CN108545769A - A kind of SnS nanocrystals and its preparation method and application - Google Patents
A kind of SnS nanocrystals and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of SnS nanocrystals, which has prismatic dodecahedron structure.The invention also discloses the preparation method of the above-mentioned SnS nanocrystals with prismatic dodecahedron structure and the applications in preparing cancer cell photo-thermal therapy material.Preparation method of the present invention can prepare the SnS nanocrystals with prismatic dodecahedron structure, and preparation process is simple, at low cost, can be suitable for industrialization large-scale production；SnS nanocrystals with prismatic dodecahedron structure can be applied to the material for preparing cancer cell photo-thermal therapy with good photo-thermal effect and biocompatibility and low cytotoxicity.
Description
Technical field
The present invention relates to a kind of SnS nanocrystals, further relate to the preparation method of above-mentioned SnS nanocrystals and its are used to prepare
Application in cancer cell photo-thermal therapy material, belongs to technical field of nano material.
Background technology
SnS has honest and clean due to having Sn and S reserves abundant on stronger extinction coefficient and the earth near infrared region
Valence, efficient, nontoxic three big feature, become the preferred material of cancer cell photo-thermal therapy.
It is one of most important study frontier in material science to prepare ultra-thin semiconductor SnS nanometer sheets using solwution method,
A large amount of research has been carried out to this both at home and abroad.The method used at present is mostly oil phase method, and oil phase method needs are used many toxic
Organic solvent.Hydro-thermal method is applied to synthesize a variety of inorganic semiconductor nanometer materials as a kind of using water as the method for reaction medium
Material, so far, many SnS Nano/microns crystal with special appearance structure have all been synthesized by domestic and international scientist
Come, but still without document about the report with granatohedron SnS nanocrystals.
Invention content
Goal of the invention：Technical problem to be solved by the invention is to provide a kind of SnS nanocrystals, the SnS nanocrystals
With prismatic dodecahedron structure.
The present invention also technical problems to be solved are to provide the preparation method of above-mentioned SnS nanocrystals, the preparation method energy
The SnS nanocrystals with prismatic dodecahedron structure are enough prepared, and preparation process is simple, at low cost, work can be suitable for
Industryization mass produces.
The last technical problems to be solved of the present invention are to provide above-mentioned SnS nanocrystals and are used to prepare cancer cell photo-thermal therapy
Application in material.
In order to solve the above technical problems, the technology used in the present invention means are：
A kind of SnS nanocrystals, the SnS nanocrystals have prismatic dodecahedron structure.
The preparation method of above-mentioned SnS nanocrystals, includes the following steps：
Step 1, the desired amount of stanniferous presoma, sulfur-bearing presoma and surfactant is soluble in water, after mixing,
100~120min, preferably 110min are reacted at 180~220 DEG C；
Step 2, collecting reaction product can be obtained the SnS crystal with prismatic dodecahedron structure after washing.
Wherein, in step 1, the stanniferous presoma is at least one of dichloro stannous, butter of tin or stannous sulfate,
It is preferred that stannous chloride.
Wherein, in step 1, the sulfur-bearing presoma is thiocarbamide, thioacetamide, vulcanized sodium, L-cysteine or reduction
At least one of type glutathione, preferably L-cysteine.
Wherein, in step 1, the surfactant is polyvinylpyrrolidone.
Wherein, the molecular weight of the polyvinylpyrrolidone is 1300000.
Wherein, in step 1, the mixing molar ratio of the stanniferous presoma and sulfur-bearing presoma is 1：1~12, preferably 1:1；
The mixing molar ratio of the stanniferous precursor and surfactant is 1：0.1~1.2, preferably 1:0.4.
Application of the above-mentioned SnS nanocrystals in preparing cancer cell photo-thermal therapy material.
Compared with the prior art, technical solution of the present invention have the advantage that for：
Preparation method of the present invention can prepare the SnS nanocrystals with prismatic dodecahedron structure, and preparation process
Simply, at low cost, industrialization large-scale production can be suitable for；SnS nanocrystals with prismatic dodecahedron structure have
Good photo-thermal effect and biocompatibility and low cytotoxicity, therefore can be applied to and prepare cancer cell photo-thermal
The material for the treatment of.
