CN116809947B - Method for preparing Au nano-rod by imidazole and/or cyclic quaternary ammonium salt surfactant - Google Patents
Method for preparing Au nano-rod by imidazole and/or cyclic quaternary ammonium salt surfactant Download PDFInfo
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- 239000002073 nanorod Substances 0.000 title claims abstract description 81
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 64
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- 238000000034 method Methods 0.000 title claims abstract description 35
- -1 cyclic quaternary ammonium salt Chemical class 0.000 title claims abstract description 25
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- 150000002500 ions Chemical class 0.000 claims abstract description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 18
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 239000002253 acid Substances 0.000 claims abstract description 11
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- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- URRISVSZHXGKJJ-UHFFFAOYSA-M cyclohexyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C1CCCCC1 URRISVSZHXGKJJ-UHFFFAOYSA-M 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 6
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 5
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-methylmorpholine Substances CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- UTCSSFWDNNEEBH-UHFFFAOYSA-N imidazo[1,2-a]pyridine Chemical compound C1=CC=CC2=NC=CN21 UTCSSFWDNNEEBH-UHFFFAOYSA-N 0.000 claims 2
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- 239000000203 mixture Substances 0.000 description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
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- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- ORIZJEOWAFVTGA-UHFFFAOYSA-N 1-hexadecylimidazole Chemical compound CCCCCCCCCCCCCCCCN1C=CN=C1 ORIZJEOWAFVTGA-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- NYDGOZPYEABERA-UHFFFAOYSA-N 5-chloro-1-methylimidazole Chemical compound CN1C=NC=C1Cl NYDGOZPYEABERA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing Au nanorods by imidazole and/or cyclic quaternary ammonium salt surfactant, which comprises the following steps: (1) Providing a surfactant, wherein the surfactant is imidazole quaternary ammonium salt and/or cyclic quaternary ammonium salt; (2) Preparing the surfactant into a surfactant aqueous solution; (3) Mixing a part of the aqueous solution of the surfactant with a solution containing Au ions, and adding citric acid and NaBH 4 A solution, forming an Au seed solution; (4) Heating the Au seed solution in a water bath to obtain Au seeds; (5) Mixing the other part of the surfactant aqueous solution with silver ion solution and Au ion-containing solution, adding acid liquor, and then adding the Au seeds to prepare the Au nanorods. The Au nano rod with controllable size is prepared by the invention, the longitudinal absorption spectrum can reach about 900nm, the Au nano rod can be dispersed in water-based solution for a long time, the agglomeration phenomenon is avoided, and the cytotoxicity is low.
Description
Technical Field
The invention belongs to the technical field of functional structure nano material preparation, and particularly relates to a method for preparing an Au nano rod by using imidazole and/or cyclic quaternary ammonium salt surfactant.
Background
Au particles are a nanomaterial with good biocompatibility. The structures of Au nanospheres, nanoclusters, nanorods, nanosatellites and the like have been widely studied in terms of biological imaging, contrast agents, fluorescent probes, drug carriers, photothermal treatment and the like due to the surface properties of the Au nanospheres, nanoclusters, nanorods, nanosatellites and the like. The Au nano rod has the transverse and longitudinal plasma resonance absorption, wherein the longitudinal absorption position is adjustable according to the length-diameter ratio of the nano rod, and can be controlled in an infrared two-region at present>1100cm -1 ) Within the range. The infrared light has strong tissue penetrating power and can reach the body groupThe deep position of the tissue can be heated to 43-45 ℃ within a few minutes, so that the effect of killing cancer cells is achieved.
The current preparation method of Au nanorods is mainly to lead the heterogeneous growth formation of the Au nanorods through a surfactant Cetyl Trimethyl Ammonium Bromide (CTAB). The concentration, ratio of the various materials in the preparation process, the pH value of the solution, the reaction time and the like have important influences on the size of the finally formed nanorods. In the prior art, surfactant head groups are found to have a certain influence on the generated nanorods, and the research on the surfactant head groups is relatively few. In the application of Au nanorods prepared by CTAB-based surfactant, CTAB has stronger toxicity to cells, so that the CTAB can be removed by adopting a surface treatment method to be applied to the biological field. However, this removal process is complicated in steps and sometimes CTAB is not completely removed, so a new method of preparing Au nanorods is required to achieve low toxicity.
