CN104030360B - A kind of MoS2the controlledly synthesis of nanometer sheet and synchronous surface method of modifying - Google Patents
A kind of MoS2the controlledly synthesis of nanometer sheet and synchronous surface method of modifying Download PDFInfo
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Abstract
The present invention relates to a kind of MoS2The controlledly synthesis of nanometer sheet and synchronous surface method of modifying, described method includes: with four thio ammonium molybdate for Mo source and S source, or with ammonium molybdate for Mo source and with thiourea for S source, it is dissolved in the mixed solvent of water or water and Polyethylene Glycol, after 200 220 DEG C of heat treatments 12 18 hours, separating, washing obtains MoS2Nanometer sheet, wherein controls Mo source and the kind in S source, concentration and/or solvent for use to control described MoS2The size of nanometer sheet.
Description
Technical field
The invention belongs to Bio-Nano-Materials field, be specifically related to a kind of controlledly synthesis and the MoS of synchronous surface modification2The preparation method of nanometer sheet.
Background technology
Cancer is one of dangerous diseases of current threat human health." the 2012 China's tumor registration annual report " display issued according to whole nation tumor Register, China resident is 13% because of the probability of cancer mortality, has 1 people dead because of cancer 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 treatment of cancer.Operative treatment takes local excision's tumor tissues, it will usually patient's body and mind is brought huge wound.Chemotherapy and radiation method is to treat two kinds of Main Means of cancer at present, but both approaches treatment cancer all also exists a series of deficiency.Chemotherapy easily causes the toxic and side effects of each organ of whole body, and tumor can be made to produce multidrug resistance, affects therapeutic effect.Radiotherapy also has the biggest toxic and side effects to biological organs, and range of application has significant limitation.Day by day pursue today of high-quality life people, develop new cancer treatment method, improve the quality of life of patient, extend the life cycle of tumor patient, there is important research and Practical significance undoubtedly.
Light thermal ablation therapy technology, i.e. photo-thermal therapy, being the micro-/noinvasive tumor therapeuticing method of a kind of novelty of rising in recent years, it utilizes optothermal material absorb and near-infrared laser is converted to heat, makes tumor tissues local heating cause tumour ablation dead and then kill tumor cell targetedly.Near infrared light (wave-length coverage: 700-1100nm) has good biological tissue's penetrance, penetrate process light attenuation by absorption little and almost to normal biological tissue not damaged, thus present good application prospect at biomedical sector particularly therapeutic field of tumor.It is to need have the nano material absorbing and being converted into by near infrared light heat that near infrared light plays the premise of diagnosis and treatment effect in vivo.
At present, the optical-thermal conversion material of research report is divided into organic compound/polymer (such as indocyanine green, polypyrrole nano-particle), tungsten oxide nano, nano copper sulfate particle, carbon nanomaterial (such as Graphene) and noble metal nanometer material (such as gold nanorods, the nanometer sheet of palladium) etc..For noble metal nanometer material, it can occur obvious morphology change under near-infrared laser radiation condition, ultimately results in the skew of absworption peak and significantly affects the light thermal property of material.The absorptance of material with carbon element compares relatively low, the shortcoming such as photothermal conversion efficiency is low, limits it and applies further.Transient metal sulfide is (such as MoS2, MoSe2, WS2And WSe2) the important research direction in optothermal material field is become because having the advantage such as low cost, low toxicity.This kind of transient metal sulfide has " class sandwich " structure of stratiform more, is between each metallic atom of same layer and is combined by covalent bond, then combines with more weak Van der Waals force between layer-layer.The construction features of this uniqueness makes they application in the field such as environmental protection, the energy get the attention.But, metal sulfide in the research of biomedical sector also in the starting stage.
As a member of metal sulfide, MoS2Nano 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 strong absorption, MoS2Nanometer sheet but rarely has report as optothermal material for the research of oncotherapy.Chou et al. have studied chemical stripping MoS first2Sheet (ceMoS2) preparation, absorption characteristic near infrared light, and have rated ceMoS under the irradiation of near infrared light at cellular level2Fragmentation effect (Angewandte Chemie, 2013,125:4254-4258.) to cancerous cell.But, this ceMoS2Sheet footpath at about 1um, it is impossible to meet intravenous needs, and then be not suitable for internal tumor tissues being melted.At present, hydrothermal/solvent full-boiled process is synthesis MoS2The main method of nano material.Conventional Mo source mainly includes ammonium molybdate, sodium molybdate, ammonium thiomolybdate, acetic acid molybdenum dimer etc., and S source mainly includes elemental sulfur, Carbon bisulfide, hydrogen sulfide, thiourea etc., the MoS obtained2Pattern mostly be lamellar or tubulose.The MoS of the Hydrothermal Synthesis of document report at present2Sheet footpath many at more than 200nm, its colloidal stability also needs to be investigated.Liu et al. is recently reported (Adv.Mater.2014, DOI:10.1002/adma.201305256) and prepares the sheet footpath MoS at about 200nm by the method for chemical stripping2Nanometer sheet, and the MoS reducing chemical stripping is modified by further PEG2Sheet footpath, finally given the diameter MoS at about 50nm2-PEG nanometer sheet.Due to MoS2Nanometer sheet itself cannot be connected with the Organic substance carbochain such as PEG and realize surface and modify by image-stone ink alkenes material with carbon element like that by the way of " π-pi-conjugated ", therefore the technique that the synthesis having been reported and surface PEG are modified is extremely complex, and cannot realize MoS2Effective control of nanometer sheet pattern.Up to now, this area is not yet developed one and can be synchronized realization to MoS2The method that the controlledly synthesis of nanometer sheet and surface PEG are modified.