Description of the drawings
Fig. 1 is the stereoscan photograph (scale for the prismatic dodecahedron SnS nanocrystals that in the present invention prepared by embodiment 1
Length is 0.5 μm)；
Fig. 2 is the stereoscan photograph (scale for the prismatic dodecahedron SnS nanocrystals that in the present invention prepared by embodiment 1
Length is 0.2 μm)；
Fig. 3 is that the transmission electron microscope for the low magnifying power of prismatic dodecahedron SnS nanocrystals that in the present invention prepared by embodiment 1 shines
Piece；
Fig. 4 is that the high resolution TEM for the prismatic dodecahedron SnS nanocrystals that in the present invention prepared by embodiment 1 shines
Piece；
Fig. 5 is the scanning transmission electron microscope photo for the prismatic dodecahedron SnS nanocrystals that in the present invention prepared by embodiment 1；
Fig. 6 is Sn, the high-resolution X-ray photoelectron spectroscopy of 3d；
Fig. 7 is the high-resolution X-ray photoelectricity for the prismatic dodecahedron SnS nanocrystals that in the present invention prepared by embodiment 1
Sub- power spectrum；
Fig. 8 is the XRD spectrum for the prismatic dodecahedron SnS nanocrystals that in the present invention prepared by embodiment 1；
Fig. 9 is the prismatic dodecahedron SnS nanocrystals that in the present invention prepared by embodiment 1 and prismatic prepared by embodiment 2
The ultraviolet-visible light of dodecahedron SnS nanocrystals-near infrared spectrum comparison；
Ultraviolet-visible light-near infrared lights of the RD SnS NC that in Figure 10 present invention prepared by embodiment 1 in various concentration
Spectrum；
Figure 11 is the pass of RD SnS NC concentration and absorbance under the laser of 785nm that in the present invention prepared by embodiment 1
System；
Figure 12 is under the laser irradiation of 785nm, and the photo-thermal of the RD SnS NCs water slurries of pure water and various concentration adds
Heating curve；
Figure 13 is the light of the RD SnS NCs water slurries of pure water and various concentration after the laser of 785nm irradiates 10min
According to image；
Figure 14 is 785nm laser irradiation RD SnS NCs water slurries (0.5mgmL-1) 10min then natural coolings
Heating curve；
Figure 15 is the heat balance time constant of the hot-cast socket of 785nm laser irradiation RD SnS NCs water slurries；
Figure 16 is 785nm laser irradiation RD SnS NCs water slurries (0.5mgmL-1) and then natural cooling, cycle five
The laser power of secondary heating curve, 785nm is 0.8Wcm-2；
RD SnS NCs when Figure 17 is without 785nm laser irradiations are to the cytotoxicities of HeLa and 3T3 cells；
Figure 18 is the 0.3mgmL after the 785nm laser irradiation cultures of different capacity density-1RD SnS NCs suspend
Cell survival rate of the liquid to HeLa；
Figure 19 is 0.3mgmL-1The Calcein AM/PI of RD SnS NCs suspension carry out confocal celling imagings；
Figure 20 is in 25 μ L PBS solutions of HeLa cell tumor-bearing mices intratumor injection and RD SNS NCS water slurries
(2mg·mL-1) after 2 hours, (1Wcm under 785nm laser irradiations-2) thermal-induced imagery；
Figure 21 is the temperature variation curve of 785nm laser irradiations mouse tumor after 6 minutes；
Figure 22 uses PBS, the mouse of RD SnS NCs, PBS+ illumination and RD SnS NCs+ photo-irradiation treatments relatively swollen respectively
The variation of knurl product；
Figure 23 is the mouse weight for using PBS, RD SnS NCs, PBS+ illumination and RD SnS NCs+ photo-irradiation treatments respectively
Variation；
Figure 24 is for the representative photo (top) of 14 days tumor-bearing mices after different disposal and 1 day after different disposal
Mice tumor sections image (lower section)；
Figure 25 injects 25 μ L PBS (pH=7.4,10mM) or RD SNS under no 785nm laser irradiations, from mouse peritoneal
NCS water slurries (2mgmL-1) 1 day hematoxylin eosin staining histotomy, the amplification factor of all pictures is 200
Times；
Figure 26 injects 25 μ L PBS (pH=7.4,10mM) or RD SNS under no 785nm laser irradiations, from mouse peritoneal
NCS water slurries (2mgmL-1) 7 days hematoxylin eosin staining histotomy, the amplification factor of all pictures is 200
Times；
Figure 27 is the grading curve of prismatic dodecahedron SnS crystal prepared by the embodiment of the present invention 2；
Figure 28 is the stereoscan photograph of prismatic dodecahedron SnS crystal prepared by the embodiment of the present invention 2；
Figure 29 is the grading curve of prismatic dodecahedron SnS crystal prepared by comparative example 1 of the present invention；
Figure 30 is the stereoscan photograph of prismatic dodecahedron SnS crystal prepared by comparative example 1 of the present invention；
Figure 31 is the stereoscan photograph of prismatic dodecahedron SnS crystal prepared by comparative example 2 of the present invention；
Figure 32 is the stereoscan photograph of prismatic dodecahedron SnS crystal prepared by comparative example 3 of the present invention.