Disclosure of Invention
In view of the problems of the prior art, in a first aspect, the present invention aims to provide a method for preparing Au nanorods by using imidazole and/or cyclic quaternary ammonium salt surfactants. In a second aspect, the present invention aims to provide a low toxicity Au nanorod. In a third aspect, the present invention aims to provide the use of a low toxicity Au nanorod. The invention provides a method for preparing Au nano-rods with controllable size by utilizing imidazole quaternary ammonium salt and/or cyclic quaternary ammonium salt, which can be applied to the biomedical industry such as photothermal therapy and the like. The invention can prepare the Au nano-rod with controllable size, and reduces the surface toxicity of the Au nano-rod by selecting the surfactant with a certain functional group. The methods or uses of the invention are for non-diagnostic and non-therapeutic purposes of disease.
The invention adopts the following technical scheme:
in a first aspect, the present application provides a method for preparing Au nanorods from imidazole and/or cyclic quaternary ammonium salt surfactants, the method comprising the steps of:
(1) Providing a surfactant, wherein the surfactant is imidazole quaternary ammonium salt and/or cyclic quaternary ammonium salt;
(2) Preparing the surfactant into a surfactant aqueous solution;
(3) Mixing a part of the aqueous solution of the surfactant with a solution containing Au ions, and adding citric acid and NaBH 4 A solution, forming an Au seed solution;
(4) Heating the Au seed solution in a water bath to obtain Au seeds;
(5) Mixing the other part of the surfactant aqueous solution with silver ion solution and Au ion-containing solution, adding acid liquor, and then adding the Au seeds to prepare the Au nanorods.
In combination with the first aspect, in some possible embodiments, the substituted imidazole and/or substituted tertiary amine is mixed with 1-bromohexadecane in an organic solvent, and then refluxed for 24 hours to 48 hours, and the organic solvent is removed to obtain the surfactant.
In combination with the first aspect, in some possible embodiments, the imidazole with substituents and/or the tertiary amine with substituents is mixed with 1-bromohexadecane in an organic solvent, then refluxed for 24 to 48 hours, the organic solvent is removed to obtain a crude product, and the surfactant is obtained after recrystallization, washing and drying.
For purposes of example and not limitation, in some embodiments, the organic solvent is at least one of acetonitrile, methanol, ethanol, ethyl acetate.
For purposes of illustration and not limitation, in some embodiments imidazoles with different substituents (avoiding substitution of large functional groups at both the 4,5 positions) and/or various tertiary amines (e.g., about 1.0 eq) are mixed with 1-bromohexadecane (e.g., about 1.0 eq) in an organic solvent (e.g., acetonitrile). The mixture was refluxed for 24 hours to 48 hours. Removing the organic solvent by rotary evaporation to obtain oily or solid crude product, recrystallizing with ethyl acetate and/or petroleum ether, filtering, washing with petroleum ether, and drying at 40-60deg.C to obtain the final product.
With reference to the first aspect, in some possible embodiments, the surfactant comprises at least one of N-hexadecyl 1-methylimidazole bromide, N-hexadecyl 1-methyl 5-chloroimidazole bromide, N-hexadecyl 1-t-butylimidazole bromide, N-hexadecyl 1-phenylimidazole bromide, N-hexadecyl imidazo [1,2a ] pyridine, N-hexadecyl 4-methylmorpholine bromide, N-hexadecyl 1-methylpiperidine bromide, N-hexadecyl 1-methylpyrrolidine bromide, N-hexadecyl triethylenediamine bromide, N-hexadecyl dimethylcyclohexylammonium bromide.
Alternatively, in some possible embodiments, the surfactant comprises at least one of N-hexadecyl 1-methylimidazole bromide, N-hexadecyl 1-methyl 5-chloroimidazole bromide, N-hexadecyl 1-t-butylimidazole bromide, N-hexadecyl 1-phenylimidazole bromide, N-hexadecyl imidazo [1,2a ] pyridine bromide, N-hexadecyl 4-methylmorpholine bromide, N-hexadecyl 1-methylpiperidine bromide, N-hexadecyl 1-methylpyrrolidine bromide, N-hexadecyl triethylenediamine bromide, N-hexadecyl dimethylcyclohexylammonium bromide.
With reference to the first aspect, in some possible embodiments, the concentration of the aqueous surfactant solution in step (3) is from 0.01mol/L to 0.5mol/L, for example from 0.05mol/L to 0.2mol/L, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5mol/L, etc., but is not limited to the recited values, other non-recited values or ranges within the range of values are equally applicable.