Summary of the invention
Cannot synchronize to realize MoS it is contemplated that fill up2The blank that the controlledly synthesis of nanometer sheet and surface PEG are modified, the invention provides a kind of controlledly synthesis and the MoS of synchronous surface modification2Nanometer sheet and preparation method thereof.
The invention provides a kind of MoS2The preparation method of nanometer sheet, described method includes:
With four thio ammonium molybdate for Mo source and S source, or with ammonium molybdate for Mo source and with thiourea for S source, being dissolved in the mixed solvent of water or water and Polyethylene Glycol, after 200 220 DEG C of heat treatments 12 18 hours, separating, washing obtains MoS2Nanometer sheet, wherein controls Mo source and the kind in S source, concentration and/or solvent for use to control described MoS2The size of nanometer sheet.
It is preferred that with four thio ammonium molybdate for Mo source and S source, the concentration controlling four thio ammonium molybdate is the 1-6mg/mL MoS with prepared sheet footpath as 40-125nm2Nanometer sheet.
It is preferred that with water as solvent, with four thio ammonium molybdate for Mo source and S source, control the concentration of four thio ammonium molybdate be 4-6mg/mL be the MoS of 50 ± 10nm with prepared sheet footpath2Nanometer sheet.
It is preferred that with the mixed solvent of water and Polyethylene Glycol as solvent, with four thio ammonium molybdate for Mo source and S source, control the concentration of four thio ammonium molybdate be 4-6mg/mL be the MoS of 79 ± 15nm with prepared sheet footpath2Nanometer sheet.
It is preferred that with the mixed solvent of water and Polyethylene Glycol as solvent, with four thio ammonium molybdate for Mo source and S source, control the concentration of four thio ammonium molybdate be 1-3mg/mL be the MoS of 79 ± 15nm with prepared sheet footpath2Nanometer sheet.
It is preferred that with ammonium molybdate for Mo source and with thiourea for S source, the concentration controlling ammonium molybdate is 20-50mg/mL, and the concentration of thiourea is the 50～80g/mL MoS with prepared sheet footpath as 160-345nm2Nanometer sheet.
It is preferred that with water as solvent, with ammonium molybdate for Mo source and with thiourea for S source, preparing sheet footpath is the MoS of 195 ± 34nm2Nanometer sheet.
It is preferred that with the mixed solvent of water and Polyethylene Glycol as solvent, with ammonium molybdate for Mo source and with thiourea for S source, preparing sheet footpath is the MoS of 296 ± 47nm2Nanometer sheet.
It is preferred that when the solvent selected is added with PEG, described MoS2Nanometer sheet connects PEG molecule.
It is preferred that water is 1:(0.5 2.5 with the volume ratio of Polyethylene Glycol in described mixed solvent).
Beneficial effects of the present invention:
Present invention process is simple, and product is easy to get；The MoS in the different sheet footpaths prepared2(MoS2-PEG) nanometer sheet has good blood compatibility and biocompatibility.The MoS of synthesis2-PEG nanometer sheet can absorb near infrared light and it is converted into heat energy and makes radiation position local heating, kills tumor cell；The colloidal stability of nano material can be strengthened at nano grain surface grafting PEG, improve the biocompatibility of material, reduce the non-specific phagocytosis to nano material of the body reticuloendothelial system, make nano material be enriched in tumor region more, improve the therapeutic effect to tumor；
The present invention is by adding a certain proportion of PEG400 (preferably, distilled water and the volume ratio of PEG400 employed in the present invention are 1:0.5-1:1.5) in hydrothermal/solvent thermal response system, at synthesis MoS2While nanometer sheet, a step realizes MoS2The structure regulating of nanometer sheet and surface PEG are modified.The a small amount of H produced in course of reaction2S gas can be removed by the way of follow-up aqueous ethanolamine cleaning effectively.Therefore, the preparation method of the present invention is simple, yield is high, is suitable for large-scale industrial and produces；
In one embodiment, it is the MoS of 79 ± 15nm by of the present invention footpath2-PEG nanometer sheet is scattered in the NaCl injection of 0.9%, is injected in lotus has the Balb/C nude mouse of 4T1 breast cancer tumour model by tail vein injection mode by 200uL, is 1W/cm by power density after 24 hours2, wavelength be that the near-infrared laser of 808nm irradiates tumor 5 minutes.Experimental result finds, injection sheet footpath is the MoS of 79 ± 15nm2The growth of-PEG nanometer sheet group mouse tumor volume is substantially suppressed.And under equal conditions, only inject the MoS that sheet footpath is 79 ± 15nm2-PEG nanometer sheet not irradiating laser, the NaCl injection parallel laser of injection 0.9% irradiate, and three groups of small mouse tumors of the NaCl injection of only injection 0.9% increase substantially.This test result indicate that of the present invention footpath is the MoS of 79 ± 15nm2-PEG nanometer sheet has good anti-tumor in vivo effect, has potential application prospect in fields such as oncotherapys.
