CN114588261B - 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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- CN114588261B CN114588261B CN202210242009.8A CN202210242009A CN114588261B CN 114588261 B CN114588261 B CN 114588261B CN 202210242009 A CN202210242009 A CN 202210242009A CN 114588261 B CN114588261 B CN 114588261B
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- acetylacetonate
- octadecene
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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 109
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 206010028980 Neoplasm Diseases 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 103
- 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 44
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 42
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 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 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- 239000013049 sediment Substances 0.000 claims description 18
- 238000004062 sedimentation Methods 0.000 claims description 18
- 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
- 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 12
- 238000001816 cooling Methods 0.000 claims description 9
- -1 copper sulfide octadecene Chemical compound 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
- 150000003839 salts Chemical class 0.000 claims description 4
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical group [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 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229940124597 therapeutic agent Drugs 0.000 claims description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 37
- 229910052742 iron Inorganic materials 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 abstract description 10
- 238000003384 imaging method Methods 0.000 abstract description 9
- 230000031700 light absorption Effects 0.000 abstract description 6
- 239000003446 ligand Substances 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
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 229910001437 manganese ion Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 238000000862 absorption spectrum Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 238000003745 diagnosis Methods 0.000 description 4
- 239000000126 substance Substances 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
- 238000012512 characterization method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 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 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 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
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- QYJPSWYYEKYVEJ-FDGPNNRMSA-L copper;(z)-4-oxopent-2-en-2-olate Chemical compound [Cu+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QYJPSWYYEKYVEJ-FDGPNNRMSA-L 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation 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
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical group [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 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
- 238000011056 performance test Methods 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 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 cationic exchange method is adopted to synthesize the iron and manganese ion doped copper sulfide nano particles, the method is simple, the near infrared absorption of the sample can be still kept under the condition of 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 ligand exchange reaction to transfer into a water phase, so that the catalytic effect of Fenton reaction and the magnetic resonance imaging effect are enhanced while the photothermal treatment enhancement is shown in the aspect of resisting tumors, and the metal ion doped copper sulfide nano particles can be used for photoacoustic 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
The diagnosis and treatment technology is an important research direction in the field of life health science, and development of novel diagnosis and treatment materials combines diagnosis and treatment, so that the method has important significance for the development of accurate medical treatment. Heretofore, various nano-formulations composed of gold-based nanomaterials, carbon-based nanomaterials, organic compounds, inorganic semiconductor compounds, and the like have been widely developed for photodiagnosis and treatment of tumors. Among them, copper sulfide nanomaterial is widely used as a photothermal diagnosis and treatment agent due to its 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 aspect of biological application, the copper sulfide has the advantages of low toxicity and good colloid stability.
The copper sulfide nano-particles have the photoacoustic imaging capability, and copper sulfide can chelate magnetic resonance imaging ions such as iron, manganese and the like through surface ligands in order to further improve the imaging effect. The chelation of iron ions also imparts chemical kinetic therapeutic capabilities to the composite, or induces cell-produced pig iron deathAnd (5) processing. However, these complexes are less stable in blood and are easily dissociated. In addition, cuFeS is easy to obtain by directly doping metal ions during the synthesis of copper sulfide 2 And the like, which causes near infrared absorption to disappear. Zhaojie Wang et al published literature "Synthesis of one-for-all type Cu 5 FeS 4 nanocrystals with improved near infrared photothermal and Fenton effects for simultaneous imaging and therapy of tumor "is to prepare three kinds of Cu by direct doping x Fe y S z Samples comprising FeS 2 、CuFeS 2 And Cu 5 FeS 4 A nanomaterial. The test results showed that as the Cu/Fe molar ratio increased from 0/1.0 to 1.0/1.0 and 5.0/1.0, the Localized Surface Plasmon Resonance (LSPRs) characteristic peak shifted to longer wavelengths, increasing the photothermal conversion efficiency from 24.4% to 36.6% and 45.9%. From this article, it is known that CuFeS is produced in a one-step process 2 Is relatively poor, cu 5 FeS 4 Although exhibiting photothermal enhancement effects, this is also mentioned in the paper as being caused by the fact that the material has a high concentration of copper defects, which lead to a strong LSPRs effect and then to an increased NIR light absorption; however, to achieve near infrared absorption adjustment, the copper/iron ratio in the nanoparticles is changed to adjust the copper defects. However, increasing the copper/iron ratio at one time results in limited iron content, which affects the Fenton reaction and thus the chemical kinetics treatment effect, and the article also mentions that when the iron content is low, the material can ensure the absorption of more than 1000nm, but the iron content cannot be increased, so that the preparation of the metal ion doped copper sulfide by a one-step method is limited to a certain extent in practical application.