With reference to the first aspect, in some possible embodiments, the concentration of the aqueous surfactant solution in step (5) is from 0.01mol/L to 0.5mol/L, for example from 0.05mol/L to 0.15mol/L, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5mol/L, etc., but is not limited to the recited values, other non-recited values or ranges within the range of values are equally applicable.
With reference to the first aspect, in some possible embodiments, the concentration of the silver ion solution is 1mmol/L to 10mmol/L, for example, 1,2, 3, 4,5, 6, 7, 8, 9, 10mmol/L, etc., but is not limited to the recited values, and other non-recited values or ranges within the range of values are equally applicable.
With reference to the first aspect, in some possible embodiments, the concentration of the solution containing Au ions in step (3) is 1mmol/L to 50mmol/L, for example, 1,2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50mmol/L, etc., but is not limited to the recited values, and other non-recited values or ranges within the range of values are equally applicable.
With reference to the first aspect, in some possible embodiments, the concentration of the solution containing Au ions in step (5) is 0.1mmol/L to 5mmol/L, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1,2, 3, 4, 5mmol/L, etc., but is not limited to the recited values, and other non-recited values or ranges within the range of values are equally applicable.
With reference to the first aspect, in some possible embodiments, the concentration of the hydroquinone solution is from 0.1mol/L to 1mol/L, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1mol/L, etc., but is not limited to the recited values, and other non-recited values or ranges within the range of values are equally applicable.
With reference to the first aspect, in some possible embodiments, the NaBH 4 The concentration of the solution is 1mmol/L to 50mmol/L, for example, 1,2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50mmol/L, etc., but is not limited to the recited values, and other non-recited values or ranges within the recited values are equally applicable.
With reference to the first aspect, in some possible embodiments, the silver ion solution comprises a silver nitrate solution.
Bonding ofIn a first aspect, in some possible embodiments, the Au ion-containing solution comprises or is HAuCl 4 A solution.
With reference to the first aspect, in some possible embodiments, the acid solution comprises hydrochloric acid and/or ascorbic acid.
With reference to the first aspect, in some possible embodiments, the temperature of the water bath heating in step (4) is from 70 ℃ to 90 ℃, e.g. 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90 ℃.
With reference to the first aspect, in some possible embodiments, after adding the Au seeds in step (5), standing in a water bath at 30 ℃ to 40 ℃ for 18 hours to 24 hours, to prepare the Au nanorods.
With reference to the first aspect, in some possible embodiments, synthesis of the seed: adding HAuCl into a centrifuge tube 4 Mixing the solution with surfactant solution at room temperature, adding citric acid solution, and adding freshly prepared cold NaBH 4 A solution. The mixture turned from pale yellow to brown, indicating the formation of gold seeds. The seed solution was then heated in a water bath to gradually change the color of the seed solution from brown to red. Finally, the heat-treated seed solution was removed from the bath and stored at room temperature.
Preparing a growth solution: adding AgNO into a centrifuge tube 3 Solution, aqueous surfactant solution, and then adding HAuCl 4 The solution was mixed by shaking vigorously. To this solution was added aqueous hydrochloric acid and ascorbic acid and the resulting mixture was vigorously shaken until clear. Finally, the seeds prepared before are added, mixed by shaking vigorously and then left to stand in a water bath overnight.
And finally adding a certain amount of synthesized seeds, shaking vigorously, mixing, and standing in a water bath overnight.
According to a first aspect, as an alternative embodiment, the present application provides a method for preparing Au nanorods from imidazole and/or cyclic quaternary ammonium salt surfactants, the method comprising the steps of:
(1) Providing a surfactant, wherein the surfactant is imidazole quaternary ammonium salt and/or cyclic quaternary ammonium salt;
(2) Preparing the surfactant into a surfactant aqueous solution;
(3) Mixing the surfactant aqueous solution with silver ion solution and Au ion-containing solution, adding acid solution, hydroquinone solution and NaBH 4 And (3) preparing a solution to obtain the Au nanorod.
In an alternative embodiment, the substituted imidazole and/or substituted tertiary amine is mixed with 1-bromohexadecane in an organic solvent and then refluxed for 24 hours to 48 hours, and the organic solvent is removed to obtain the surfactant.
In an alternative embodiment, the imidazole with substituents and/or tertiary amine with substituents is mixed with 1-bromohexadecane in an organic solvent, then refluxed for 24 to 48 hours, the organic solvent is removed to obtain a crude product, and the surfactant is obtained after recrystallization, washing and drying.
For purposes of example and not limitation, in some embodiments, the organic solvent is at least one of acetonitrile, methanol, ethanol, ethyl acetate.