Accompanying drawing explanation
Fig. 1 shows that preparing sheet footpath in embodiments of the present invention is respectively the MoS of 50 ± 10nm2Nanometer sheet (a), the MoS of 79 ± 15nm2-PEG nanometer sheet (b), the MoS of 103 ± 22nm2-PEG nanometer sheet (c), the MoS of 195 ± 34nm2Nanometer sheet (d) and the MoS of 296 ± 47nm2The TEM figure of-PEG nanometer sheet (e) and flake diameter distribution figure thereof；
Fig. 2 shows the MoS in the different sheet footpaths of preparation in embodiments of the present invention2Or MoS2The Fourier transform infrared spectroscopy figure of-PEG nanometer sheet；
Fig. 3 shows the MoS in the different sheet footpaths of preparation in embodiments of the present invention2Or MoS2The UV-visible-near infrared absorption of-PEG nanometer sheet；
Fig. 4 shows that in embodiments of the present invention, sheet footpath is the MoS of 79 ± 15nm (a), 103 ± 22nm (b) and 296 ± 47nm (c)2-PEG nanometer sheet hydration kinetics diameter in normal saline；
Fig. 5 shows the MoS in the different sheet footpaths of preparation in embodiment of the present invention2Or MoS2The X ray diffracting spectrum (a) of-PEG nanometer sheet and x-ray photoelectron spectroscopy spectrogram (b) of Mo and S；
Fig. 6 a shows and uses the MoS in the different sheet footpaths of preparation in embodiment of the present invention2Or MoS2The concentration of Mo prepared by-PEG nanometer sheet is the suspension of 100ppm or distilled water is 0.6W/cm at power2808nm laser emission under water temperature with the change schematic diagram of radiated time；
Fig. 6 b shows and uses the MoS that sheet footpath is 79 ± 15nm of preparation in embodiment of the present invention2The concentration of Mo prepared by-PEG nanometer sheet be the suspension of 100ppm be 0.6W/cm at power2808nm laser emission under water temperature change and radiation number of times relation；
Fig. 7 a shows the MoS that sheet footpath is 79 ± 15nm of preparation in the embodiments of the present invention containing variable concentrations2The UV-visible-near infrared absorption figure of the suspension of-PEG nanometer sheet；
Fig. 7 b shows that in density be 0.6W/cm2Near-infrared laser irradiate under, containing in embodiment of the present invention preparation MoS2The concentration of-PEG nanometer sheet (sheet footpath is 79 ± 15nm) is respectively the situation of change figure of the suspension water temperature of 100ppm and 200ppm；
Fig. 7 c shows containing the MoS of preparation in the embodiment of the present invention of (concentration of Mo is 100ppm) under same concentration2The suspension water temperature of-PEG nanometer sheet (sheet footpath is 79 ± 15nm) is with the situation of change of laser intensity；
Fig. 8 shows that in embodiments of the present invention, sheet footpath is the MoS of 79 ± 15nm2The hemolysis rate of-PEG nanometer sheet and the relation (a) of concentration, and the MoS containing variable concentrations2Prothrombin time (PT), fibrinogen content (FIB) and Activated partial thromboplastin time (APTT) value (b) that the fresh plasma of-PEG nanometer sheet (sheet footpath 79 ± 15nm) measures after hatching 5min；
Fig. 9 shows and the MoS containing variable concentrations Mo2-PEG nanometer sheet (sheet footpath is 79 ± 15nm) suspension hatch 24h altogether after the survival rate of mouse mastopathy cell (4T1 cell) and photo-thermal therapy effect (cell is 1.0W/cm through power2808nm laser emission 5min) the Trypan Blue result figure (dead cell can be blueness by trypan blue dye) of cell after (a) and laser treatment.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment are merely to illustrate the present invention below in conjunction with accompanying drawing and following embodiment, and the unrestricted present invention.
The present invention relates to a kind of MoS2The controlledly synthesis of nanometer sheet and synchronous surface method of modifying, method can be one of:
(1) four thio ammonium molybdate is dissolved in distilled water, the stainless steel cauldron of the polyparaphenylene liner that after stirring, gained solution is transferred to 100mL volume seals reaction a period of time, products therefrom is cleaned for several times with aqueous ethanolamine and distilled water respectively, obtains the MoS that sheet footpath is 50 ± 10nm2Nanometer sheet；
(2) four thio ammonium molybdate is dissolved in the mixed solution of distilled water and Polyethylene Glycol, the stainless steel cauldron of the polyparaphenylene liner that after stirring, gained solution is transferred to 100mL volume seals reaction a period of time, products therefrom is cleaned for several times with aqueous ethanolamine and distilled water respectively, obtains the MoS that sheet footpath is 79 ± 15nm2-PEG nanometer sheet；
(3) other conditions are constant, only change the concentration of four thio ammonium molybdate in step (2), sheet footpath is the MoS of 103 ± 22nm2-PEG nanometer sheet；
(4) ammonium molybdate and thiourea are dissolved in distilled water, the stainless steel cauldron of the polyparaphenylene liner that after stirring, gained solution is transferred to 100mL volume seals reaction a period of time, products therefrom is cleaned for several times with aqueous ethanolamine and distilled water respectively, obtains the MoS that sheet footpath is 195 ± 34nm2Nanometer sheet；
(5) other conditions are constant, only by changing the component of solvent in step (4), obtain the MoS that sheet footpath is 296 ± 47nm2-PEG nanometer sheet；
Present invention process is simple, and product is easy to get；The MoS of preparation2-PEG nanometer sheet has good blood compatibility, biocompatibility and extracorporeal anti-tumor effect, it is desirable to can be used for Hyperthermia for Cancer Treatment material for development further provides new approaches.
