CN109876160A - A kind of copper and iron antimony sulphur nano particle and its preparation method and application - Google Patents
A kind of copper and iron antimony sulphur nano particle and its preparation method and application Download PDFInfo
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- CN109876160A CN109876160A CN201910130556.5A CN201910130556A CN109876160A CN 109876160 A CN109876160 A CN 109876160A CN 201910130556 A CN201910130556 A CN 201910130556A CN 109876160 A CN109876160 A CN 109876160A
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Abstract
The invention discloses a kind of copper and iron antimony sulphur nano particles and its preparation method and application.The preparation method of copper and iron antimony sulphur nano particle obtains solution I the following steps are included: 1) cuprous salt and ferrous salt are dissolved in octadecylene；2) sulphur powder is dissolved in oleyl amine, obtains solution II；3) antimonic salt is dissolved in octadecylene, obtains solution III；4) solution I is added in solution II, sufficiently reacts, obtains reaction mixture I；5) reaction mixture I is added in solution III, sufficiently reacts, obtains reaction mixture II, it is cooling, it is separated by solid-liquid separation.Copper and iron antimony sulphur nano particle of the invention has many advantages, such as that partial size is smaller and uniform, photothermal conversion efficiency is high, photo-thermal property is stable, near-infrared absorption ability is strong, magnetic response ability is strong, its preparation flow is relatively easy, reaction condition is easily controllable, is not necessarily to covalent coupling, it not only has good photoacoustic imaging and magnetic resonance imaging effect, but also has good tumour cell photo-thermal fragmentation effect.
Description
Technical field
The present invention relates to field of material technology, and in particular to a kind of copper and iron antimony sulphur nano particle and preparation method thereof and answers
With.
Background technique
Photoacoustic imaging (Photoacoustic Imaging, PAI) has been developed in recent years a kind of non-invasive and non-
The novel lossless of ionization type hurts Medical Imaging Technology, high sensitivity, but soft tissue resolution is lower.Magnetic resonance imaging (MRI)
It is a kind of more traditional Medical Imaging Technology, soft tissue resolution is high, but sensitivity is lower.As it can be seen that photoacoustic imaging and magnetic
Resonance image-forming has respective advantage and defect.
Photoacoustic imaging needs by near infrared region to there is the exogenous contrast agent of optical absorption characteristics to enhance photoacoustic signal,
And then its sensitivity and specificity is improved, and be representative with surface with gold nano-material (including golden stick, golden cage, gold goal etc.)
The noble metal nanometer material of plasma resonance characteristic is the photoacoustic imaging material being widely used at present.However, gold nano-material
It is with high costs, and photo and thermal stability is poor, and long-time laser irradiation will appear morphologic change and cause light absorpting ability
Decline.Copper-based multicomponent metal sulfide is that a kind of novel light absorbing material is compared with noble metal nanometer material, has synthesis technology
Simply, the advantages that photo-thermal property is more stable, low in cost, doping is easily controllable, is a kind of very promising light absorption material
Material.
If it is possible to assign copper-based multicomponent metal sulfide magnetic responsiveness energy, then be expected to develop it is a kind of both can be with
For photoacoustic imaging, and it can be used for the nano material of magnetic resonance imaging.
Summary of the invention
The purpose of the present invention is to provide a kind of copper and iron antimony sulphur nano particles and its preparation method and application.
The technical solution used in the present invention is:
A kind of preparation method of copper and iron antimony sulphur nano particle, comprising the following steps:
1) cuprous salt of octadecylene will be dissolved in and ferrous salt is dissolved in octadecylene, obtain solution I；
2) sulphur powder is dissolved in oleyl amine, obtains solution II；
3) antimonic salt that will be dissolved in octadecylene is dissolved in octadecylene, obtains solution III；
4) solution I is heated to 240~280 DEG C, solution II is heated to 80~90 DEG C, then solution II is injected into solution I
In, 240~280 DEG C of constant temperature sufficiently react, and obtain reaction mixture I；
5) solution III being injected in reaction mixture I, 240~280 DEG C of constant temperature sufficiently react, reaction mixture II is obtained,
It is cooled to room temperature, is separated by solid-liquid separation, obtain copper and iron antimony sulphur nano particle.
