CN114588261A - Preparation method and application of ion-doped copper sulfide nano particles - Google Patents
Preparation method and application of ion-doped copper sulfide nano particles Download PDFInfo
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- CN114588261A CN114588261A CN202210242009.8A CN202210242009A CN114588261A CN 114588261 A CN114588261 A CN 114588261A CN 202210242009 A CN202210242009 A CN 202210242009A CN 114588261 A CN114588261 A CN 114588261A
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- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000003384 imaging method Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 98
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 239000011259 mixed solution Substances 0.000 claims description 45
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 36
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 28
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 18
- 238000004062 sedimentation Methods 0.000 claims description 18
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical group CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 17
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000005642 Oleic acid Substances 0.000 claims description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 14
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 150000002696 manganese Chemical class 0.000 claims description 6
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 4
- 206010028980 Neoplasm Diseases 0.000 claims description 3
- ZQZQURFYFJBOCE-FDGPNNRMSA-L manganese(2+);(z)-4-oxopent-2-en-2-olate Chemical group [Mn+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZQZQURFYFJBOCE-FDGPNNRMSA-L 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000002648 combination therapy Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 40
- 229910052742 iron Inorganic materials 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000003446 ligand Substances 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002595 magnetic resonance imaging Methods 0.000 abstract description 3
- 230000000259 anti-tumor effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000005341 cation exchange Methods 0.000 abstract description 2
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 2
- 238000007669 thermal treatment Methods 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 238000000862 absorption spectrum Methods 0.000 description 10
- 239000002086 nanomaterial Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical group [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 229910052951 chalcopyrite Inorganic materials 0.000 description 4
- 238000003745 diagnosis Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910052948 bornite Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000001659 chemokinetic effect Effects 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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Abstract
The invention discloses a preparation method and application of ion-doped copper sulfide nano particles; the preparation method is characterized in that the copper sulfide nano-particles doped with iron and manganese ions are synthesized by a cation exchange method, the method is simple, the near-infrared absorption of a sample can be still maintained under higher doping concentration, the Fenton reaction can be smoothly and efficiently carried out, and the NIR light absorption and Fenton reaction effects of the material are ensured; the metal ion-doped copper sulfide nano particles can be connected with a hydrophilic ligand through a ligand exchange reaction and transferred into a water phase, show photo-thermal treatment enhancement in the anti-tumor aspect, simultaneously enhance Fenton reaction catalytic effect and magnetic resonance imaging effect, and can be used for photo-acoustic imaging.
Description
Technical Field
The invention belongs to the technical field of nano biomedicine, and particularly relates to a preparation method and application of ion-doped copper sulfide nano particles.
Background
Diagnosis and treatment technology is an important research direction in the field of life health science, novel diagnosis and treatment materials are developed to combine diagnosis and treatment, and the method has important significance for development of accurate medical treatment. Up to now, various nanopreparations composed of gold-based nanomaterials, carbon-based nanomaterials, organic compounds, inorganic semiconductor compounds, etc. have been widely developed for the photo-diagnosis and treatment of tumors. Among them, copper sulfide nanomaterials are widely used as photothermal diagnostic reagents due to their excellent photothermal efficiency and in vivo biodegradability. Compared with the traditional plasma material, the copper sulfide nano material has the advantages of lower raw material cost, simple synthesis method, easy adjustment of near infrared absorption and the like. In the biological application aspect, the copper sulfide has the advantages of low toxicity and good colloid stability.