In alternative embodiments, the surfactant comprises at least one of N-hexadecyl 1-methylimidazole bromide, N-hexadecyl 1-methyl 5-chloroimidazole bromide, N-hexadecyl 1-t-butylimidazole bromide, N-hexadecyl 1-phenylimidazole bromide, N-hexadecyl imidazo [1,2a ] pyridine, N-hexadecyl 4-methylmorpholine bromide, N-hexadecyl 1-methylpiperidine bromide, N-hexadecyl 1-methylpyrrolidine bromide, N-hexadecyl triethylenediamine bromide, N-hexadecyl dimethylcyclohexylammonium bromide.
In alternative embodiments, the surfactant comprises at least one of N-hexadecyl 1-methylimidazole bromide, N-hexadecyl 1-methyl 5-chloroimidazole bromide, N-hexadecyl 1-t-butylimidazole bromide, N-hexadecyl 1-phenylimidazole bromide, N-hexadecyl imidazo [1,2a ] pyridine, N-hexadecyl 4-methylmorpholine bromide, N-hexadecyl 1-methylpiperidine bromide, N-hexadecyl 1-methylpyrrolidine bromide, N-hexadecyl triethylenediamine bromide, N-hexadecyl dimethylcyclohexylammonium bromide.
In alternative embodiments, the aqueous surfactant solution has a concentration of 0.01 to 0.5mol/L, such as 0.05 to 0.2mol/L, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5mol/L, etc., but is not limited to the recited values, as other non-recited values or ranges within the recited range of values are equally applicable.
In alternative embodiments, the concentration of the silver ion solution is 1mmol/L to 10mmol/L, e.g., 1,2, 3, 4,5, 6, 7, 8, 9, 10mmol/L, etc., but is not limited to the recited values, as other non-recited values or ranges within the range of values are equally applicable.
In alternative embodiments, the concentration of the Au ion-containing solution is 1mmol/L to 50mmol/L, e.g., 1,2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50mmol/L, etc., but is not limited to the recited values, as other non-recited values or ranges within the range of values are equally applicable.
In alternative embodiments, the concentration of the hydroquinone solution is from 0.1mol/L to 1mol/L, e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1mol/L, etc., but is not limited to the recited values, as other non-recited values or ranges within the range of values are equally applicable.
In an alternative embodiment, the NaBH 4 The concentration of the solution is 1mmol/L to 50mmol/L, for example, 1,2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50mmol/L, etc., but is not limited to the exemplified valuesOther non-recited values or ranges within this range are equally applicable.
In an alternative embodiment, the silver ion solution comprises a silver nitrate solution.
In an alternative embodiment, the Au ion-containing solution comprises or is HAuCl 4 A solution.
In an alternative embodiment, the acid solution comprises hydrochloric acid.
In an alternative embodiment, the aqueous surfactant solution is mixed with silver ion solution and Au ion-containing solution in step (3), and acid solution, hydroquinone solution and NaBH are added 4 The solution is mixed and then kept stand in a water bath at 30-40 ℃ for overnight, and the Au nano-rod is prepared.
For purposes of illustration and not limitation, in some embodiments, silver nitrate, a concentration of an aqueous surfactant solution, and HAuCl are gradually added to a centrifuge tube 4 The solutions were mixed. An amount of hydrochloric acid and an aqueous solution of hydroquinone were added and the resulting mixture was vigorously shaken until clear. Finally adding cold freshly prepared NaBH 4 The aqueous solution was finally stirred to homogenize the mixed solution and allowed to stand overnight in a water bath.
In a second aspect, the present application provides Au nanorods prepared according to the aforementioned method.
In a third aspect, the application provides the use of the Au nanorods in the manufacture of a medicament for treating cancer.
With reference to the third aspect, in some possible embodiments, the cancer may be liver cancer, e.g. treating HepG2 cells.
The term "plurality" as used herein includes two, three, four or more, and the like.
The external environment referred to herein generally refers to conditions at room temperature, which may be, for example, 15 ℃ to 35 ℃, but is not intended to exclude other conditions. In the actual course of operation, the temperature of the experimental conditions will vary according to the specific needs.
The normal temperature referred to herein is typically, but not exclusively, 15 ℃ to 35 ℃.
Unless otherwise specified herein, the purity grade of a substance purchased or used herein is chemically pure, analytically pure, or preferably is superior pure, more preferably is superior pure.
