate in step (2), get final product to obtain the sheet footpath MoS that is 103 ± 22nm
2-PEG nanometer sheet;
(4) ammonium molybdate and thiocarbamide are dissolved in distilled water, after stirring, gained solution is transferred to sealed reaction for some time in the stainless steel cauldron of contraposition polyphenyl liner of 100mL volume, products therefrom is cleaned for several times with the thanomin aqueous solution and distilled water respectively, obtain the MoS that sheet footpath is 195 ± 34nm
2nanometer sheet;
(5) other conditions are constant, only, by changing the component of solvent in step (4), obtain the MoS that sheet footpath is 296 ± 47nm
2-PEG nanometer sheet;
Technique of the present invention is simple, and product is easy to get; The MoS of preparation
2-PEG nanometer sheet has good blood compatibility, biocompatibility and extracorporeal anti-tumor effect, expects to can be used for Hyperthermia for Cancer Treatment material new approaches are provided for further developing.
Described a kind of MoS
2in the controlledly synthesis of nanometer sheet and synchronous surface modifying method (1), the concentration of described four thio ammonium molybdate is 4-6mg/mL.
Described a kind of MoS
2in the controlledly synthesis of nanometer sheet and synchronous surface modifying method (2), the concentration of described four thio ammonium molybdate is 4-6mg/mL, and the volume ratio of distilled water and PEG is 1:0.5-1:2.5.
Described a kind of MoS
2in the controlledly synthesis of nanometer sheet and synchronous surface modifying method (2), the molecular weight of described PEG is 200,300 or 400 dalton.
Described a kind of MoS
2in the controlledly synthesis of nanometer sheet and synchronous surface modifying method (3), the concentration of described four thio ammonium molybdate is 1-4mg/mL.
Described a kind of MoS
2in the controlledly synthesis of nanometer sheet and synchronous surface modifying method (4), the concentration of described ammonium molybdate is 20-50mg/mL, and the concentration of thiocarbamide is 50-80mg/mL.
Described a kind of MoS
2in the controlledly synthesis of nanometer sheet and synchronous surface modifying method (5), described solvent composition is the mixing solutions of distilled water and PEG, and the volume ratio of distilled water and PEG400 is 1:0.5-1:2.5.
Described a kind of MoS
2in the controlledly synthesis of nanometer sheet and synchronous surface modifying method method (1)-(5), described churning time is 30-90 minute, and in tetrafluoroethylene autoclave, temperature of reaction is 200-220 ℃, and the reaction times is 12-18 hour.The concentration of the thanomin aqueous solution is 40-60% (volume ratio), and the wash number of the thanomin aqueous solution and distilled water is 3-5 time.
This patent regulates and controls MoS by add the simple method of PEG in solvent thermal solvent
2the pattern of nanometer sheet, and a step realizes MoS
2surface PEG modify.Through contriver, study discovery, the PEG by adding certain volume, in solvent thermal reaction system, can make MoS by solvent thermal reaction
2-PEG nanometer sheet, by changing Mo and S source category and the concentration in solvent thermal reaction system, can realize MoS
2the controlledly synthesis of-PEG nanometer sheet.
Technique of the present invention is simple, and product is easy to get; The MoS in the different sheets footpath preparing
2(MoS
2-PEG) nanometer sheet has good blood compatibility and biocompatibility.Synthetic MoS
2-PEG nanometer sheet can absorb near infrared light and it is converted into heat energy and makes radiation position local heating, kills tumour cell; At nano grain surface grafting PEG, can strengthen the colloidal stability of nano material, improve the biocompatibility of material, reduce body reticuloendothelial system the non-specific of nano material engulfed, make nano material be enriched in more tumor region, improve the result for the treatment of to tumour.