The copper sulfide nanoparticles have photoacoustic imaging capability, and in order to further improve imaging effect, the copper sulfide can chelate magnetic resonance imaging ions such as iron, manganese and the like through surface ligands. Chelation of iron ions also allows for chemokinetic therapeutic capabilities of the composite material, or induces a process of iron death by the cells. However, these complexes are less stable in blood and tend to dissociate. In addition, CuFeS can be easily obtained by directly doping metal ions during copper sulfide synthesis2Etc. to make the near infrared absorption disappear. The document "Synthesis of one-for-all type Cu" published by Zoojie Wang et al5FeS4Three Cu ions are prepared in a direct doping manner by using nanocrystals with improved side of doped photo thermal and Fenton efficiencies for simultaneous electron imaging and thermal of molecularxFeySzSample comprising FeS2、CuFeS2And Cu5FeS4And (3) nano materials. The test results showed that as the Cu/Fe molar ratio was increased from 0/1.0 to 1.0/1.0 and 5.0/1.0, the peak characteristic of Localized Surface Plasmon Resonances (LSPRs) was shifted to longer wavelengths, and the photothermal conversion efficiency was increased from 24.4% to 36.6% and 45.9%. From this article it is known that CuFeS is prepared in a one-step process2Is relatively poor in near infrared absorption, Cu5FeS4Although the effect of photothermal enhancement is shown, it is mentioned in the article thatDue to the high concentration of copper defects in the material, Cu defects lead to strong LSPRs effects and then to increased NIR light absorption; however, to adjust the near infrared absorption, the copper/iron ratio in the nanoparticles needs to be changed to adjust the copper defects. However, increasing the copper/iron ratio results in a limited iron content, which affects the performance of fenton's reaction and thus the effect of the chemo-kinetic therapy, and it is mentioned in the article that when the iron content is low, the material can ensure the absorption of more than 1000nm, but the iron content is increased, so that the one-step preparation of metal ion-doped copper sulfide is limited in practical application.
Chinese patent CN 107572592B discloses a photo-thermal material suitable for near-infrared light excitation and a preparation method thereof, wherein a second metal ion is introduced on the basis of unit copper sulfide to form multi-element metal sulfide powder CuFeS2CuFeS disclosed in the patent2Although the nano-material is prepared in a step-by-step mode, the temperature used in the preparation is 220-310 ℃, so that the nano-material with a uniform and stable structure is obtained, but the nano-material is not a composite material which takes copper sulfide as a core and is doped with metal on the surface of the core, the near infrared absorption of the copper sulfide is caused by defects, the light absorption of the copper sulfide is deteriorated due to the structure, and the figure 4 in the specification shows that CuFeS has a good photo-thermal effect on a sample2The concentration of (B) is 1.0mM, CuFeS2The amount of the organic solvent is large, and the application of the material is limited due to the characteristic.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a preparation method and application of a novel ion-doped copper sulfide nano particle.
The technical scheme of the invention is as follows: a preparation method of ion-doped copper sulfide nano particles specifically comprises the following steps:
s1, adding sulfur powder into a mixed solution of oleic acid and octadecene, heating to be completely dissolved under the protection of nitrogen, and then cooling the solution to 55 ℃;
s2, adding copper acetylacetonate into the mixed solution of oleylamine and octadecene, and dissolving at 55 ℃;
s3, adding a certain amount of the solution obtained in the step S1 into the solution obtained in the step S2, heating to 80-140 ℃ under the protection of nitrogen, and keeping the reaction for 1-2 hours;
s4, adding ethanol into the reaction solution for sedimentation, centrifugally collecting copper sulfide precipitate, and dispersing the copper sulfide precipitate in octadecene to obtain a copper sulfide solution;
s5, adding a ferric salt or manganese salt solution into the mixed solution of oleylamine and octadecene, and dissolving at 55 ℃;
s6, adding the copper sulfide octadecylene solution obtained in the step S4 into the solution obtained in the step S5, heating to 80-140 ℃ under the protection of nitrogen, and maintaining the reaction for 20-40 min;
and S7, adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the ion-doped copper sulfide nano particle solution dispersed in chloroform.
Further, in step S1, the concentration of the sulfur powder solution is 180-200 mmol/L.
Further, in step S3, the molar ratio of copper acetylacetonate to sulfur powder is 1:1 to 10.
Further, in step S5, the iron salt is ferric acetylacetonate or ferrous acetylacetonate, and the manganese salt is manganese (ii) acetylacetonate.
Further, in step S5, the molar ratio of the iron salt or manganese salt to the copper acetylacetonate is 0.1-1: 1.
An ion-doped copper sulfide nanoparticle prepared based on the preparation method; the ion-doped copper sulfide nano particle can be applied to photoacoustic imaging; can also be used for preparing tumor combined therapeutic agent or tool.