Chinese patent CN 107572592B discloses a photo-thermal material suitable for near infrared excitation and a preparation method thereof, which introduces a second metal ion on the basis of unit copper sulfide to form multi-element metal sulfide powder CuFeS 2 CuFeS disclosed in the patent 2 Although the preparation is carried out in a stepwise manner, the temperature used in the preparation is 220-310 ℃, so that a nano material with uniform and stable structure is obtained instead ofThe copper sulfide is used as the core, and the metal is doped on the surface of the core, and the near infrared absorption of the copper sulfide is caused by defects, so that the light absorption of the copper sulfide is poor, and as can be seen from the figure 4 of the specification, the CuFeS has better photo-thermal effect on the sample 2 The concentration of CuFeS is 1.0mM 2 This property also limits the application of the material, with a large amount of (c).
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a novel preparation method and application of ion doped copper sulfide nano particles.
The technical scheme of the invention is as follows: the preparation method of the ion doped copper sulfide nano particle specifically comprises the following steps:
s1, adding sulfur powder into a mixed solution of oleic acid and octadecene, heating to completely dissolve under the protection of nitrogen, and then cooling the solution to 55 ℃;
s2, adding copper acetylacetonate into a 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 maintaining the reaction for 1-2 h;
s4, adding ethanol into the reaction solution for sedimentation, centrifugally collecting copper sulfide sediment, and dispersing the copper sulfide sediment in octadecene to obtain copper sulfide solution;
s5, adding ferric salt or manganese salt solution into the mixed solution of oleylamine and octadecene, and dissolving at 55 ℃;
s6, adding the copper sulfide octadecene 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, and dispersing in chloroform after centrifugal washing to obtain the ion doped copper sulfide nanoparticle solution dispersed in chloroform.
Further, in the step S1, the concentration of the sulfur powder solution is 180-200 mmol/L.
Further, in the step S3, the molar ratio of the copper acetylacetonate to the sulfur powder is 1:1-10.
Further, in step S5, the iron salt is iron acetylacetonate or ferrous acetylacetonate, and the manganese salt is manganese (ii) acetylacetonate.
Further, in the step S5, the molar ratio of the ferric salt or the manganese salt to the cupric acetylacetonate is 0.1-1:1.
An ion-doped copper sulfide nanoparticle prepared based on the above preparation method; the ion doped copper sulfide nano particles can be applied to photoacoustic imaging; can also be used for preparing tumor combined therapeutic agents or tools.
The beneficial effects of this application are:
1. the method is simple, the stability is high, the doping process is carried out at a lower temperature, the prepared inner core of the doped material is copper sulfide, only the surface of the material is doped with metal ions, the material has high-concentration copper defects, a strong LSPRs effect can occur, and better NIR light absorption is caused; the doped material is prepared, so that the copper defect is not required to be regulated by improving the copper/iron ratio, and strong near infrared absorption can be kept when the iron/copper ratio is 1:1, so that Fenton reaction can be smoothly and efficiently carried out, and the NIR light absorption and 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 a hydrophilic ligand through ligand exchange reaction to transfer into a water phase, so that the catalytic effect of Fenton reaction and the magnetic resonance imaging effect are enhanced while the photothermal treatment enhancement is shown in the aspect of resisting tumors, and the metal ion doped copper sulfide nano particles can be used for photoacoustic 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 region by adjusting the proportion of oleic acid and octadecene, and have the phenomenon of red shift or blue shift.