The present invention is by add a certain proportion of PEG400 (preferably, the distilled water adopting in the present invention and the volume ratio of PEG400 are 1:0.5-1:1.5) in hydrothermal/solvent thermal response system, at synthetic MoS
2in the time of nanometer sheet, a step realizes MoS
2the structure regulating of nanometer sheet and surface PEG are modified.The a small amount of H producing in reaction process
2s gas can be removed effectively by the mode of follow-up thanomin aqueous cleaning.Therefore, preparation method of the present invention is simple, output is high, is applicable to large-scale industrial and produces.
In one embodiment, the MoS that is 79 ± 15nm by of the present invention footpath
2-PEG nanometer sheet is scattered in 0.9% NaCl injection liquid, and 200uL is injected into lotus by tail vein injection mode to be had in the Balb/C nude mouse of 4T1 breast cancer tumour model, after 24 hours, by power density, is 1W/cm
2, wavelength is 808nm near-infrared laser irradiates tumour 5 minutes.Experimental result is found, the MoS that injection sheet footpath is 79 ± 15nm
2the growth of-PEG nanometer sheet group mouse tumor volume is subject to obvious inhibition, and under equal conditions, only injects the MoS that sheet footpath is 79 ± 15nm
2-PEG nanometer sheet not irradiating laser, injection 0.9% NaCl injection liquid parallel laser is irradiated, and it is obvious only to inject three groups of small mouse tumor propagations of NaCl injection liquid of 0.9%.This experimental result shows the MoS that of the present invention footpath is 79 ± 15nm
2-PEG nanometer sheet has good anti-tumor in vivo effect, in fields such as oncotherapies, has potential application prospect.
Fig. 1 shows the MoS that the sheet footpath of preparing in embodiment of the present invention is respectively (a) 50 ± 10nm
2the MoS of nanometer sheet, (b) 79 ± 15nm
2the MoS of-PEG nanometer sheet, (c) 103 ± 22nm
2the MoS of-PEG nanometer sheet, (d) 195 ± 34nm
2nanometer sheet and (e) MoS of 296 ± 47nm
2tEM figure and the flake diameter distribution figure thereof of-PEG nanometer sheet;
Fig. 2 shows the MoS in the different sheets footpath of preparing in embodiment of the present invention
2or MoS
2the Fourier transform infrared spectroscopy figure of-PEG nanometer sheet.As can be seen from the figure, except sheet footpath is the MoS of 50 ± 10nm and 195 ± 34nm
2outside nanometer sheet, other respectively organize material at 1060cm
-1the vibration absorption peak of all demonstrated-C-O-of place, illustrates that PEG400 molecular chain has successfully been connected to MoS
2the surface of nanometer sheet;
Fig. 3 shows the MoS in the different sheets footpath of preparing in embodiment of the present invention
2or MoS
2ultraviolet-visible-the near-infrared absorption spectrum of-PEG nanometer sheet suspension (concentration of Mo is 40ppm).As seen from Figure 3, when the concentration of Mo is identical, except the sheet footpath MoS that is 195 ± 34nm
2outside sheet suspension, the suspension of other sheet footpath nanometer sheet materials all can absorb the near-infrared laser that the wavelength of some strength is 808nm.Can estimate, this part near-infrared laser that above-mentioned differing materials absorbs will be converted into heat, thereby possess near-infrared absorption-thermal transition ability;
Fig. 4 shows the MoS that the sheet footpath of preparing in embodiment of the present invention is 79 ± 15nm (a), 103 ± 22nm (b) and 296 ± 47nm (c)
2the hydration kinetics diameter of-PEG nanometer sheet in physiological saline.Be scattered in physiological saline after 24h above-mentioned three kinds of MoS
2the hydration kinetics diameter of-PEG nanometer sheet does not occur significantly to change, and testimonial material has good colloidal stability, for further laying a good foundation in live body assessment of levels their photo-thermal conversion, killing tumor cells ability;
Fig. 5 shows the MoS in the different sheets footpath of preparing in embodiment of the present invention
2or MoS