Specific implementation mode
Technical scheme of the present invention is described further below in conjunction with the drawings and specific embodiments.
Embodiment 1
The present invention has the preparation method of the SnS nanocrystals of granatohedron structure, specifically makes with the following method
It is standby to form：
By 1mmol stannous chlorides, 1mmolL- cysteines and 0.4mmol polyvinylpyrrolidones (PVP), it is dissolved in 75mL
Mixed solution is made in water, wherein the molecular weight of polyvinylpyrrolidone is 1300000；Mixed solution is transferred to reaction kettle
Middle heating, controlling reaction temperature is 200 DEG C, after reacting 110min, the product centrifugal treating that will be obtained, then wash sample with water and alcohol
The SnS nanocrystals with prismatic dodecahedron structure, abbreviation RD SnS NC is made in product.Yield has been more than 95%.
The pattern and ingredient of RD SnS NC passes through scanning electron microscope, transmission electron microscope, high resolution TEM and power spectrum respectively
It is characterized.Stereoscan photograph and transmission electron microscope photo difference are as shown in Figures 1 to 3, the reaction time be 110min after obtain
The average grain diameter of RD SnS NC be 202~288nm, grain size height it is uniform and dispersion, by figure it is observed that crystal has
Typical granatohedron structure.As shown in figure 4, high resolution TEM photo is shown in crystal interplanar distance is
0.338nm can belong to (222) crystal face of cube SnS nanocrystals.EDS elemental analyses in Fig. 5 show that Sn and S elements exist
It is equally distributed in RD SnS NCs, and the element ratio in the RD SnS NCs prepared is 1:1.
Fig. 6 and Fig. 7 has further confirmed that the formation of RD SnS NCs.Fig. 6 is shown and Sn2+(3d5/2) corresponding 486.1eV
With with Sn2+(3d3/2) corresponding 494.6eV combination energy, Fig. 7 shows the combinations of the 2p of 161.0 and 162.0eVS spectrally
Can, it is attributable to S 2p respectively3/2With S 2p1/2。
The present embodiment 1 prepare RD SnS NCs XRD spectrum as shown in figure 8, RD SnS NC lattice constantThe SnS of cubic phase can be belonged to.
RD SnS NC prepared by the present embodiment 1 are carried out to the measurement of extinction coefficient epsilon, extinction coefficient can be by shown in formula (I)
Lang Bo-Beer law calculated, in Formulas I, A is the absorbance of RD SnS NCs water slurries at 785nm, and L is stone
The length of English test tube, unit are cm, and C is the concentration of RD SnS NC, unit gL-1,
RD SnS NC prepared by the present embodiment 1 carry out the measurement of Photothermal characterisation, prepare respectively various concentration (0,0.1,
0.3、0.1、0.3mg·mL-1) RD SnS NC water slurries, respectively take 100 μ L to be added in PCR pipe, be using wavelength
785nm, power 0.8Wcm-2Laser irradiated, real-time thermal imaging note is carried out to sample with infrared thermal imaging camera
Record and quantization.Photo and thermal stability is tested：It is 785nm using wavelength, power 0.8Wcm-2100 microlitres of laser irradiation RD
SnS NCs water slurries (0.7mgmL-1) 6 minutes, it is then shut off laser natural cooling, such retest 5 times.