Described a kind of MoS2In the controlledly synthesis of nanometer sheet and synchronous surface method of modifying (1), the concentration of described four thio ammonium molybdate is 4-6mg/mL.
Described a kind of MoS2In the controlledly synthesis of nanometer sheet and synchronous surface method of modifying (2), the concentration of described four thio ammonium molybdate be the volume ratio of 4-6mg/mL, distilled water and PEG be 1:0.5-1:2.5.
Described a kind of MoS2In the controlledly synthesis of nanometer sheet and synchronous surface method of modifying (2), the molecular weight of described PEG is 200,300 or 400 dalton.
Described a kind of MoS2In the controlledly synthesis of nanometer sheet and synchronous surface method of modifying (3), the concentration of described four thio ammonium molybdate is 1-4mg/mL.
Described a kind of MoS2In the controlledly synthesis of nanometer sheet and synchronous surface method of modifying (4), the concentration of described ammonium molybdate is 20-50mg/mL, and the concentration of thiourea is 50-80mg/mL.
Described a kind of MoS2In the controlledly synthesis of nanometer sheet and synchronous surface method of modifying (5), it is 1:0.5-1:2.5 that described group of solvents becomes the volume ratio of the mixed solution of distilled water and PEG, distilled water and PEG400.
Described a kind of MoS2In the controlledly synthesis of nanometer sheet and synchronous surface method of modifying method (1)-(5), described mixing time is 30-90 minute, and in politef autoclave, reaction temperature is 200-220 DEG C, and the response time is 12-18 hour.The concentration of aqueous ethanolamine is 40-60% (volume ratio), and the wash number of aqueous ethanolamine and distilled water is 3-5 time.
This patent regulates and controls MoS by the straightforward procedure adding PEG in solvent thermal solvent2The pattern of nanometer sheet, and step realization is to MoS2Surface PEG modify.Study discovery through inventor, by the PEG of interpolation certain volume in solvent thermal reaction system, MoS can be prepared by solvent thermal reaction2-PEG nanometer sheet, by changing Mo and the S source category in solvent thermal reaction system and concentration, it is possible to achieve to MoS2The controlledly synthesis of-PEG nanometer sheet.
Present invention process is simple, and product is easy to get；The MoS in the different sheet footpaths prepared2(MoS2-PEG) nanometer sheet has good blood compatibility and biocompatibility.The MoS of synthesis2-PEG nanometer sheet can absorb near infrared light and it is converted into heat energy and makes radiation position local heating, kills tumor cell；The colloidal stability of nano material can be strengthened at nano grain surface grafting PEG, improve the biocompatibility of material, reduce the non-specific phagocytosis to nano material of the body reticuloendothelial system, make nano material be enriched in tumor region more, improve the therapeutic effect to tumor.
The present invention is by adding a certain proportion of PEG400 (preferably, distilled water and the volume ratio of PEG400 employed in the present invention are 1:0.5-1:1.5) in hydrothermal/solvent thermal response system, at synthesis MoS2While nanometer sheet, a step realizes MoS2The structure regulating of nanometer sheet and surface PEG are modified.The a small amount of H produced in course of reaction2S gas can be removed by the way of follow-up aqueous ethanolamine cleaning effectively.Therefore, the preparation method of the present invention is simple, yield is high, is suitable for large-scale industrial and produces.
In one embodiment, it is the MoS of 79 ± 15nm by of the present invention footpath2-PEG nanometer sheet is scattered in the NaCl injection of 0.9%, is injected in lotus has the Balb/C nude mouse of 4T1 breast cancer tumour model by tail vein injection mode by 200uL, is 1W/cm by power density after 24 hours2, wavelength be that the near-infrared laser of 808nm irradiates tumor 5 minutes.Experimental result finds, injection sheet footpath is the MoS of 79 ± 15nm2The growth of-PEG nanometer sheet group mouse tumor volume is substantially suppressed, and only injects the MoS that sheet footpath is 79 ± 15nm under equal conditions2-PEG nanometer sheet not irradiating laser, the NaCl injection parallel laser of injection 0.9% irradiate, and three groups of small mouse tumors of the NaCl injection of only injection 0.9% increase substantially.This test result indicate that of the present invention footpath is the MoS of 79 ± 15nm2-PEG nanometer sheet has good anti-tumor in vivo effect, has potential application prospect in fields such as oncotherapys.