Compared with the prior art, the invention has the beneficial effects that:
the Au nano-rods with controllable size are prepared from the imidazole quaternary ammonium salt and/or the cyclic quaternary ammonium salt, the longitudinal absorption spectrum can reach about 900nm, the Au nano-rods can be dispersed in water-based solution for a long time, no agglomeration phenomenon occurs after the Au nano-rods are placed for at least 7 to 10 days, and the cytotoxicity of the Au nano-rods protected by a plurality of surfactants in high dosage is obviously lower than that of the Au nano-rods protected by CTAB.
Drawings
Fig. 1 shows a TEM image of Au nanorods prepared in example 1;
fig. 2 shows a TEM image of Au nanorods prepared in example 4;
FIG. 3 shows the absorption spectra of Au nanorods prepared in N-hexadecyl 1-methylimidazole bromide (MIB) and N-hexadecyl 1-methylpyrrole bromide (MPD) solutions, respectively.
Detailed Description
In order to better explain the present invention, embodiments of the present application will be described in detail with reference to specific examples, but those skilled in the art will understand that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Unless defined otherwise, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.
The use of any and all examples, or exemplary language (such as, for example, ") provided herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention unless explicitly stated.
As used in this application, the term "about" is used to describe and illustrate small variations. When used in connection with an event or circumstance, the terms can refer to instances where the event or circumstance occurs precisely and instances where it occurs to the close approximation. For example, when used in connection with a numerical value, the term can refer to a range of variation of less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. Additionally, amounts, ratios, and other numerical values are sometimes presented herein in a range format. It is to be understood that such range format is used for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
The exemplary invention described herein may suitably lack any one or more of the element limitations not specifically disclosed herein. Thus, the terms "comprising," "including," "containing," and the like are to be construed broadly and without limitation. In addition, the term expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms of description not including any equivalents of the features shown and described, but rather, in accordance with the claims, various modifications are possible within the scope of the invention. Thus, while the invention has been specifically disclosed by preferred embodiments and optional features, modification of the invention disclosed herein may be resorted to by those skilled in the art, and such modifications and variations are considered to be within the scope of this invention.
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 10" are disclosed, the described ranges should be interpreted to include ranges of "1 to 10", "1 to 9", "1 to 8", "1 to 7", "1 to 6", "1 to 5", "1 to 4", "1 to 3", "1 to 2", "1 to 3 and 5 to 10", "1 to 4 and 8", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In the detailed description and claims, a list of items connected by the terms "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means only a; only B; or A and B. In another example, if items A, B and C are listed, then the phrase "at least one of A, B and C" means only a; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements.
Furthermore, the terms "first," "second," "third," and the like, as used herein, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying a number of technical features which are indicated. Thus, a feature defining "a first", "a second", and "a third" may explicitly or implicitly include at least one such feature. In the description of the embodiments of the present disclosure, the meaning of "plurality" is at least two, such as two, three, etc., unless explicitly specified otherwise.
Example 1
A method for preparing Au nano-rods with low toxicity comprises the step of preparing the Au nano-rods in N-hexadecyl brominated 1-methylimidazole solution.
0.1mol of 1-methylimidazole and 0.1mol of bromohexadecane were mixed in acetonitrile, and the mixture was allowed to react well under stirring at 80℃for 24 hours. The solvent was removed by rotary evaporation. Recrystallizing with ethyl acetate, filtering, washing with petroleum ether, and drying at 50deg.C to obtain the product N-hexadecyl 1-methylimidazole bromide.
Into a centrifuge tube, 300. Mu.L of 4mM silver nitrate was added followed by 10mL (0.075M) of the N-hexadecyl brominated 1-methylimidazole solution prepared above, and 500. Mu.L of 10mM HAuCl 4 The solution was then added with 10. Mu.L hydrochloric acid and 660. Mu.L, 0.24M hydroquinone (hydroquinone) and vigorously stirred until the solution became clear. Subsequently, freshly prepared NaBH was added at about 5 ℃ 4 (20. Mu.L, 10 mM) aqueous solution, and the mixture was stirred and allowed to stand in a water bath at 35℃overnight to give a low-toxicity Au nanorod. The embodiment preparesThe Au nano-rod with controllable size can be dispersed in water-based solution for a long time, no agglomeration phenomenon occurs after being placed for 10 days, and the cytotoxicity in high dosage is obviously lower than that of the Au nano-rod protected by CTAB.
FIG. 1 shows a TEM image (scale 50 nm) of Au nanorods prepared in a solution of N-hexadecyl 1-methylimidazole bromide.