RD SnS NC prepared by the present embodiment 1 are carried out to the detection of photothermal conversion efficiency, the photothermal conversion of RD SnS NC
Efficiency can be calculated by formula (II)：
Wherein, TMaxIt is the maximum temperature of RD SnS NC water slurries, TSurrIt is the temperature of ambient enviroment, (TMax-Tsurr)
=44, Q0The energy absorbed by sample cell (PCR pipe) can be absorbed by the photo-thermal of the PCR pipe containing only 100 μ L deionized waters
It measures, (Q0=16mW), I is 0.8Wcm-2(it is 0.385cm in light radiation area2In the case of), A is at 785nm wavelength
RD SnS nc water slurries absorbance value (A=2.1), h is thermal conversion factor, and S is the surface area of sample cell, and hS can lead to
It crosses formula (III) to be calculated, is 3.1mW/ DEG C,
In formula (III), τsIt is the hot-cast socket time constant of system, mDFor the quality of water, cDFor the specific heat capacity (4.2J/ of water
g·℃).It finally calculates and learns, the 39.4% of the photothermal conversion efficiency of RD SnS NC.
Using the optical of ultraviolet-visible light-near infrared spectrum (UV-Vis-NIR) spectroscopy measurements RD SnS NC
Can, the results are shown in Figure 9, and it is 202~288nm that RD SnS NC have very strong absorbability, average-size near infrared region
RD SnS NC there is absorption peak at 705nm, light thermit powders of the RD SnS NC as photo-thermal therapy cancer may be selected.By Figure 10
With Figure 11 it is found that RD SnS NCs show very strong absorbance near infrared region, there is 36.8Lg at 785nm-1·cm-1Extinction coefficient.The extinction coefficient is far above the gold nanorods (3.9Lg reported-1·cm-1), nano graphene oxide
(3.6L·g-1·cm-1), nanometer redox graphene (24.6Lg-1·cm-1) and many semi-conducting materials, such as black phosphorus
Quantum dot (14.8Lg-1·cm-1)、MoS2(29.2L·g-1·cm-1)、WS2(14.8L·g-1·cm-1)、Cu2-xSe
(8.5L·g-1·cm-1) etc..
By monitor RD SnS NC water slurries wavelength be 785nm, energy density 0.8Wcm-2Laser under spoke
According to temperature change research RD SnS NC Photothermal characterisation, as a result as shown in Figures 12 and 13,785nm laser irradiation after, RD
The temperature of SnS NC water slurries is apparently higher than pure water, and showing RD SnS NCs has good photo-thermal effect.Due to photo-thermal
The concentration of the presence of effect, higher SnS NCs can be such that solution temperature increases more.When NCs water slurry concentration reaches
0.7mg·mL-1When, 785nm laser irradiations after five minutes, the temperature of NCs water slurries can rapidly increase to 70 DEG C.From
785nm laser irradiation RD SnS NCs suspension is then shut off laser in 10 minutes, detects the RD SnS NCs suspension of the process
Temperature change, calculating acquires that heat balance time constant is 135.9s, photothermal conversion efficiency is 39.4% (such as the institutes of Figure 14 and 15
Show).The photothermal conversion efficiency of RD SnS NC is far above many light thermit powders reported, such as Cu2-xSe (22%), Cu9S5
(25.7%), black phosphorus quantum dot (28.4%) and TixTa1-xSyOz(39.2%).For test repeatability, NCs water is had studied
The laser ON/OFF process in 5 periods of suspension, as a result as shown in figure 16, adjacent peak temperature indifference shows weight for a long time
The RD SnS NCs of multiple laser irradiation have good photo and thermal stability.
The good biocompatibility of nano material is most important to its biomedical applications.Here, thin using HeLa and 3T3
Born of the same parents determine RD SnS NCs' as model, with 3- (4,5- dimethylthiazole -2-yl) -2,5- hexichol tetrazolium bromo-amines (MTT)
Bio-toxicity.As shown in figure 17, when the concentration of RD SnS NCs is less than 0.3mgmL-1When, HeLa and 3T3 cells are in no laser
The lower survival rate for being incubated 24 hours of irradiation is more than 87%, shows that RD SnS nc have low cytotoxicity.It has studied and is received 785
The HeLa cells of in vitro culture and the in vitro culture of NCs under rice laser irradiation, determine the PTT effects of NCs.HeLa cells and RD
SnS NCs(0.3mg·mL-1) be incubated with overnight, and the 10min under 785nm laser irradiations.As can be seen from Figure 18, only
There is the laser irradiation of 785nm to have no significant effect cell survival rate, and RD SnS NCs (0.3mgmL-1) addition cause
Cell survival rate of the HeLa cells under 785 laser irradiations drastically declines.It is carried out using the bis- staining kits of Calcein-AM/PI
Confocal cell imaging further demonstrates the photo-thermal effect of RD SnS NCs.Only dead cell could be dyed by PI.From Figure 19
In, RD SnS NCs have very strong lethal effect under 785nm laser irradiations to HeLa cells, illustrate that RD SnS NCs may
It is the potential PTT medicaments of oncotherapy.Calcein AM staining send out green fluorescence, indicator cells survival, and PI is dyed
Red fluorescence is then sent out, indicates cell death.