Preferably, the cuprous salt, ferrous salt, sulphur powder, the molar ratio of antimonic salt are 1:(0.1~1): (0.5~2.5):
(0.2~1.2).
Preferably, the step 1) cuprous salt is stannous chloride, cuprous bromide, cuprous iodide, cuprous sulfate, cuprous acetate
One of.
Preferably, the step 1) ferrous salt is frerrous chloride, ferrous bromide, iron iodide, ferrous sulfate, ferrous acetate
One of.
Preferably, the step 3) antimonic salt is antimony chloride, antimony sulfate, nitric acid antimony, antimony acetate, one in acetylacetone,2,4-pentanedione antimony
Kind.
Preferably, the time of the step 4) reaction is 3~90min.
Preferably, the time of the step 5) reaction is 3~90min.
The beneficial effects of the present invention are: copper and iron antimony sulphur nano particle of the invention is with partial size, smaller and uniform, photo-thermal turns
The advantages that high-efficient, photo-thermal property is stable, near-infrared absorption ability is strong, magnetic response ability is strong is changed, preparation flow is relatively simple
List, reaction condition are easily controllable, are not necessarily to covalent coupling, not only have good photoacoustic imaging and magnetic resonance imaging effect, and
And also there is good tumour cell photo-thermal fragmentation effect.
Detailed description of the invention
Fig. 1 is the TEM photo of the copper and iron antimony sulphur nano particle of embodiment 1.
Fig. 2 is the Stem-mapping photo of the copper and iron antimony sulphur nano particle of embodiment 1.
Fig. 3 is the XRD diagram of the copper and iron antimony sulphur nano particle of embodiment 1.
Fig. 4 is the T2WI magnetic resonance imaging figure and relaxation rate-Fe concentration relationship of the copper and iron antimony sulphur nano particle of embodiment 1
Figure.
Fig. 5 is the B-H loop of the copper and iron antimony sulphur nano particle of embodiment 1.
Fig. 6 is the photo-thermal heating curve of the copper and iron antimony sulphur nano particle of embodiment 1.
Fig. 7 is heating-down cycles curve of the copper and iron antimony sulphur nano particle of embodiment 1.
Fig. 8 is the TEM photo of the copper and iron antimony sulphur nano particle of embodiment 2.
Fig. 9 is the TEM photo of the copper and iron antimony sulphur nano particle of embodiment 3.
Specific embodiment
The present invention will be further explained combined with specific embodiments below and explanation.
Embodiment 1:
A kind of preparation method of copper and iron antimony sulphur nano particle, comprising the following steps:
1) 0.45mmol stannous chloride and 0.45mmol frerrous chloride are dissolved in 7mL octadecylene, stir logical nitrogen 0.5h, obtains
To solution I；
2) 1mmol sulphur powder is dissolved in 3mL oleyl amine, obtains solution II；
3) 0.38mmol antimony trichloride is dissolved in 5mL octadecylene, obtains solution III；
4) solution I is heated to 260 DEG C, solution II is heated to 85 DEG C, then solution II is rapidly injected in solution I, 260
DEG C isothermal reaction 3min, obtains reaction mixture I；
5) solution III being rapidly injected in reaction mixture I, 260 DEG C of isothermal reaction 3min obtain reaction mixture II,
It is cooled to room temperature, reaction product is moved into centrifuge tube, methanol is added, repeated centrifugation three times, obtains copper and iron antimony sulphur nano particle.
(the small figure in the upper left corner is the TEM photo of copper and iron antimony sulphur nano particle manufactured in the present embodiment in Fig. 1 as shown in Figure 1
Grain size distribution).
The Stem-mapping photo of copper and iron antimony sulphur nano particle manufactured in the present embodiment is as shown in Figure 2.
(ordinate is absorption intensity to the XRD diagram of copper and iron antimony sulphur nano particle manufactured in the present embodiment, horizontal seat as shown in Figure 3
It is designated as 2 θ of the angle of diffraction).