Fig. 1 shows that in embodiment of the present invention, the sheet footpath of preparation is respectively the MoS of (a) 50 ± 10nm2Nanometer sheet, the MoS of (b) 79 ± 15nm2-PEG nanometer sheet, the MoS of (c) 103 ± 22nm2-PEG nanometer sheet, the MoS of (d) 195 ± 34nm2Nanometer sheet and the MoS of (e) 296 ± 47nm2The TEM figure of-PEG nanometer sheet and flake diameter distribution figure thereof；
Fig. 2 shows the MoS in the different sheet footpaths of preparation in embodiment of the present invention2Or MoS2The Fourier transform infrared spectroscopy figure of-PEG nanometer sheet.It can be seen that except the MoS that sheet footpath is 50 ± 10nm and 195 ± 34nm2Outside nanometer sheet, other respectively organize material at 1060cm-1Place all shows the vibration absorption peak of-C-O-, illustrates that PEG400 strand is the most successfully connected to MoS2The surface of nanometer sheet；
Fig. 3 shows the MoS in the different sheet footpaths of preparation in embodiment of the present invention2Or MoS2The UV-visible-near infrared absorption (concentration of Mo is 40ppm) of-PEG nanometer sheet suspension.As seen from Figure 3, when the concentration of Mo is identical, except sheet footpath is the MoS of 195 ± 34nm2Outside sheet suspension, the suspension of other sheet footpath nanometer sheet materials all can absorb the near-infrared laser that wavelength is 808nm of some strength.It is contemplated that this part near-infrared laser that above-mentioned different materials absorbs translates into heat, thus possesses near-infrared absorption-thermal transition ability；
Fig. 4 shows the MoS that sheet footpath is 79 ± 15nm (a), 103 ± 22nm (b) and 296 ± 47nm (c) of preparation in embodiment of the present invention2-PEG nanometer sheet hydration kinetics diameter in normal saline.It is scattered in normal saline after 24h, above-mentioned three kinds of MoS2There is not significantly change in the hydration kinetics diameter of-PEG nanometer sheet, it was demonstrated that material has good colloidal stability, for laying a good foundation in their photothermal deformation of live body assessment of levels, killing tumor ability further；
Fig. 5 shows the MoS in the different sheet footpaths of preparation in embodiment of the present invention2Or MoS2(a) X ray diffracting spectrum of-PEG nanometer sheet and the x-ray photoelectron spectroscopy spectrogram of (b) Mo and S.Such as a in Fig. 5, the X ray diffracting spectrum of the material of different-diameter and MoS2Standard diagram (JCPD 73-1508) each crystal plane is the most identical.Except the MoS that sheet footpath is 195 ± 34nm, 50 ± 10nm2Outside nanometer sheet, other are respectively organized material and occur in that a new diffraction maximum between 2 θ=7.5-10 °, it may be possible to because part PEG400 segment is embedded into MoS2Lamella in caused.Being analyzed composition and the atomic valence of material surface element by x-ray photoelectron spectroscopy further, the corresponding relation of absworption peak and Mo and S atom electron orbit is as shown in b in Fig. 5.Documents understands the valence state of Mo and S in each product and is Mo4+And S2-.After PEG strand introduces, Mo3/2d, Mo5/2d, the combination of S1/2p, S3/2p track can all reduce.Being possibly due to after PEG is introduced to solvent thermal reaction system, the product of gained is unstable MoS2-PEG is inorganic/organic hybrid system；
Fig. 6 (a) be the concentration of Mo be 100ppm, suspension and the distilled water of different sheet footpaths nanometer sheet material are 0.6W/cm at power2808nm laser emission under water temperature with the change schematic diagram of radiated time；Fig. 6 (b) shows the MoS that sheet footpath is 79 ± 15nm2The suspension of-PEG nanometer sheet is 0.6W/cm at power2808nm laser emission under water temperature change and radiation number of times relation.From Fig. 6 a it can be seen that different materials shows different thermal transition abilities.Sheet footpath is the MoS of 79 ± 15nm2-PEG nanometer sheet can make the distilled water temperature of 3mL raise about 5.5 ° in 5min, demonstrates optimal near-infrared laser absorption-thermal transition performance.Additionally, sheet footpath is the MoS of 79 ± 15nm2-PEG nanometer sheet shows good heat stability.As shown in Figure 6 b, after 10 laser irradiate intensification-laser shutdown cooling experimentation, this material still keeps good photothermal deformation ability.Therefore the present invention chooses the MoS that sheet footpath is 79 ± 15nm2-PEG nanometer sheet is for follow-up photo-thermal therapy tumor research；
Fig. 7 (a) is the MoS that sheet footpath is 79 ± 15nm of variable concentrations2The UV-visible-near infrared absorption figure of-PEG nanometer sheet.At very low concentrations, MoS2-PEG nanometer sheet still can absorb the near-infrared laser of a length of 808nm of subwave.Form with heat is discharged by this fraction of laser light absorbed, and then can impart the light thermal property of material own.Fig. 7 (b) is for being 0.6W/cm in density2Near-infrared laser irradiate under, concentration is respectively the MoS of 100ppm and 200ppm2The situation of change of-PEG nanometer sheet (sheet footpath is 79 ± 15nm) suspension water temperature.It is obvious that the MoS of high concentration2-PEG nanometer sheet more efficiently can carry out photothermal deformation and raise water temperature.Fig. 7 (c) is under same concentration (concentration of Mo is 100ppm), MoS2-PEG nanometer sheet (sheet footpath is 79 ± 15nm) suspension water temperature is with the situation of change of laser intensity.Laser intensity is the highest, and energy is the biggest, and then water temperature raises the highest (respectively 7.77 DEG C, 9.38 DEG C and 13.41 DEG C), shows good photothermal deformation ability；