The beneficial effect of this application does:
1. according to the method, the metal iron and manganese ion doped copper sulfide nano particles are synthesized by adopting a cation exchange method, the method is simple, the stability is high, the doping process is carried out at a lower temperature, the prepared doped material has a copper sulfide core, only metal ions are doped on the surface of the material, the material has a copper defect with higher concentration, a strong LSPRs effect can occur, and better NIR light absorption is further caused; the prepared doped material does not need to improve the copper/iron ratio to adjust the copper defect, and can still keep strong near-infrared absorption when the iron/copper ratio is 1:1, so that the Fenton reaction can be smoothly and efficiently carried out, and the NIR light absorption and the Fenton reaction effect of the material are ensured;
2. the metal ion-doped copper sulfide nano particles prepared by the method can be connected with hydrophilic ligands through ligand exchange reaction and transferred into a water phase, show photo-thermal treatment enhancement in the anti-tumor aspect, enhance Fenton reaction catalytic effect and magnetic resonance imaging effect, and can be used for photo-acoustic imaging;
3. the metal ion-doped copper sulfide nano-particles prepared by the method can change the absorption spectrum of the metal ion-doped copper sulfide nano-particles in a near infrared light region by adjusting the proportion of oleic acid and octadecene, and the phenomenon of red shift or blue shift occurs.
Drawings
FIG. 1 is a TEM image of Fe-doped Cu sulfide nanoparticles obtained in example one;
FIG. 2 is the absorption spectrum of the Fe-doped copper sulfide nanoparticles obtained in the first, second and third examples;
FIG. 3 is a graph showing the energy spectrum analysis of the Fe-doped copper sulfide nanoparticles obtained in the first example;
FIG. 4 is an X-ray diffraction pattern of iron-doped copper sulfide nanoparticles obtained in example one;
FIG. 5 is the absorption spectrum of the Fe-doped copper sulfide nanoparticles obtained in example V;
FIG. 6 is a photo-acoustic image of the aqueous solution of Fe-doped copper sulfide nano-particles obtained in example VIII;
FIG. 7 is a graph of photothermal temperature over time at different concentrations for the aqueous iron-doped copper sulfide nanoparticle solution obtained in example VIII;
FIG. 8 shows the Fe-doped copper sulfide nanoparticles and H obtained in example eight2O2And a time-dependent change of the absorption spectrum of the TMB mixed aqueous solution.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1: preparation of iron-doped copper sulfide nano particles
1) Dissolving sulfur powder in a mixed solution of oleic acid and octadecene, wherein the volume ratio of the oleic acid in the mixed solution is 50%, the concentration of the sulfur powder solution is 200mmol/L, heating to be completely dissolved under the protection of nitrogen, and then cooling the solution to 55 ℃;
2) adding copper acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of copper acetylacetonate is 16.7mmol/L, and the copper acetylacetonate is dissolved at 55 ℃;
3) adding the solution obtained in the step 1) into the solution obtained in the step 2), heating to 120 ℃ under the protection of nitrogen and maintaining for 1 h;
4) adding ethanol into the reaction solution for sedimentation, centrifuging, collecting copper sulfide precipitate, and dispersing the copper sulfide precipitate in octadecene to obtain 50mmol/L copper sulfide solution;
5) adding ferric acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of ferric acetylacetonate is 6.66mmol/L, and the ferric acetylacetonate is dissolved at 55 ℃;
6) adding the octadecylene solution of copper sulfide obtained in the step 4) into the solution obtained in the step 5) to enable the molar ratio of iron to copper to be 0.2:1, heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 30 min;
7) adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nano particle solution dispersed in chloroform.
The iron-doped copper sulfide nanoparticles prepared in this example were characterized, and the transmission electron microscopy image is shown in fig. 1, from which it can be seen that the prepared doped copper sulfide nanoparticles have uniform size and good dispersibility. The absorption spectrum is shown in fig. 2, and the prepared iron-doped copper sulfide nano particles can control the absorption peak to be near 1064 nm. EDS energy spectrum analysis chart is shown in figure 3, which shows that the iron element is successfully doped into the copper sulfide nano-scaleIn the particle. The X-ray diffraction pattern is shown in FIG. 4, which indicates that the product is covellite-type copper sulfide, not CuFeS2And Cu5FeS4And the like.