Drawings
FIG. 1 is a transmission electron microscope image of iron-doped copper sulfide nanoparticles obtained in example I;
FIG. 2 is an absorption spectrum of the iron-doped copper sulfide nanoparticles obtained in the first, second and third embodiments;
FIG. 3 is a spectrum analysis chart of the iron-doped copper sulfide nanoparticle obtained in the first embodiment;
FIG. 4 is an X-ray diffraction pattern of the iron-doped copper sulfide nanoparticles obtained in example I;
FIG. 5 is an absorption spectrum of iron-doped copper sulfide nanoparticles obtained in example five;
FIG. 6 is a photo-acoustic image of an aqueous solution of iron-doped copper sulfide nanoparticles obtained in example eight;
FIG. 7 is a graph showing the change of photothermal temperature with time of the iron-doped copper sulfide nanoparticle aqueous solution obtained in example eight at different concentrations;
FIG. 8 shows iron-doped copper sulfide nanoparticles and H obtained in example eight 2 O 2 And an absorption spectrum of the TMB mixed aqueous solution over time.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit of the invention are intended to be within the scope of the present 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 completely dissolve 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 the 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 for 1h;
4) Adding ethanol into the reaction solution for sedimentation, centrifugally collecting copper sulfide sediment, and dispersing the copper sulfide sediment 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 the oleylamine in the mixed solution is 33.3%, the concentration of the ferric acetylacetonate is 6.66mmol/L, and the solution is dissolved at 55 ℃;
6) Adding the octadecene solution of the 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 30min;
7) And adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nanoparticle solution dispersed in chloroform.
The iron-doped copper sulfide nano particles prepared in the embodiment are characterized, a transmission electron microscope image is shown in fig. 1, and the prepared doped copper sulfide nano particles are uniform in size and good in dispersibility. The absorption spectrum is shown in figure 2, and the prepared iron-doped copper sulfide nano particle can control the absorption peak to be in the vicinity of 1064 nm. The EDS spectrum analysis chart is shown in fig. 3, and shows that the iron element is successfully doped into the copper sulfide nano particles. The X-ray diffraction pattern is shown in FIG. 4, which shows that the product is copper indigotite type sulfide, rather than CuFeS 2 And Cu 5 FeS 4 And (3) an isomorphous form.
Example two, preparation of iron-doped copper sulfide nanoparticle
1) Dissolving sulfur powder in oleic acid, wherein the concentration of the sulfur powder solution is 200mmol/L, heating to completely dissolve 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 the 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 1h;
4) Adding ethanol into the reaction solution for sedimentation, centrifugally collecting copper sulfide sediment, and dispersing the copper sulfide sediment 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 the oleylamine in the mixed solution is 33.3%, the concentration of the ferric acetylacetonate is 6.66mmol/L, and the solution is dissolved at 55 ℃;
6) Adding the copper sulfide octadecene 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 30min;
7) And adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nanoparticle solution dispersed in chloroform.
The iron-doped copper sulfide nano-particles prepared in the embodiment are characterized, an absorption spectrum is shown in fig. 2, and the prepared nano-particles have an absorption peak near 1000nm, and have obvious blue shift compared with the embodiment I.
Embodiment III, preparation of iron-doped copper sulfide nanoparticle
1) Dissolving sulfur powder in octadecene, wherein the concentration of the sulfur powder solution is 200mmol/L, heating to completely dissolve 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 the 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 1h;
4) Adding ethanol into the reaction solution for sedimentation, centrifugally collecting copper sulfide sediment, and dispersing the copper sulfide sediment 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 the oleylamine in the mixed solution is 33.3%, the concentration of the ferric acetylacetonate is 6.66mmol/L, and the solution is dissolved at 55 ℃;
6) Adding the copper sulfide octadecene 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 30min;
7) And adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nanoparticle solution dispersed in chloroform.