In Fig. 8, (a) shows the MoS that sheet footpath is 79 ± 15nm2The hemolysis rate of-PEG nanometer sheet and the relation of concentration；B () shows the MoS containing variable concentrations2Prothrombin time (PT), fibrinogen content (FIB) and Activated partial thromboplastin time (APTT) value that the fresh plasma of-PEG nanometer sheet (sheet footpath 79 ± 15nm) measures after hatching 5min.As shown in (a) in Fig. 8, after the Mo of erythrocyte Yu variable concentrations hatches 1h jointly, hemolysis rate, all below 5%, does not i.e. observe obvious haemolysis in investigating concentration range.After the material of variable concentrations and blood plasma jointly being hatched, all within normal range, there is not significant change in PT, FIB and APTT of experimental group compared with blank group.In a word, within the scope of experimental concentration, material has good blood compatibility, provides guarantee for Subsequent secure ground intravenous medical treatment；
In Fig. 9, a shows the MoS with variable concentrations2-PEG nanometer sheet (sheet footpath is 79 ± 15nm) suspension hatch 24h altogether after the survival rate of mouse mastopathy cell (4T1 cell) and photo-thermal therapy effect (cell is 1.0W/cm through power2808nm laser emission 5min).The evaluation means of cell survival rate is Cell counting Kit (CCK-8 test kit) counting method.In the range of experimental concentration (0-500 μ g/mL), in the case of not applying the near-infrared laser radiation of 808nm wavelength, the survival rate of 4T1 cell is not affected by concentration, and survival rate is all more than 90%, i.e. sheet footpath is the MoS of 79 ± 15nm2-PEG has good cell compatibility.And through 808nm laser emission 5min, and continue to cultivate after 24h, the survival rate of 4T1 cell substantially reduces；The concentration of material is the highest, and the suppression to the growth of 4T1 cell is the most obvious.When the concentration of Mo is 500ppm, the suppression efficiency of tumor is alreadyd more than 90%.The Trypan Blue result (dead cell can be blueness by trypan blue dye) of cell after b is laser treatment in Fig. 9, optical microscope microscopy result shows overwhelming majority cell apoptosis, further demonstrates that the MoS that sheet footpath is 79 ± 15nm2-PEG nanometer sheet has good Vitro Tumor photo-thermal therapy effect.
List some exemplary embodiments further below so that the present invention is better described.It should be understood that; the above-mentioned embodiment that the present invention describes in detail; and following example are merely to illustrate the present invention rather than limit the scope of the present invention, some nonessential improvement and adjustment that those skilled in the art makes according to the foregoing of the present invention belong to protection scope of the present invention.It addition, concrete proportioning in following technological parameter, time, temperature etc. are the most only exemplary, those skilled in the art can select suitably value in the range of above-mentioned restriction.
Embodiment 1
Weigh 0.3g four thio ammonium molybdate (purchased from Changsha Jing Kang new material Science and Technology Ltd.), mix with 60mL distilled water, stir 1h under room temperature, obtain clear transparent solutions.The stainless steel cauldron of the polyparaphenylene liner that gained solution is transferred to 100mL volume seals.Reactor is inserted 220 DEG C of heat treatment 12h in high temperature oven, after room temperature, centrifugation reactant mixture, and the ethanolamine solutions and distilled water with 50% respectively washs 5 times, obtains MoS2Nanometer sheet.Tem observation result (a in Fig. 1) shows, obtained MoS2Present irregular lamellar structure.The diameter (at least measuring 50) of nanometer sheet, MoS is measured with Image J 1.40G software (http://rsb.info.nih.gov/ij/download.html, National Institutes of Health, the U.S.)2A diameter of 50 ± 10nm of lamella.
Embodiment 2
Weigh 0.3g four thio ammonium molybdate (purchased from Changsha Jing Kang new material Science and Technology Ltd.), mix with 30mL distilled water, stir 1h under room temperature, obtain clear transparent solutions.Then, in above-mentioned solution, add 30mLPEG400 (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), continue to stir 1h at room temperature.The stainless steel cauldron of the polyparaphenylene liner that gained solution is transferred to 100mL volume seals.Reactor is inserted 220 DEG C of heat treatment 12h in high temperature oven, after room temperature, centrifugation reactant mixture, and the ethanolamine solutions and distilled water with 50% respectively washs 5 times, obtains MoS2-PEG nanometer sheet.Tem observation result (b in Fig. 1) shows, obtained MoS2Present irregular lamellar structure, a diameter of 79 ± 15nm of lamella.FTIR result (Fig. 2) shows that PEG400 has successfully been connected to MoS2The surface of nanometer sheet, and effectively improve the colloidal stability (a in Fig. 4) of nanometer sheet.