EXAMPLE two preparation of iron-doped copper sulphide nanoparticles
1) Dissolving sulfur powder in oleic acid, wherein the concentration of a sulfur powder solution is 200mmol/L, heating to be completely dissolved under the protection of nitrogen, and then cooling the solution to 55 ℃;
2) adding copper acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of copper acetylacetonate is 16.7mmol/L, and the copper acetylacetonate is dissolved at 55 ℃;
3) adding the solution obtained in the step 1) into the solution obtained in the step 2), heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 1 h;
4) adding ethanol into the reaction solution for sedimentation, centrifuging, collecting copper sulfide precipitate, and dispersing the copper sulfide precipitate in octadecene to obtain 50mmol/L copper sulfide solution;
5) adding ferric acetylacetonate into the mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of ferric acetylacetonate is 6.66mmol/L, and the ferric acetylacetonate is dissolved at 55 ℃;
6) adding the copper sulfide octadecylene solution obtained in the step 4) into the solution obtained in the step 5) to enable the molar ratio of iron to copper to be 0.2:1, heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 30 min;
7) adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nano particle solution dispersed in chloroform.
The iron-doped copper sulfide nanoparticles prepared in this example were characterized, and the absorption spectrum is shown in fig. 2, and the absorption peak of the prepared nanoparticles is in the vicinity of 1000nm, which is significantly blue-shifted with respect to that of the first example.
EXAMPLE III preparation of iron-doped copper sulphide nanoparticles
1) Dissolving sulfur powder in octadecene, wherein the concentration of a sulfur powder solution is 200mmol/L, heating to be completely dissolved under the protection of nitrogen, and then cooling the solution to 55 ℃;
2) adding copper acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of copper acetylacetonate is 16.7mmol/L, and the copper acetylacetonate is dissolved at 55 ℃;
3) adding the solution obtained in the step 1) into the solution obtained in the step 2), heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 1 h;
4) adding ethanol into the reaction solution for sedimentation, centrifuging, collecting copper sulfide precipitate, and dispersing the copper sulfide precipitate in octadecene to obtain 50mmol/L copper sulfide solution;
5) adding ferric acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of ferric acetylacetonate is 6.66mmol/L, and the ferric acetylacetonate is dissolved at 55 ℃;
6) adding the copper sulfide octadecylene solution obtained in the step 4) into the solution obtained in the step 5) to enable the iron/copper molar ratio to be 0.2:1, heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 30 min;
7) adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nano particle solution dispersed in chloroform.
The absorption spectrum of the iron-doped copper sulfide nanoparticles prepared in this example is shown in fig. 2, and the absorption peak of the prepared iron-doped copper sulfide nanoparticles is near 1200nm and has a significant red shift relative to that of the first example.
EXAMPLE four preparation of iron-doped copper sulphide nanoparticles
1) Dissolving sulfur powder in a mixed solution of oleic acid and octadecene, wherein the volume ratio of the oleic acid in the mixed solution is 50%, the concentration of the sulfur powder solution is 200mmol/L, heating to be completely dissolved under the protection of nitrogen, and then cooling the solution to 55 ℃;
2) adding copper acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of copper acetylacetonate is 16.7mmol/L, and the copper acetylacetonate is dissolved at 55 ℃;
3) adding the solution obtained in the step 1) into the solution obtained in the step 2), heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 1 h;
4) adding ethanol into the reaction solution for sedimentation, centrifuging, collecting copper sulfide precipitate, and dispersing the copper sulfide precipitate in octadecene to obtain 50mmol/L copper sulfide solution;
5) adding ferric acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of ferric acetylacetonate is 3.33mmol/L, and the ferric acetylacetonate is dissolved at 55 ℃;
6) adding the copper sulfide octadecylene solution obtained in the step 4) into the solution obtained in the step 5) to enable the iron/copper molar ratio to be 0.1:1, heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 30 min;
7) adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nano particle solution dispersed in chloroform.
Characterization of the iron-doped copper sulfide nanoparticles prepared in this example shows that iron element can be successfully doped into copper sulfide nanoparticles.
EXAMPLE V preparation of iron-doped copper sulphide nanoparticles
1) Dissolving sulfur powder in a mixed solution of oleic acid and octadecene, wherein the volume ratio of the oleic acid in the mixed solution is 50%, the concentration of the sulfur powder solution is 200mmol/L, heating to be completely dissolved under the protection of nitrogen, and then cooling the solution to 55 ℃;
2) adding copper acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of copper acetylacetonate is 16.7mmol/L, and the copper acetylacetonate is dissolved at 55 ℃;
3) adding the solution obtained in the step 1) into the solution obtained in the step 2), heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 1 h;
4) adding ethanol into the reaction solution for sedimentation, centrifuging, collecting copper sulfide precipitate, and dispersing the copper sulfide precipitate in octadecene to obtain 50mmol/L copper sulfide solution;
5) adding ferric acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of ferric acetylacetonate is 16.7mmol/L, and the ferric acetylacetonate is dissolved at 55 ℃;
6) adding the copper sulfide octadecylene solution obtained in the step 4) into the solution obtained in the step 5) to enable the iron/copper molar ratio to be 1:1, heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 30 min;
7) adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nano particle solution dispersed in chloroform.