The T2WI magnetic resonance imaging figure (the small figure in the upper left corner) and relaxation of copper and iron antimony sulphur nano particle manufactured in the present embodiment
Rate-Fe concentration relationship figure is as shown in Figure 4.
The B-H loop of copper and iron antimony sulphur nano particle manufactured in the present embodiment is as shown in Figure 5.
(compound concentration is 100 μ to the photo-thermal heating curve of copper and iron antimony sulphur nano particle manufactured in the present embodiment as shown in Figure 6
The copper and iron antimony sulphur nanoparticles solution of g/mL carries out laser irradiation, laser irradiation condition are as follows: 808nm, 1W/cm2, measure copper and iron
The relationship that the temperature of antimony sulphur nanoparticles solution changes over time).
(compound concentration is as shown in Figure 7 for heating-down cycles curve of copper and iron antimony sulphur nano particle manufactured in the present embodiment
The copper and iron antimony sulphur nanoparticles solution of 100 μ g/mL carries out laser irradiation, laser irradiation condition are as follows: 808nm, 1W/cm2, laser
Irradiation 500s, stop 1000s as 1 circulation, recycle 4 times, what the temperature of measurement copper and iron antimony sulphur nanoparticles solution changed over time
Relationship).
As shown in Figure 1: copper-zinc-tin-sulfur nano particle has nano-grade size, and partial size is concentrated mainly on 15~20nm, and big
It is small it is uniform, crystallinity is preferable.
As shown in Figure 2: containing copper, iron, four kinds of antimony, sulphur members in the nano particle of Stem-mapping photo display preparation
Element.
As shown in Figure 3: copper and iron antimony sulphur nano particle has very high phase purity, good crystallinity, and without miscellaneous peak.
As shown in Figure 4: the concentration of copper and iron antimony sulphur nanoparticles solution is bigger, image more black (the small figure in the upper left corner, Cong Zuozhi
Right copper and iron antimony sulphur nanoparticles solution concentration be followed successively by 0mmol/L, 0.0625mmol/L, 0.125mmol/L, 0.25mmol/L,
0.5mmol/L and 1mmol/L), and relaxation rate and Fe concentration have good linear relationship.
As shown in Figure 5: copper and iron antimony sulphur nano particle shows as the intensity of magnetization with the increasing of applied field strengths at room temperature
Add and be rapidly reached saturation, and without hysteresis.
As shown in Figure 6: copper and iron antimony sulphur nanoparticles solution (100 μ g/mL) is with laser irradiation (808nm, 1W/cm2) time
Extend, solution temperature gradually rises, and highest can be warming up to 67.9 DEG C, shows that it turns with good near-infrared absorption and photo-thermal
Transducing power.
As shown in Figure 7: heating-cooling 4 circulations of observation find copper and iron antimony sulphur nanoparticles solution (100 μ g/mL) every
In a heating-down cycles, temperature can rise to 60 DEG C or more, and the temperature difference does not change significantly, and show prepared receive
Rice grain has good photo and thermal stability.
Embodiment 2:
A kind of preparation method of copper and iron antimony sulphur nano particle, comprising the following steps:
1) 0.4mmol cuprous iodide and 0.05mmol ferrous nitrate are dissolved in 7mL octadecylene, stir logical nitrogen 0.5h, obtains
To solution I；
2) 0.5mmol sulphur powder is dissolved in 3mL oleyl amine, obtains solution II；
3) 0.4mmol antimony trichloride is dissolved in 5mL octadecylene, obtains solution III；
4) solution I is heated to 260 DEG C, solution II is heated to 85 DEG C, then solution II is rapidly injected in solution I, 260
DEG C isothermal reaction 30min, obtains reaction mixture I；
5) solution III being rapidly injected in reaction mixture I, 260 DEG C of isothermal reaction 30min obtain reaction mixture II,
It is cooled to room temperature, reaction product is moved into centrifuge tube, methanol is added, repeated centrifugation three times, obtains copper and iron antimony sulphur nano particle.
The TEM photo of copper and iron antimony sulphur nano particle manufactured in the present embodiment is as shown in Figure 8.