Example 2
A method for preparing Au nano-rods with low toxicity comprises the step of preparing Au nano-rods in N-hexadecyl 1-methyl 5-chloroimidazole bromide solution.
0.1mol of 1-methyl-5-chloroimidazole and 0.1mol of bromohexadecane were mixed in acetonitrile and reacted sufficiently under stirring at 80℃for 24 hours. The solvent was removed by rotary evaporation. Recrystallizing with ethyl acetate, filtering, washing with petroleum ether, and drying at 50deg.C to obtain the product N-hexadecyl 1-methyl-5-chloroimidazole bromide.
Into a centrifuge tube, 300. Mu.L of 4mM silver nitrate was added, followed by 10mL (0.1M) of the N-hexadecyl brominated 1-methyl 5-chloroimidazole solution prepared above, and 500. Mu.L of 10mM HAuCl 4 The solution was then added with 10. Mu.L hydrochloric acid and 660. Mu.L, 0.24M hydroquinone (hydroquinone) and vigorously stirred until the solution became clear. Subsequently, freshly prepared NaBH was added at about 5 ℃ 4 (20. Mu.L, 10 mM) aqueous solution, and the mixture was stirred and allowed to stand in a water bath at 35℃overnight to give a low-toxicity Au nanorod. The Au nano-rod with controllable size can be dispersed in water-based solution for a long time, no agglomeration phenomenon occurs after the Au nano-rod is placed for 10 days, and cytotoxicity in high dosage is obviously lower than that of the Au nano-rod protected by CTAB.
Example 3
A method for preparing Au nano-rods with low toxicity comprises the step of preparing Au nano-rods in N-hexadecyl 1-methylpiperidine bromide solution.
0.1mol of 1-methylpiperidine and 0.1mol of bromohexadecane were mixed in acetonitrile and reacted sufficiently under stirring at 80℃for 24 hours. The solvent was removed by rotary evaporation. Recrystallizing with ethyl acetate, filtering, washing with petroleum ether, and drying at 50deg.C to obtain the product N-hexadecyl 1-methylpiperidine bromide.
Into a centrifuge tube, 600. Mu.L of 4mM silver nitrate was added, followed by 10mL (0.1M) of the N-hexadecyl brominated 1-methylpiperidine solution prepared above, and 500. Mu.L of 10mM HAuCl 4 The solution was then added with 10. Mu.L hydrochloric acid and 660. Mu.L, 0.24M hydroquinone (hydroquinone) and vigorously stirred until the solution became clear. Subsequently, freshly prepared NaBH was added at about 5 ℃ 4 (5. Mu.L, 10 mM) aqueous solution, and the mixture was stirred and allowed to stand in a water bath at 35℃overnight to give a low-toxicity Au nanorod. The Au nano-rod with controllable size can be dispersed in water-based solution for a long time, no agglomeration phenomenon occurs after the Au nano-rod is placed for 10 days, and cytotoxicity in high dosage is obviously lower than that of the Au nano-rod protected by CTAB.
Example 4
A method for preparing Au nano-rods with low toxicity comprises the step of preparing Au nano-rods in N-hexadecyl brominated 1-methylpyrrole solution.
0.1mol of 1-methylpyrrole and 0.1mol of bromohexadecane were mixed in acetonitrile and reacted sufficiently under stirring at 80℃for 24 hours. The solvent was removed by rotary evaporation. Recrystallizing with ethyl acetate, filtering, washing with petroleum ether, and drying at 50deg.C to obtain the product N-hexadecyl 1-methylpyrrolidine bromide.
10mM HAuCl was added to a 15ml centrifuge tube 4 After mixing 240. Mu.L of the solution with 10mL of 0.1M N-hexadecyl brominated 1-methylpyrrolidine solution vigorously at room temperature, 2mL of 0.1M citric acid solution was added, followed by 500. Mu.L of freshly prepared cold 0.1M NaBH 4 The solution, the mixture turned from pale yellow to brown. Then heating the seed solution in water bath at 80 ℃ for 3-4 h to change the color of the seed solution from brown to red gradually, and preserving at room temperature for standby.