The iron-doped copper sulfide nano-particles prepared in the embodiment are characterized, an absorption spectrum is shown as a graph in fig. 2, and the absorption peak of the prepared iron-doped copper sulfide nano-particles is near 1200nm, so that the iron-doped copper sulfide nano-particles have obvious red shift compared with the embodiment.
Example IV, preparation of 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 completely dissolve 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 the 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 1h;
4) Adding ethanol into the reaction solution for sedimentation, centrifugally collecting copper sulfide sediment, and dispersing the copper sulfide sediment 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 the oleylamine in the mixed solution is 33.3%, the concentration of the ferric acetylacetonate is 3.33mmol/L, and the solution is dissolved at 55 ℃;
6) Adding the copper sulfide octadecene 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 0.1:1, heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 30min;
7) And adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nanoparticle solution dispersed in chloroform.
Characterization of the iron-doped copper sulfide nanoparticles prepared in this example shows that elemental iron can be successfully doped into copper sulfide nanoparticles.
Fifth embodiment, preparation of 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 completely dissolve 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 the 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 1h;
4) Adding ethanol into the reaction solution for sedimentation, centrifugally collecting copper sulfide sediment, and dispersing the copper sulfide sediment 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 the oleylamine in the mixed solution is 33.3%, the concentration of the ferric acetylacetonate is 16.7mmol/L, and the ferric acetylacetonate is dissolved at 55 ℃;
6) Adding the copper sulfide octadecene solution obtained in the step 4) into the solution obtained in the step 5) to ensure that the molar ratio of iron to copper is 1:1, heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 30min;
7) And adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nanoparticle 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, and the absorption spectrum of the obtained material is shown in fig. 5, and it can be seen from the graph that under the condition of high iron/copper molar ratio, the sample can still maintain excellent LSPR absorption.
Example six preparation of ferrous 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 completely dissolve 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 the 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 1h;
4) Adding ethanol into the reaction solution for sedimentation, centrifugally collecting copper sulfide sediment, and dispersing the copper sulfide sediment 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 the 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 octadecene solution obtained in the step 4) into the solution obtained in the step 5) to enable the molar ratio of ferrous iron to copper to be 0.2:1, heating to 120 ℃ under the protection of nitrogen, and maintaining the reaction for 30min;
7) And adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the iron-doped copper sulfide nanoparticle solution dispersed in chloroform.
The iron-doped copper sulfide nano particles prepared by the embodiment are characterized in that the iron (II) element can be successfully doped into the copper sulfide nano particles, and the obtained doped copper sulfide nano particles are uniform in size and good in dispersibility.
Embodiment seven, preparation of manganese-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 completely dissolve 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 the 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 1h;
4) Adding ethanol into the reaction solution for sedimentation, centrifugally collecting copper sulfide sediment, and dispersing the copper sulfide sediment 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 the oleylamine in the mixed solution is 33.3%, the concentration of the manganese acetylacetonate is 6.66mmol/L, and the solution is dissolved at 55 ℃;
6) Adding the copper sulfide octadecene 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 30min;
7) And adding ethanol into the reaction solution for sedimentation, centrifugally washing, and dispersing in chloroform to obtain the manganese-doped copper sulfide nanoparticle solution dispersed in chloroform.
Characterization of the manganese-doped copper sulfide nanoparticles prepared in this example shows that manganese (ii) element can be successfully doped into copper sulfide nanoparticles.
Example eight preparation of doped copper sulfide nanoparticle aqueous solution:
taking 0.5mL of the chloroform solution (12.8 mg/mL) of the iron-doped copper sulfide nano particles prepared in the fifth embodiment, dropwise adding the chloroform solution into ultrapure water (4 mL) containing DSPE-PEG5000 (35 mg) while stirring, and stirring by ultrasonic waves to uniformly disperse; and 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 was verified and tested as follows:
1. near infrared two-zone photoacoustic imaging
An iron-doped copper sulfide nanoparticle aqueous solution with the concentration of 1.0mg/mL is prepared, 200 mu L is taken in a small test tube, and then imaging is carried out by a photoacoustic imager, as shown in fig. 6, and the result shows that the nanoparticle has excellent photoacoustic imaging capability.