2the x-ray photoelectron spectroscopy spectrogram of (a) X ray diffracting spectrum of-PEG nanometer sheet and (b) Mo and S.As a in Fig. 5, the X ray diffracting spectrum of the material of different diameter and MoS
2each crystal plane of standard diagram (JCPD73-1508) is substantially identical.Except sheet footpath is the MoS of 195 ± 34nm, 50 ± 10nm
2outside nanometer sheet, other are respectively organized material and between 2 θ=7.5-10 °, have occurred a new diffraction peak, may be because part PEG400 segment is embedded into MoS
2lamella in due to.Further by x-ray photoelectron spectroscopy, the composition of material surface element and atom valence state are analyzed, the corresponding relation of absorption peak and Mo and S atom electronic orbit is as shown in b in Fig. 5.In known each product of documents, the valence state of Mo and S is Mo
4+and S
2-.After PEG molecular chain is introduced, Mo3/2d, Mo5/2d, the combination of S1/2p, S3/2p track can all reduce.May be that the product of gained is unsettled MoS because PEG is introduced into after solvent thermal reaction system
2-PEG is inorganic/organic hybrid system;
Fig. 6 (a) is for the concentration of Mo is 100ppm, and suspension and the distilled water of different sheets footpath nanometer sheet material are 0.6W/cm at power
2808nm laser radiation under water temperature with the variation schematic diagram of radiated time; Fig. 6 (b) shows the MoS that sheet footpath is 79 ± 15nm
2the suspension of-PEG nanometer sheet is 0.6W/cm at power
2808nm laser radiation under water temperature change and the relation of radiation number of times.From Fig. 6 a, can find out, different materials has demonstrated different thermal transition abilities.Sheet footpath is the MoS of 79 ± 15nm
2-PEG nanometer sheet can make 5.5 ° of left and right of distilled water temperature rising of 3mL in 5min, demonstrates best near-infrared laser absorption-thermal transition performance.In addition the MoS that, sheet footpath is 79 ± 15nm
2-PEG nanometer sheet has demonstrated good thermostability.As shown in Figure 6 b, after 10 laser radiation intensification-laser shutdowns cooling experimentation, this material still keeps good photo-thermal transfer capability.Therefore the present invention chooses the MoS that sheet footpath is 79 ± 15nm
2-PEG nanometer sheet is for follow-up photo-thermal therapy tumor research;
The MoS that the sheet footpath that Fig. 7 (a) is different concns is 79 ± 15nm
2ultraviolet-visible-near-infrared absorption spectrum figure of-PEG nanometer sheet.Under low-down concentration, MoS
2the near-infrared laser that-PEG nanometer sheet still can absorption portion wavelength is 808nm.This part laser absorbing discharges the form with heat, and then can give material light thermal property own.Fig. 7 (b) is is 0.6W/cm in density
2near-infrared laser irradiate under, concentration is respectively the MoS of 100ppm and 200ppm
2the changing conditions of-PEG nanometer sheet (sheet footpath is 79 ± 15nm) suspension water temperature.Clearly, the MoS of high density
2-PEG nanometer sheet can be carried out photo-thermal conversion and rising water temperature more effectively.Fig. 7 (c) is under same concentration (concentration of Mo is 100ppm), MoS
2-PEG nanometer sheet (sheet footpath is 79 ± 15nm) suspension water temperature is with the changing conditions of laser intensity.Laser intensity is higher, and energy is larger, and then water temperature rising higher (being respectively 7.77 ℃, 9.38 ℃ and 13.41 ℃), has shown good photo-thermal transfer capability;
In Fig. 8, (a) shows the MoS that sheet footpath is 79 ± 15nm
2the hemolysis rate of-PEG nanometer sheet and the relation of concentration; (b) show the MoS that contains different concns
2the fresh plasma of-PEG nanometer sheet (sheet footpath 79 ± 15nm) is hatched prothrombin time (PT), fibrinogen content (FIB) and activated partial thrombin time (APTT) value of measuring after 5min.As shown in (a) in Fig. 8, when the Mo of erythrocyte and different concns is hatched after 1h jointly, hemolysis rate, all below 5%, is not observed obvious haemolysis in investigating concentration range.After the material of different concns and blood plasma are hatched jointly, the PT of experimental group, FIB and APTT all, in normal range, compare considerable change do not occur with blank group.In a word, within experimental concentration scope, material has good blood compatibility, for the follow-up treatment of intravenous injection safely provides assurance;