Characterization of the iron-doped copper sulfide nanoparticles prepared in this example showed that iron was successfully doped into the copper sulfide nanoparticles, and the absorption spectrum of the resulting material is shown in fig. 5, from which it can be seen that the sample still maintains excellent LSPR absorption at high iron/copper molar ratio.
EXAMPLE sixthly, preparation of a ferrous iron-doped copper sulfide nanoparticle
1) Dissolving sulfur powder in a mixed solution of oleic acid and octadecene, wherein the volume ratio of the oleic acid in the mixed solution is 50%, the concentration of the sulfur powder solution is 200mmol/L, heating to be completely dissolved under the protection of nitrogen, and then cooling the solution to 55 ℃;
2) adding copper acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of copper acetylacetonate is 16.7mmol/L, and the copper acetylacetonate is dissolved at 55 ℃;
3) adding the solution obtained in the step 1) into the solution obtained in the step 2), heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 1 h;
4) adding ethanol into the reaction solution for sedimentation, centrifuging, collecting copper sulfide precipitate, and dispersing the copper sulfide precipitate in octadecene to obtain 50mmol/L copper sulfide solution;
5) adding ferrous acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of the ferrous acetylacetonate is 6.66mmol/L, and the ferrous acetylacetonate is dissolved at 55 ℃;
6) adding the copper sulfide octadecylene solution obtained in the step 4) into the solution obtained in the step 5) to enable the molar ratio of ferrous to copper to be 0.2:1, heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 30 min;
7) adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nano particle solution dispersed in chloroform.
The iron-doped copper sulfide nanoparticles prepared in the embodiment are characterized, the iron (II) element can be successfully doped into the copper sulfide nanoparticles, and the obtained doped copper sulfide nanoparticles have uniform size and good dispersibility.
EXAMPLE seven preparation of manganese-doped copper sulphide nanoparticles
1) Dissolving sulfur powder in a mixed solution of oleic acid and octadecene, wherein the volume ratio of the oleic acid in the mixed solution is 50%, the concentration of the sulfur powder solution is 200mmol/L, heating to be completely dissolved under the protection of nitrogen, and then cooling the solution to 55 ℃;
2) adding copper acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of the copper acetylacetonate is 16.7mmol/L, and the copper acetylacetonate is dissolved at 55 ℃;
3) adding the solution obtained in the step 1) into the solution obtained in the step 2), heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 1 h;
4) adding ethanol into the reaction solution for sedimentation, centrifuging, collecting copper sulfide precipitate, and dispersing the copper sulfide precipitate in octadecene to obtain 50mmol/L copper sulfide solution;
5) adding manganese (II) acetylacetonate into a mixed solution of oleylamine and octadecene, wherein the volume ratio of oleylamine in the mixed solution is 33.3%, the concentration of manganese acetylacetonate is 6.66mmol/L, and the manganese acetylacetonate is dissolved at 55 ℃;
6) adding the copper sulfide octadecylene solution obtained in the step 4) into the solution obtained in the step 5), heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 30 min;
7) adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the manganese-doped copper sulfide nano particle solution dispersed in chloroform.
The manganese-doped copper sulfide nanoparticles prepared in the embodiment are characterized, and the result shows that the manganese (II) element can be successfully doped into the copper sulfide nanoparticles.
Example eight, preparation of an aqueous solution of doped copper sulphide nanoparticles:
0.5mL of the chloroform solution of iron-doped copper sulfide nanoparticles (12.8mg/mL) prepared in example V was added dropwise to ultrapure water (4mL) containing DSPE-PEG5000(35mg) with stirring, and the mixture was stirred with ultrasonic wave and dispersed uniformly; heating in water bath to volatilize chloroform at 60 ℃ and finally preparing the iron-doped copper sulfide nano particle aqueous solution with the concentration of 1.6 mg/mL.