Embodiment 3
Weigh 0.15g four thio ammonium molybdate (purchased from Changsha Jing Kang new material Science and Technology Ltd.), mix with 30mL distilled water, stir 1h under room temperature, obtain clear transparent solutions.Then, in above-mentioned solution, add 30mLPEG400 (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), continue to stir 1h at room temperature.The stainless steel cauldron of the polyparaphenylene liner that gained solution is transferred to 100mL volume seals.Reactor is inserted 220 DEG C of heat treatment 12h in high temperature oven, after room temperature, centrifugation reactant mixture, and the ethanolamine solutions and distilled water with 50% respectively washs 5 times, obtains MoS2-PEG nanometer sheet.Tem observation result (c in Fig. 1) shows, obtained MoS2-PEG presents irregular lamellar structure, a diameter of 103 ± 22nm of lamella.FTIR result (Fig. 2) shows that PEG400 has successfully been connected to MoS2The surface of nanometer sheet, and effectively improve the colloidal stability (b in Fig. 4) of nanometer sheet.
Embodiment 4
Weigh 1.236g Ammonium Molybdate Tetrahydrate and 2.283g thiourea (being purchased from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), mix with 35mL distilled water, stir 1h under room temperature, obtain clear transparent solutions.The stainless steel cauldron of the polyparaphenylene liner that gained solution is transferred to 100mL volume seals.Reactor is inserted 220 DEG C of heat treatment 18h in high temperature oven, after room temperature, centrifugation reactant mixture, and the ethanolamine solutions and distilled water with 50% respectively washs 5 times, obtains MoS2Nanometer sheet.Tem observation result (d in Fig. 1) shows, obtained MoS2Present irregular lamellar structure, a diameter of 195 ± 34nm of lamella.
Embodiment 5
Weigh 1.236g Ammonium Molybdate Tetrahydrate and 2.283g thiourea (being purchased from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), mix with 17.5mL distilled water, stir 1h under room temperature, obtain clear transparent solutions.Then, in above-mentioned solution, add 17.5mLPEG400 (purchased from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), continue to stir 1h at room temperature.The stainless steel cauldron of the polyparaphenylene liner that gained solution is transferred to 100mL volume seals.Reactor is inserted 220 DEG C of heat treatment 18h in high temperature oven, after room temperature, centrifugation reactant mixture, and the ethanolamine solutions and distilled water with 50% respectively washs 5 times, obtains MoS2-PEG nanometer sheet.Tem observation result (e in Fig. 1) shows, obtained MoS2-PEG presents irregular lamellar structure, a diameter of 296 ± 47nm of lamella.FTIR result (Fig. 2) shows that PEG400 has successfully been connected to MoS2The surface of nanometer sheet, and effectively improve the colloidal stability (c in Fig. 4) of nanometer sheet.
Embodiment 6
The nanometer sheet material in different sheet footpaths is dispersed in the glass cuvette (12.5mm × 12.5mm × 45mm) equipped with 3mL distilled water, obtains the suspension that Mo concentration is 100ppm, take 3mL distilled water as comparison.With the near-infrared laser of 808nm wavelength, (power density is 0.6W/cm2) irradiate the cuvette equipped with liquid to be measured, and by thermometric software records water temperature situation over time.For detecting the photo and thermal stability of material, reirradiation sheet footpath is 79 ± 15nm material 10 times, the temperature change value of water after record irradiation every time；
From Fig. 6 a it can be seen that different materials shows different thermal transition abilities.Sheet footpath is the MoS of 79 ± 15nm2-PEG nanometer sheet can make the distilled water temperature of 3mL raise about 5.5 ° in 5min, demonstrates optimal near-infrared laser absorption-thermal transition performance.Additionally, sheet footpath is the MoS of 79 ± 15nm2-PEG nanometer sheet shows good heat stability.As shown in Figure 6 b, after 10 laser irradiate intensification-laser shutdown cooling experimentation, this material still keeps good photothermal deformation ability.
Embodiment 7
It is the MoS of 79 ± 15nm by sheet footpath2-PEG nanometer sheet is scattered in the glass cuvette (12.5mm × 12.5mm × 45mm) equipped with 3mL distilled water, and with the near-infrared laser of 808nm wavelength, (power density is 0.6W/cm2) irradiate the cuvette equipped with liquid to be measured.Change the concentration of Mo in suspension, and the density of near-infrared laser respectively, by thermometric software records water temperature situation over time；
Such as Fig. 7 (b), it is 0.6W/cm in density2Near-infrared laser irradiate under, the MoS of high concentration (Mo concentration is 200ppm)2-PEG nanometer sheet more efficiently can carry out photothermal deformation and raise water temperature.Fig. 7 (c) is under same concentration (concentration of Mo is 100ppm), MoS2-PEG nanometer sheet (sheet footpath is 79 ± 15nm) suspension water temperature is with the situation of change of laser intensity.Laser intensity is the highest, and energy is the biggest, and then water temperature raises the highest (respectively 7.77 DEG C, 9.38 DEG C and 13.41 DEG C), shows good photothermal deformation ability.
Embodiment 8
It is the MoS of 79 ± 15nm by sheet footpath2-PEG nanometer sheet is scattered in equipped with in the normal saline suspension of 1.5mL erythrocyte, changes the concentration of Mo in suspension respectively, and hatches 1h at room temperature；
In Fig. 8 shown in (a), after the Mo of erythrocyte Yu variable concentrations hatches 1h jointly, hemolysis rate, all below 5%, does not i.e. observe obvious haemolysis in investigating concentration range.After being hatched by the blood plasma of the material containing variable concentrations, in Fig. 8, PT, FIB and APTT of experimental group shown in (b) are all within normal range, and significant change does not occur compared with blank group.In a word, within the scope of experimental concentration, material has good blood compatibility, provides guarantee for Subsequent secure ground intravenous medical treatment.