Into a 15ml centrifuge tube, 4mM AgNO was added 3 500. Mu.L of solution, 8ml of 0.1M aqueous solution of N-hexadecyl 1-methylpyrrolidine bromide, and then 0.48mM of HAuCl were added 4 8mL of the solution, and shaking vigorously to mix. Then, 100. Mu.L of hydrochloric acid and 120. Mu.L of a 0.1M aqueous solution of ascorbic acid were added, and the resulting mixture was vigorously shaken until clear. Finally adding 200 mu L of the prepared seed solution, shaking vigorously, mixing, and adding 35 ℃ waterStanding in bath overnight to obtain low toxicity Au nanorods. The Au nano-rod with controllable size can be dispersed in water-based solution for a long time, no agglomeration phenomenon occurs after the Au nano-rod is placed for 10 days, and cytotoxicity in high dosage is obviously lower than that of the Au nano-rod protected by CTAB.
Fig. 2 shows TEM pictures (scale 50 nm) of Au nanorods prepared in a solution of N-hexadecyl bromo 1-methylpyrrole.
FIG. 3 shows the absorption spectra of Au nanorods prepared in N-hexadecyl 1-methylimidazole bromide (MIB) and N-hexadecyl 1-methylpyrrole bromide (MPD) solutions, respectively.
Example 5
A method for preparing Au nano-rods with low toxicity comprises the step of preparing Au nano-rods in N-hexadecyl brominated 4-methylmorpholine solution.
0.1mol of 4-methylmorpholine is mixed with 0.1mol of bromohexadecane in acetonitrile, and the mixture is stirred and maintained at 80 ℃ for complete reaction for 24 hours. The solvent was removed by rotary evaporation. Recrystallizing with ethyl acetate, filtering, washing with petroleum ether, and drying at 50deg.C to obtain the product N-hexadecyl 4-methylmorpholine bromide.
10mM HAuCl was added to a 15ml centrifuge tube 4 After mixing 240. Mu.L of the solution with 10mL of a 0.1M solution of N-hexadecyl brominated 4-methylmorpholine vigorously at room temperature, 2mL of a 0.2M citric acid solution was added, followed by 500. Mu.L of freshly prepared cold 0.1M NaBH 4 The solution, the mixture turned from pale yellow to brown. Then heating the seed solution in water bath at 80 ℃ for 3-4 h to change the color of the seed solution from brown to red gradually, and preserving at room temperature for standby.
Into a 15ml centrifuge tube, 4mM AgNO was added 3 300. Mu.L of solution, 5ml of 0.1M aqueous solution of N-hexadecyl 4-methylmorpholine bromide, and then 0.48mM of HAuCl were added 4 5mL of the solution, and shaking vigorously to mix. Then, 5. Mu.L of hydrochloric acid and 120. Mu.L of a 0.1M aqueous solution of ascorbic acid were added, and the resulting mixture was vigorously shaken until clear. Finally, 100 mu L of the prepared seed solution is added, and after being mixed by intense shaking, the mixture is stood in a water bath at 35 ℃ for overnight to obtain the low-toxicity Au nano-rod. The present example prepares the dimensionsThe controllable Au nano-rod can be dispersed in a water-based solution for a long time, no agglomeration phenomenon occurs after the Au nano-rod is placed for 10 days, and the cytotoxicity in a high dosage is obviously lower than that of the Au nano-rod protected by CTAB.
Cytotoxicity test
HepG2 cells were selected to test the cytotoxicity of the different Au nanorods. At 6X 10 per well 3 Individual cells (100 μl) were seeded in 96-well plates for 24h, then 10 μl Au nanorod aqueous solution was added, incubation was continued for 24h, and cell viability was tested by MTT method. The concentration of the sample (Au concentration) was 100. Mu.g/mL.
Table 1:
| sample name | Cell viability (%) |
| N-hexadecyl brominated 1-Methylimidazole (MIB) | 72 |
| N-hexadecyl brominated 1-methyl 5-Chloroimidazole (CMI) | 48 |
| N-hexadecyl brominated 1-tert-butylimidazole (TIB) | 30 |
| N-hexadecyl brominated 1-phenylimidazole (MIP) | 32 |
| N-hexadecyl imidazole bromide [1,2a ]]And Pyridine (IAP) | 57 |
| N-hexadecyl 4-methylmorpholine bromide (M)ML) | 41 |
| N-hexadecyl brominated 1-Methylpiperidine (MPP) | 62 |
| N-hexadecyl brominated 1-Methylpyrrolidine (MPD) | 53 |
| N-hexadecyl triethylenediamine bromide (DABCO) | 28 |
| N-hexadecyldimethyl cyclohexylammonium bromide (DCMH) | 59 |
| Cetyl trimethylammonium bromide (CTAB) | 23 |
The foregoing description of the embodiments of the present invention should not be construed as limiting the scope of the invention, but rather should be construed in view of the appended claims, as well as any equivalents thereof, or direct or indirect application in other relevant arts.