Applications of the RD SnS NC that the present embodiment 1 obtains in mouse HeLa tumours PTT.When mouse tumor volume increases
To~60mm3When, the mouse used in zoopery is randomly divided into 4 groups, every group 5.Every group of mouse is in tumor center region
PBS solution or RD SnS NCs water slurries are injected, with 785nm laser (1Wcm-2) irradiate 10 minutes.Meanwhile with PBS or RD
SnS NCs solution injects mouse, but does not have laser irradiation, carries out controllable experimental.With mouse during infrared hot cameras record irradiation
Temperature changing situation.As shown in figs 20 and 21, under 785nm laser irradiations, the tumor temperature of NCs suspension injection is in 6min
It is interior, increase to 54 DEG C from 30 DEG C.In contrast, the temperature for the tumour injected with PBS solution and the temperature irradiated with 785 nanometer lasers
Degree is only increased slightly.By the monitoring to tumor volume change, the photo-thermal therapy effects of NCs in vivo are had studied.Two after treatment
The every two days records of length and width of tumour in week are primary.As shown in figure 22, with RD SnS NCs and 785nm laser therapies
Mouse tumor melts completely.However, the tumour growth of other three control groups is rapid, gross tumor volume increases by 8 than initial size~
15 times.The weight of these mouse is increased slightly within the PTT times, shows that PTT processes do not have serious side effect (Figure 23).In order to
It further confirms that photo-thermal therapy effect, every group of two mouse are condemned to death after various treatments in one day, then uses haematoxylin and she
Red colouring (H＆E) carries out histologic analysis to corresponding tumour.Figure 24 shows the representative histopathology image of tumour.It can be with
It observes, serious destruction is subject to using the tumour cell of RD SnS NCs and 785nm laser therapies, such as more vacuoles,
The cell and the nuclei of condensation of atrophy.However, other three control groups are without apparent abnormal.These results indicate that RD SnS NCs
It is strictly a kind of effective tumour PTT medicaments in medical application.
In biomedical applications, the biocompatibilities of RD SnS NCs in vivo are also had evaluated.Intravenous injection 1 day or 7
After it RD SnS NCs, mouse is put to death, and histological examination is carried out to major organs.Meanwhile it being extracted from the eyeground of mouse
Blood is used for whole blood.As shown in figs. 25 and 26, apparent organ damage and intra-articular lesion are had no, shows RD SnS NCs
Without serious side effects.On the other hand, in the Balbc mouse of health, full blood count is carried out to injecting RD SnS NCs in 1 day.
The result shows that all parameters measured from whole blood are almost normal, and in normal range (NR) (as shown in table 1).These points
Analysis the result shows that, RD SnS NCs in vivo have preferable PTT biocompatibilities, have no toxic side effect.
Table 1 is injected intravenously 25 μ L 2mgmL-1Mouse whole blood cell count of the SnS NCs solution after 1 day
Embodiment 2
The method that embodiment 2 prepares the SnS nanocrystals with granatohedron structure, specific steps and embodiment 1
It is essentially identical, it the difference is that only that the reaction time is 120min, prepared by embodiment 2 has granatohedron structure
SnS nanocrystals are denoted as RD SnS NC-2.
Embodiment 2 prepares the grading curve and SEM photograph point of the SnS nanocrystals with granatohedron structure
Not as in figs. 27 and 28, after reacting 120min, the grain size of SnS crystal is 463~531nm.Ultraviolet-visible light-near-infrared
Spectrum shows occur strong absworption peak at 745nm.
Comparative example 1
The method that comparative example prepares SnS crystal, specific steps are substantially the same manner as Example 1, the difference is that only
Reaction time is 140min.