Embodiment 9
Select 4T1 cell as sample, be the MoS of 79 ± 15nm by CCK-8 method checking sheet footpath2The biocompatibility of-PEG nanometer sheet and external photo-thermal therapy tumor effect.Specifically comprise the following steps that collection logarithmic (log) phase 4T1 cell, be inoculated in 96 porocyte culture plates with the density of 8000 cells/well, be placed in CO2After incubator cultivates 24h, in each hole, add the MoS of gradient concentration2-PEG nanometer sheet suspension also cultivates 24h.According to CCK-8 test kit description, in every hole, add 10mL CCK-8 working solution.After continuing to cultivate 1h, BioTek microplate reader is utilized to read the light absorption value at 405nm, the impact on the division of 4T1 cell of the assay variable concentrations material；
External photo-thermal therapy tumor effect evaluation procedure is as follows: collects logarithmic (log) phase 4T1 cell, is inoculated in 96 porocyte culture plates with the density of 8000 cells/well, is placed in CO2After incubator cultivates 24h, in each hole, add the MoS of gradient concentration2-PEG nanometer sheet suspension.Then with wavelength be 808nm near-infrared laser bundle radiate culture plate, every hole radiation 5min, laser intensity is 1W/cm2.After continue to be placed in CO2After incubator cultivates 24h, by the survival rate of 4T1 cell after the evaluation laser emission of CCK-8 test kit；
As shown in a in Fig. 9, in the range of experimental concentration (0-500 μ g/mL), it is the MoS of 79 ± 15nm with sheet footpath2After-PEG nanometer sheet hatches 24h altogether, the survival rate of 4T1 cell is all more than 90%, i.e. sheet footpath is the MoS of 79 ± 15nm2-PEG has good cell compatibility.Through 808nm laser emission 5min and continue to cultivate after 24h, the survival rate of 4T1 cell substantially reduces；The concentration of material is the highest, and the suppression to the growth of 4T1 cell is the most obvious.When the concentration of Mo is 500ppm, the suppression efficiency of tumor is alreadyd more than 90%.Owing to dead cell can be blueness by trypan blue dye, therefore Trypan Blue is used to have rated the antitumous effect of material qualitatively.As shown in b in Fig. 9, optical microscope microscopy result shows that overwhelming majority cell is contaminated for blueness, i.e. cell apoptosis, consistent with CCK-8 experimental result, further demonstrates that the MoS that sheet footpath is 79 ± 15nm2-PEG nanometer sheet has good Vitro Tumor photo-thermal therapy effect.
Claims (7)
1. a MoS2The preparation method of nanometer sheet, it is characterised in that described method includes:
With four thio ammonium molybdate for Mo source and S source, or with ammonium molybdate for Mo source and with thiourea for S source, being dissolved in the mixed solvent of water or water and Polyethylene Glycol, after 200 220 DEG C of heat treatments 12 18 hours, separating, washing obtains MoS2Nanometer sheet, wherein controls Mo source and the kind in S source, concentration and/or solvent for use to control described MoS2The size of nanometer sheet, with four thio ammonium molybdate for Mo source and S source, the concentration controlling four thio ammonium molybdate is the 1-6mg/mL MoS with prepared sheet footpath as 40-125nm2Nanometer sheet, or, with ammonium molybdate for Mo source and with thiourea for S source, the concentration controlling ammonium molybdate is 20-50mg/mL, and the concentration of thiourea is the 50-80mg/mL MoS with prepared sheet footpath as 160-345nm2Nanometer sheet.
Preparation method the most according to claim 1, it is characterised in that with water as solvent, with four thio ammonium molybdate for Mo source and S source, control four thio ammonium molybdate concentration be 4-6mg/mL be the MoS of 50 ± 10nm with prepared sheet footpath2Nanometer sheet.
Preparation method the most according to claim 1, it is characterised in that with the mixed solvent of water and Polyethylene Glycol as solvent, with four thio ammonium molybdate for Mo source and S source, control the concentration of four thio ammonium molybdate be 4-6mg/mL be the MoS of 79 ± 15nm with prepared sheet footpath2Nanometer sheet.
Preparation method the most according to claim 1, it is characterised in that with water as solvent, with ammonium molybdate for Mo source and with thiourea for S source, preparing sheet footpath is the MoS of 195 ± 34nm2Nanometer sheet.
Preparation method the most according to claim 1, it is characterised in that with the mixed solvent of water and Polyethylene Glycol as solvent, with ammonium molybdate for Mo source and with thiourea for S source, preparing sheet footpath is the MoS of 296 ± 47nm2Nanometer sheet.
6. according to the preparation method described in claim 3 or 5, it is characterised in that described MoS2Nanometer sheet connects PEG molecule.
7. according to the preparation method described in claim 3 or 5, it is characterised in that in described mixed solvent, water is 1:(0.5 2.5 with the volume ratio of Polyethylene Glycol).
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