2. Testing of photo-thermal properties
The influence of different concentrations on the photo-thermal conversion effect of the iron-doped copper sulfide nanoparticle aqueous solution is studied. Respectively preparing iron-doped copper sulfide nano particle (10, 20, 35, 50 mug/mL) solutions with different concentrations, and measuring that the mass light absorption coefficient at 1064nm can reach 23.2 L.g -1 . 200. Mu.L of the solution was placed in a 200. Mu.L centrifuge tube, and a 1064nm laser was used as an excitation light source with a laser power density set at 1W/cm 2 Irradiating for 10min, and reading the temperature of the solution by using a thermal infrared imager. The above experiment was repeated with pure water as a reference. The experimental results are shown in FIG. 7, which shows that the temperature of the nanoparticle solution is obviously increased along with the increase of the concentration of the material, and the laser power density is 1W/cm 2 Under the condition of 35ug/mL solution temperature reaching more than 65 degrees, the photo-thermal conversion efficiency reaching 42.7 percent, which shows that the iron-doped copper sulfide nano particle has good photo-thermal property.
2. Chemical kinetics Performance test
Iron-doped CuS nanoparticles (10 μg/mL) were dispersed in phosphate buffer (0.01 m,2 mL) at ph=5.5, TMB (0.4 mM) and H were added 2 O 2 (10 mM). The absorption spectra of the test mixtures were sampled at 0min, 10min, 20min, 30min, respectively. The experimental results show that the absorbance of the absorption spectrum at 652nm is obviously increased 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 kinetics.
The foregoing has outlined and described the basic principles, features, and advantages of the present invention. However, the foregoing is merely specific examples of the present invention, and the technical features of the present invention are not limited thereto, and any other embodiments that are derived by those skilled in the art without departing from the technical solution of the present invention are included in the scope of the present invention.
Claims (6)
1. The preparation method of the ion doped copper sulfide nano particle is characterized by comprising the following steps of:
s1, adding sulfur powder into a mixed solution of oleic acid and octadecene, heating to completely dissolve under the protection of nitrogen, and then cooling the solution to 55 ℃;
s2, adding copper acetylacetonate into a 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, and heating to 80-140 ℃ under the protection of nitrogen o C, maintaining the reaction for 1-2 h;
s4, adding ethanol into the reaction solution for sedimentation, centrifugally collecting copper sulfide sediment, and dispersing the copper sulfide sediment in octadecene to obtain copper sulfide solution;
s5, adding ferric salt or manganese salt solution into the mixed solution of oleylamine and octadecene, and dissolving at 55 ℃;
s6, adding the copper sulfide octadecene solution obtained in the step S4 into the solution obtained in the step S5, and heating to 80-140 ℃ under the protection of nitrogen o C, maintaining the reaction for 20-40 min;
s7, adding ethanol into the reaction solution for sedimentation, and dispersing in chloroform after centrifugal washing to obtain an ion doped copper sulfide nanoparticle solution dispersed in chloroform;
in the step S5, the molar ratio of the ferric salt or the manganese salt to the copper acetylacetonate is 0.1-1:1.
2. The method for preparing ion-doped copper sulfide nanoparticles according to claim 1, wherein in the step S1, the concentration of the sulfur powder solution is 180-200 mmol/L.
3. The method for preparing ion-doped copper sulfide nanoparticles according to claim 1, wherein in the step S3, a 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 acetylacetonate ii.
5. An ion-doped copper sulfide nanoparticle, wherein the nanoparticle is prepared by the method of any one of claims 1 to 4.
6. Use of the ion-doped copper sulphide nanoparticles according to claim 5 for the preparation of a tumor combination therapeutic agent or tool.
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