Comparative example 1 prepare SnS crystal grading curve and SEM photograph respectively as shown in figures 29 and 30,
After reacting 140min, the grain size of SnS crystal is 1.41~2.31 μm.
By the comparison of embodiment 1, embodiment 2 and comparative example 1 it is found that the reaction time can control the shape of product form
At.
Comparative example 2
The method that comparative example 2 prepares SnS crystal, specific steps are substantially the same manner as Example 1, the difference is that only
The molecular weight of PVP is 400000.The SEM photograph difference of SnS crystal prepared by comparative example 2 is as shown in figure 31.
Comparative example 3
The method that comparative example 3 prepares SnS crystal, specific steps are substantially the same manner as Example 1, the difference is that only
The molecular weight of PVP is 360000.The SEM photograph difference of SnS crystal prepared by comparative example 3 is as shown in figure 32.
By the comparison of embodiment 1, comparative example 2 and comparative example 3 it is found that when the molecular weight of PVP is 400000
When, SnS crystal cannot form granatohedron structure, when the molecular weight of PVP is 360000, have a small amount of shape in SnS crystal
At granatohedron structure, when the molecular weight of PVP is 1300000, SnS crystal can largely form granatohedron knot
Structure, and only have granatohedron structure SnS crystal ability with good photo-thermal effect and biocompatibility and low
Cytotoxicity.
Claims (8)
1. a kind of SnS nanocrystals, it is characterised in that：The SnS nanocrystals have prismatic dodecahedron structure.
2. a kind of preparation method of SnS nanocrystals described in claim 1, which is characterized in that include the following steps：
Step 1, the desired amount of stanniferous presoma, sulfur-bearing presoma and surfactant is soluble in water, after mixing, in
100~120min is reacted at 180~220 DEG C；
Step 2, collecting reaction product can be obtained the SnS crystal with prismatic dodecahedron structure after washing.
3. the preparation method of SnS nanocrystals according to claim 2, it is characterised in that：In step 1, it is described it is stanniferous before
It is at least one of dichloro stannous, butter of tin or stannous sulfate to drive body.
4. the preparation method of SnS nanocrystals according to claim 2, it is characterised in that：In step 1, before the sulfur-bearing
Drive body is at least one of thiocarbamide, thioacetamide, vulcanized sodium, L-cysteine or reduced glutathione.
5. the preparation method of SnS nanocrystals according to claim 2, it is characterised in that：In step 1, the surface is lived
Property agent be polyvinylpyrrolidone.
6. the preparation method of SnS nanocrystals according to claim 5, it is characterised in that：The polyvinylpyrrolidone
Molecular weight be 1300000.
7. the preparation method of SnS nanocrystals according to claim 2, it is characterised in that：In step 1, it is described it is stanniferous before
The mixing molar ratio for driving body and sulfur-bearing presoma is 1：1~12；The mixing molar ratio of the stanniferous precursor and surfactant
It is 1：0.1~1.2.
8. SnS nanocrystals described in claim 1 are used to prepare the application in cancer cell photo-thermal therapy material.
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| CN (1) | CN108545769A (en) |
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| CN109516494A (en) * | 2018-10-23 | 2019-03-26 | 温州大学新材料与产业技术研究院 | A kind of method of low temperature liquid phase synthesis stannous sulfide |
| CN114381822A (en) * | 2022-01-24 | 2022-04-22 | 南通大学 | Preparation method of SnS micro-flower-doped electrostatic spinning fiber with photothermal function |
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| CN106219596A (en) * | 2016-07-19 | 2016-12-14 | 浙江大学宁波理工学院 | A kind of synthetic method of the SnS crystal with letter C shape |
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| CN106006720A (en) * | 2016-05-30 | 2016-10-12 | 昆明理工大学 | Method for preparing SnS/SnS2 heterojunction material and application of SnS/SnS2 heterojunction material |
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Cited By (3)
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| CN109516494A (en) * | 2018-10-23 | 2019-03-26 | 温州大学新材料与产业技术研究院 | A kind of method of low temperature liquid phase synthesis stannous sulfide |
| CN114381822A (en) * | 2022-01-24 | 2022-04-22 | 南通大学 | Preparation method of SnS micro-flower-doped electrostatic spinning fiber with photothermal function |
| CN114381822B (en) * | 2022-01-24 | 2023-12-22 | 南通大学 | Preparation method of SnS micron flower doped electrostatic spinning fiber with photo-thermal function |
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