In Fig. 9, a shows the MoS with different concns
2-PEG nanometer sheet (sheet footpath is 79 ± 15nm) suspension is hatched the surviving rate of mouse mastopathy cell (4T1 cell) after 24h and photo-thermal therapy effect altogether, and (cell is 1.0W/cm through power
2808nm laser radiation 5min).The evaluation means of cell survival rate is cell counting test kit (CCK-8 test kit) counting process.Within the scope of experimental concentration (0-500 μ g/mL), do not apply in the situation of near-infrared laser radiation of 808nm wavelength, the surviving rate of 4T1 cell is not subject to concentration affects, and surviving rate is all more than 90%, the MoS that sheet footpath is 79 ± 15nm
2-PEG has good cell compatibility.And through 808nm laser radiation 5min, and continue to cultivate after 24h, the surviving rate of 4T1 cell obviously reduces; The concentration of material is higher, more obvious to the inhibition of 4T1 Growth of Cells.When the concentration of Mo is 500ppm, the suppression efficiency of tumour is surpassed to 90%.In Fig. 9, b is the Trypan Blue result (dead cell can be dyed for blueness by trypan blue) of cell after laser treatment, and opticmicroscope microscopy result shows apoptosis of most cells, further shows that sheet footpath is the MoS of 79 ± 15nm
2-PEG nanometer sheet has good external tumour photo-thermal therapy effect.
Below further list some exemplary embodiments so that the present invention to be described better.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in and limit the scope of the invention for the present invention is described, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjust and all belong to protection scope of the present invention.In addition, the concrete proportioning in following processing parameter, time, temperature etc. are only also exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1
Take 0.3g four thio ammonium molybdate (purchased from Changsha Jing Kang novel material Science and Technology Ltd.), mix with 60mL distilled water, under room temperature, stir 1h, obtain clear solution.Gained solution is transferred in the stainless steel cauldron of contraposition polyphenyl liner of 100mL volume and seals.Reactor is inserted to 220 ℃ of thermal treatment 12h in high temperature oven, after naturally cooling to room temperature, centrifugation reaction mixture, and respectively wash 5 times with 50% ethanolamine solutions and distilled water, obtain MoS
2nanometer sheet.Tem observation result (a) shows resulting MoS in Fig. 1
2present irregular laminated structure.With Image J1.40G software (http://rsb.info.nih.gov/ij/download.html, National Institutes of Health, the U.S.), measure the diameter (at least measuring 50) of nanometer sheet, MoS
2the diameter of lamella is 50 ± 10nm.
Embodiment 2
Take 0.3g four thio ammonium molybdate (purchased from Changsha Jing Kang novel material Science and Technology Ltd.), mix with 30mL distilled water, under room temperature, stir 1h, obtain clear solution.Then, in above-mentioned solution, add 30mLPEG400 (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), continue under room temperature and stir 1h.Gained solution is transferred in the stainless steel cauldron of contraposition polyphenyl liner of 100mL volume and seals.Reactor is inserted to 220 ℃ of thermal treatment 12h in high temperature oven, after naturally cooling to room temperature, centrifugation reaction mixture, and respectively wash 5 times with 50% ethanolamine solutions and distilled water, obtain MoS
2-PEG nanometer sheet.Tem observation result (b in Fig. 1) shows, resulting MoS
2present irregular laminated structure, lamella diameter is 79 ± 15nm.FTIR result (Fig. 2) shows that PEG400 has successfully been connected to MoS
2the surface of nanometer sheet, and the colloidal stability that has effectively improved nanometer sheet is (in Fig. 4 a).