Embodiment 3:
A kind of preparation method of copper and iron antimony sulphur nano particle, comprising the following steps:
1) 0.405mmol stannous chloride and 0.045mmol frerrous chloride are dissolved in 7mL octadecylene, stir logical nitrogen 0.5h,
Obtain solution I；
2) 0.5mmol sulphur powder is dissolved in 3mL oleyl amine, obtains solution II；
3) 0.45mmol antimony trichloride is dissolved in 5mL octadecylene, obtains solution III；
4) solution I is heated to 260 DEG C, solution II is heated to 85 DEG C, then solution II is rapidly injected in solution I, 260
DEG C isothermal reaction 3min, obtains reaction mixture I；
5) solution III being rapidly injected in reaction mixture I, 260 DEG C of isothermal reaction 30min obtain reaction mixture II,
It is cooled to room temperature, reaction product is moved into centrifuge tube, deionized water is added, repeated centrifugation cleaning removes impurity three times, obtains
Copper and iron antimony sulphur nano particle.
The TEM photo of copper and iron antimony sulphur nano particle manufactured in the present embodiment is as shown in Figure 9.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of copper and iron antimony sulphur nano particle, it is characterised in that: the following steps are included:
1) cuprous salt of octadecylene will be dissolved in and ferrous salt is dissolved in octadecylene, obtain solution I；
2) sulphur powder is dissolved in oleyl amine, obtains solution II；
3) antimonic salt that will be dissolved in octadecylene is dissolved in octadecylene, obtains solution III；
4) solution I is heated to 240~280 DEG C, solution II is heated to 80~90 DEG C, then solution II is injected in solution I,
240~280 DEG C of constant temperature sufficiently react, and obtain reaction mixture I；
5) solution III is injected in reaction mixture I, 240~280 DEG C of constant temperature sufficiently react, and obtain reaction mixture II, cooling
It to room temperature, is separated by solid-liquid separation, obtains copper and iron antimony sulphur nano particle.
2. the preparation method of copper and iron antimony sulphur nano particle according to claim 1, it is characterised in that: the cuprous salt, Asia
Molysite, sulphur powder, the molar ratio of antimonic salt are 1:(0.1~1): (0.5~2.5): (0.2~1.2).
3. the preparation method of copper and iron antimony sulphur nano particle according to claim 1 or 2, it is characterised in that: step 1) is described
Cuprous salt is one of stannous chloride, cuprous bromide, cuprous iodide, cuprous sulfate, cuprous acetate.
4. the preparation method of copper and iron antimony sulphur nano particle according to claim 1 or 2, it is characterised in that: step 1) is described
Ferrous salt is one of frerrous chloride, ferrous bromide, iron iodide, ferrous sulfate, ferrous acetate.
5. the preparation method of copper and iron antimony sulphur nano particle according to claim 1 or 2, it is characterised in that: step 3) is described
Antimonic salt is one of antimony chloride, antimony sulfate, nitric acid antimony, antimony acetate, acetylacetone,2,4-pentanedione antimony.
6. the preparation method of copper and iron antimony sulphur nano particle according to claim 1 or 2, it is characterised in that: step 4) is described
The time of reaction is 3~90min；The time of the step 5) reaction is 3~90min.
7. a kind of copper and iron antimony sulphur nano particle, it is characterised in that: the preparation of the method as described in any one of claim 1~6
It obtains.
8. application of the copper and iron antimony sulphur nano particle as claimed in claim 7 in photoacoustic imaging.
9. application of the copper and iron antimony sulphur nano particle as claimed in claim 7 in magnetic resonance imaging.
10. application of the copper and iron antimony sulphur nano particle as claimed in claim 7 in the killing of tumour cell photo-thermal.
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| CN112007154A (en) * | 2020-08-31 | 2020-12-01 | 上海工程技术大学 | CuMo2S3Tween quantum dot and preparation method and application thereof |
| WO2022061981A1 (en) * | 2020-09-25 | 2022-03-31 | 苏州大学 | Doped metal sulfide and preparation and application thereof |
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