The performance verification and testing was as follows:
1. near-infrared two-region photoacoustic imaging
The result of preparing an iron-doped copper sulfide nanoparticle aqueous solution with the concentration of 1.0mg/mL, taking 200 muL of the aqueous solution in a small test tube, and then imaging by using a photoacoustic imager is shown in FIG. 6, which shows that the nanoparticles have excellent photoacoustic imaging capability.
2. Testing of photothermal Properties
The influence of different concentrations on the photothermal conversion effect of the iron-doped copper sulfide nanoparticle aqueous solution is researched. Iron-doped copper sulfide nano particle (10, 20, 35, 50 mu g/mL) solutions with different concentrations are prepared respectively, and the mass absorption coefficient at 1064nm can reach 23.2 L.g-1. Putting 200 μ L of the solution into a 200 μ L centrifuge tube, and using a 1064nm laser as an excitation light source with a laser power density of 1W/cm2Irradiating for 10min, and reading the solution temperature by using a thermal infrared imager. The above experiment was repeated with pure water as a reference. The experimental result is shown in FIG. 7, and the graphical result shows that the temperature of the nanoparticle solution is obviously increased along with the increase of the material concentration, and the laser power density is 1W/cm2Under the condition, the temperature of the 35ug/mL solution can reach more than 65 ℃, and the photothermal conversion efficiency can reach 42.7%, which shows that the iron-doped copper sulfide nano particles have good photothermal performance.
2. Chemical kinetics Performance test
Iron-doped CuS nanoparticles (10 μ g/mL) were dispersed in phosphate buffer (0.01M, 2mL) at pH 5.5, and TMB (0.4mM) and H were added2O2(10 mM). The absorption spectra of the mixed solution were sampled and tested at 0min, 10min, 20min and 30min, respectively. The experimental result shows that the absorbance of the absorption spectrum at 652nm is obviously increased along with the increase of the reaction time within 30 minutes, and as shown in FIG. 8, the iron-doped copper sulfide nano particles have good chemical kinetic performance.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (8)
1. A preparation method of ion-doped copper sulfide nano particles is characterized by comprising the following steps:
s1, adding sulfur powder into a mixed solution of oleic acid and octadecene, heating to be completely dissolved under the protection of nitrogen, and then cooling the solution to 55 ℃;
s2, adding copper acetylacetonate into the mixed solution of oleylamine and octadecene, and dissolving at 55 ℃;
s3, adding a certain amount of the solution obtained in the step S1 into the solution obtained in the step S2, heating to 80-140 ℃ under the protection of nitrogen, and keeping the reaction for 1-2 hours;
s4, adding ethanol into the reaction solution for sedimentation, centrifugally collecting copper sulfide precipitate, and dispersing the copper sulfide precipitate in octadecene to obtain a copper sulfide solution;
s5, adding a ferric salt or manganese salt solution into the mixed solution of oleylamine and octadecene, and dissolving at 55 ℃;
s6, adding the copper sulfide octadecylene solution obtained in the step S4 into the solution obtained in the step S5, heating to 80-140 ℃ under the protection of nitrogen, and maintaining the reaction for 20-40 min;
and S7, adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the ion-doped copper sulfide nano particle solution dispersed in chloroform.
2. The method of claim 1, wherein in step S1, the concentration of the sulfur powder solution is 180-200 mmol/L.
3. The method of claim 1, wherein in step S3, the molar ratio of copper acetylacetonate to sulfur powder is 1: 1-10.
4. The method of claim 1, wherein in step S5, the iron salt is ferric acetylacetonate or ferrous acetylacetonate, and the manganese salt is manganese (II) acetylacetonate.
5. The method according to claim 1, wherein in step S5, the molar ratio of the iron salt or manganese salt to the copper acetylacetonate is 0.1-1: 1.
6. An ion-doped copper sulfide nanoparticle, wherein the nanoparticle is prepared based on the method for preparing the ion-doped copper sulfide nanoparticle according to any one of claims 1 to 5.
7. Use of the ion-doped copper sulfide nanoparticles of claim 6 in photoacoustic imaging.
8. Use of ion-doped copper sulfide nanoparticles according to claim 6 for the preparation of a tumor combination therapy agent or tool.
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