Embodiment 3
Take 0.15g four thio ammonium molybdate (purchased from Changsha Jing Kang novel material Science and Technology Ltd.), mix with 30mL distilled water, under room temperature, stir 1h, obtain clear solution.Then, in above-mentioned solution, add 30mLPEG400 (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), continue under room temperature and stir 1h.Gained solution is transferred in the stainless steel cauldron of contraposition polyphenyl liner of 100mL volume and seals.Reactor is inserted to 220 ℃ of thermal treatment 12h in high temperature oven, after naturally cooling to room temperature, centrifugation reaction mixture, and respectively wash 5 times with 50% ethanolamine solutions and distilled water, obtain MoS
2-PEG nanometer sheet.Tem observation result (c in Fig. 1) shows, resulting MoS
2-PEG presents irregular laminated structure, and lamella diameter is 103 ± 22nm.FTIR result (Fig. 2) shows that PEG400 has successfully been connected to MoS
2the surface of nanometer sheet, and effectively improved the colloidal stability (b in Fig. 4) of nanometer sheet.
Embodiment 4
Take 1.236g Ammonium Molybdate Tetrahydrate and 2.283g thiocarbamide (all purchased from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), mix with 35mL distilled water, under room temperature, stir 1h, obtain clear solution.Gained solution is transferred in the stainless steel cauldron of contraposition polyphenyl liner of 100mL volume and seals.Reactor is inserted to 220 ℃ of thermal treatment 18h in high temperature oven, after naturally cooling to room temperature, centrifugation reaction mixture, and respectively wash 5 times with 50% ethanolamine solutions and distilled water, obtain MoS
2nanometer sheet.Tem observation result (d in Fig. 1) shows, resulting MoS
2present irregular laminated structure, lamella diameter is 195 ± 34nm.
Embodiment 5
Take 1.236g Ammonium Molybdate Tetrahydrate and 2.283g thiocarbamide (all purchased from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), mix with 17.5mL distilled water, under room temperature, stir 1h, obtain clear solution.Then, in above-mentioned solution, add 17.5mLPEG400 (purchased from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), continue under room temperature and stir 1h.Gained solution is transferred in the stainless steel cauldron of contraposition polyphenyl liner of 100mL volume and seals.Reactor is inserted to 220 ℃ of thermal treatment 18h in high temperature oven, after naturally cooling to room temperature, centrifugation reaction mixture, and respectively wash 5 times with 50% ethanolamine solutions and distilled water, obtain MoS
2-PEG nanometer sheet.Tem observation result (e in Fig. 1) shows, resulting MoS
2-PEG presents irregular laminated structure, and lamella diameter is 296 ± 47nm.FTIR result (Fig. 2) shows that PEG400 has successfully been connected to MoS
2the surface of nanometer sheet, and effectively improved the colloidal stability (c in Fig. 4) of nanometer sheet.
Embodiment 6
The nanometer sheet material in different sheets footpath is dispersed in the glass cuvette (12.5mm * 12.5mm * 45mm) that 3mL distilled water is housed, obtains the suspension that Mo concentration is 100ppm, get 3mL distilled water in contrast.With the near-infrared laser of 808nm wavelength, (power density is 0.6W/cm
2) irradiate the cuvette that liquid to be measured is housed, and pass through thermometric software records water temperature situation over time.For the photo and thermal stability of test material, reirradiation sheet footpath is 79 ± 15nm material 10 times, the each temperature change value of irradiating rear water of record;
From Fig. 6 a, can find out, different materials has demonstrated different thermal transition abilities.Sheet footpath is the MoS of 79 ± 15nm
2-PEG nanometer sheet can make 5.5 ° of left and right of distilled water temperature rising of 3mL in 5min, demonstrates best near-infrared laser absorption-thermal transition performance.In addition the MoS that, sheet footpath is 79 ± 15nm
2-PEG nanometer sheet has demonstrated good thermostability.As shown in Figure 6 b, after 10 laser radiation intensification-laser shutdowns cooling experimentation, this material still keeps good photo-thermal transfer capability.
Embodiment 7
The MoS that is 79 ± 15nm by sheet footpath
2-PEG nanometer sheet is scattered in the glass cuvette (12.5mm * 12.5mm * 45mm) that 3mL distilled water is housed, and with the near-infrared laser of 808nm wavelength, (power density is 0.6W/cm
2) irradiate the cuvette that liquid to be measured is housed.Change respectively the concentration of Mo in suspension, and the density of near-infrared laser, by thermometric software records water temperature situation over time;
As Fig. 7 (b), in density, be 0.6W/cm
2near-infrared laser irradiate under, the MoS of high density (Mo concentration is 200ppm)
2-PEG nanometer sheet can be carried out photo-thermal conversion and rising water temperature more effectively.Fig. 7 (c) is under same concentration (concentration of Mo is 100ppm), MoS
2-PEG nanometer sheet (sheet footpath is 79 ± 15nm) suspension water temperature is with the changing conditions of laser intensity.Laser intensity is higher, and energy is larger, and then water temperature rising higher (being respectively 7.77 ℃, 9.38 ℃ and 13.41 ℃), has shown good photo-thermal transfer capability.
Embodiment 8
The MoS that is 79 ± 15nm by sheet footpath
2-PEG nanometer sheet is scattered in the physiological saline suspension that 1.5mL erythrocyte is housed, and changes respectively the concentration of Mo in suspension, and hatches 1h under room temperature;
In Fig. 8, shown in (a), when the Mo of erythrocyte and different concns is hatched after 1h jointly, hemolysis rate, all below 5%, is not observed obvious haemolysis in investigating concentration range.After the blood plasma of the material containing different concns is hatched, in Fig. 8, the PT of experimental group, FIB shown in (b) and APTT, all in normal range, compare considerable change do not occur with blank group.In a word, within experimental concentration scope, material has good blood compatibility, for the follow-up treatment of intravenous injection safely provides assurance.
Embodiment 9
Select 4T1 cell as sample, the MoS that is 79 ± 15nm by CCK-8 method checking sheet footpath
2the biocompatibility of-PEG nanometer sheet and external photo-thermal therapy tumor effect.Concrete steps are as follows: collect logarithmic phase 4T1 cell, with the density of 8000 cells/well, be inoculated in 96 porocyte culture plates, be placed in CO
2in incubator, cultivate after 24h, to the MoS that adds gradient concentration in each hole
2-PEG nanometer sheet suspension is also cultivated 24h.According to CCK-8 test kit specification sheets, in every hole, add 10mLCCK-8 working fluid.Continue to cultivate after 1h, utilize BioTek microplate reader to read the light absorption value at 405nm place, the impact of assay different concns material on the division of 4T1 cell;
External photo-thermal therapy tumor effect evaluation procedure is as follows: collect logarithmic phase 4T1 cell, with the density of 8000 cells/well, be inoculated in 96 porocyte culture plates, be placed in CO
2in incubator, cultivate after 24h, to the MoS that adds gradient concentration in each hole
2-PEG nanometer sheet suspension.Then with wavelength, be 808nm near-infrared laser bundle radiation culture plate, every hole radiation 5min, laser intensity is 1W/cm
2.After continue to be placed in CO
2in incubator, cultivate after 24h, by the surviving rate of 4T1 cell after CCK-8 test kit evaluation laser radiation;
As shown in a in Fig. 9, within the scope of experimental concentration (0-500 μ g/mL), with the sheet footpath MoS that is 79 ± 15nm
2-PEG nanometer sheet is hatched after 24h altogether, and the surviving rate of 4T1 cell is all more than 90%, the MoS that sheet footpath is 79 ± 15nm
2-PEG has good cell compatibility.Through 808nm laser radiation 5min continuation, cultivate after 24h, the surviving rate of 4T1 cell obviously reduces; The concentration of material is higher, more obvious to the inhibition of 4T1 Growth of Cells.When the concentration of Mo is 500ppm, the suppression efficiency of tumour is surpassed to 90%.Because dead cell can be dyed for blueness by trypan blue, therefore adopt Trypan Blue to evaluate qualitatively the antitumous effect of material.As shown in b in Fig. 9, opticmicroscope microscopy result shows that most cells are dyed for blueness, and cell apoptosis, consistent with CCK-8 experimental result, further shows that sheet footpath is the MoS of 79 ± 15nm
2-PEG nanometer sheet has good external tumour photo-thermal therapy effect.
Claims (10)
1. a MoS
2the preparation method of nanometer sheet, is characterized in that, described method comprises:
Take four thio ammonium molybdate as Mo source and S source, or take ammonium molybdate as Mo source and take thiocarbamide as S source, in the mixed solvent of it is water-soluble or water and polyoxyethylene glycol, 200-220 ℃ of thermal treatments, after 12-18 hours, through separated, washing, obtain MoS
2nanometer sheet, wherein controls kind, concentration and/or the solvent for use in Mo source and S source to control described MoS
2the size of nanometer sheet.
2. preparation method according to claim 1, is characterized in that, take four thio ammonium molybdate as Mo source and S source, and the concentration of controlling four thio ammonium molybdate is that 1-6mg/mL be take and made the MoS that sheet footpath is 40-125nm
2nanometer sheet.
3. preparation method according to claim 2, is characterized in that, take water as solvent, take four thio ammonium molybdate as Mo source and S source, the concentration of controlling four thio ammonium molybdate is that 4-6mg/mL be take and made the MoS that sheet footpath is 50 ± 10nm
2nanometer sheet.
4. preparation method according to claim 2, is characterized in that, take the mixed solvent of water and polyoxyethylene glycol as solvent, take four thio ammonium molybdate as Mo source and S source, the concentration of controlling four thio ammonium molybdate is that 4-6mg/mL be take and made the MoS that sheet footpath is 79 ± 15nm
2nanometer sheet.
5. preparation method according to claim 2, is characterized in that, take the mixed solvent of water and polyoxyethylene glycol as solvent, take four thio ammonium molybdate as Mo source and S source, the concentration of controlling four thio ammonium molybdate is that 1-3mg/mL be take and made the MoS that sheet footpath is 79 ± 15nm
2nanometer sheet.
6. preparation method according to claim 1, is characterized in that, take ammonium molybdate as Mo source and take thiocarbamide as S source, and the concentration of controlling ammonium molybdate is 20-50mg/mL, and the concentration of thiocarbamide is that 50-80g/mL be take and made the MoS that sheet footpath is 160-345nm
2nanometer sheet.
7. preparation method according to claim 6, is characterized in that, take water as solvent, take ammonium molybdate as Mo source and take thiocarbamide as S source, make the MoS that sheet footpath is 195 ± 34nm
2nanometer sheet.
8. preparation method according to claim 6, is characterized in that, take the mixed solvent of water and polyoxyethylene glycol as solvent, take ammonium molybdate as Mo source and take thiocarbamide as S source, make the MoS that sheet footpath is 296 ± 47nm
2nanometer sheet.
9. according to the preparation method described in claim 4,5 or 8, it is characterized in that described MoS
2nanometer sheet is connected with PEG molecule.
10. according to the preparation method described in claim 4,5 or 8, it is characterized in that, in described mixed solvent, the volume ratio of water and polyoxyethylene glycol is 1:(0.5-2.5).
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