For the conditions not specified in the examples, the procedure was carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products available commercially without manufacturer awareness.
Claims (8)
1. A method for preparing Au nanorods by using imidazole and/or cyclic quaternary ammonium salt surfactants, which is characterized by comprising the following steps:
(1) Providing a surfactant which is imidazole quaternary ammonium salt and/or cyclic quaternary ammonium salt, wherein the surfactant is at least one of N-hexadecyl bromide 1-methylimidazole, N-hexadecyl bromide 1-methyl 5-chloroimidazole, N-hexadecyl bromide 1-tertiary butyl imidazole, N-hexadecyl bromide 1-phenylimidazole, N-hexadecyl bromide imidazo [1,2a ] pyridine, N-hexadecyl bromide 4-methylmorpholine, N-hexadecyl bromide 1-methylpiperidine, N-hexadecyl bromide 1-methylpyrrolidine, N-hexadecyl bromide triethylenediamine and N-hexadecyl dimethyl cyclohexyl ammonium bromide;
(2) Preparing the surfactant into a surfactant aqueous solution;
(3) Mixing a part of the aqueous solution of the surfactant with a solution containing Au ions, and adding citric acid and NaBH 4 A solution, forming an Au seed solution;
(4) Heating the Au seed solution in water bath to obtain Au seeds;
(5) Mixing the other part of the surfactant aqueous solution with silver ion solution and Au ion-containing solution, adding acid liquor, and then adding the Au seeds to prepare the Au nanorods.
2. The method according to claim 1, wherein the substituted imidazole and/or the substituted tertiary amine is mixed with 1-bromohexadecane in an organic solvent, and then refluxed for 24 hours to 48 hours, and the organic solvent is removed to obtain the surfactant.
3. The method according to claim 1, wherein the method fulfils at least one of the following conditions a to I:
A. the concentration of the aqueous surfactant solution in step (3) is 0.01mol/L to 0.5mol/L; the concentration of the aqueous surfactant solution in step (5) is 0.01mol/L to 0.5mol/L;
B. the concentration of the silver ion solution is 1mmol/L to 10mmol/L;
C. the concentration of the Au ion-containing solution in the step (3) is 1mmol/L to 50mmol/L; the concentration of the Au ion-containing solution in the step (5) is 0.1mmol/L to 5mmol/L;
D. the NaBH 4 The concentration of the solution was 1mmol/L to 50mmol/L;
E. the silver ion solution comprises a silver nitrate solution;
F. the Au ion-containing solution comprises HAuCl 4 A solution;
G. the acid solution comprises hydrochloric acid and/or ascorbic acid;
H. the water bath heating temperature in the step (4) is 70 ℃ to 90 ℃;
I. and (3) adding the Au seeds in the step (5), and then standing in a water bath at 30-40 ℃ for 18-24 hours to obtain the Au nanorods.
4. An Au nanorod prepared according to the method of any one of claims 1 to 3.
5. A method for preparing Au nanorods by using imidazole and/or cyclic quaternary ammonium salt surfactants, which is characterized by comprising the following steps:
(1) Providing a surfactant which is imidazole quaternary ammonium salt and/or cyclic quaternary ammonium salt, wherein the surfactant is at least one of N-hexadecyl bromide 1-methylimidazole, N-hexadecyl bromide 1-methyl 5-chloroimidazole, N-hexadecyl bromide 1-tertiary butyl imidazole, N-hexadecyl bromide 1-phenylimidazole, N-hexadecyl bromide imidazo [1,2a ] pyridine, N-hexadecyl bromide 4-methylmorpholine, N-hexadecyl bromide 1-methylpiperidine, N-hexadecyl bromide 1-methylpyrrolidine, N-hexadecyl bromide triethylenediamine and N-hexadecyl dimethyl cyclohexyl ammonium bromide;
(2) Preparing the surfactant into a surfactant aqueous solution;
(3) Mixing the surfactant aqueous solution with silver ion solution and Au ion-containing solution, adding acid solution, hydroquinone solution and NaBH 4 And (3) preparing a solution to obtain the Au nanorod.
6. The method according to claim 5, wherein the surfactant is obtained by mixing imidazole having a substituent and/or tertiary amine having a substituent with 1-bromohexadecane in an organic solvent and then refluxing for 24 hours to 48 hours, and removing the organic solvent.
7. The method according to claim 5, wherein the method satisfies at least one of the following conditions a to I:
A. the concentration of the surfactant aqueous solution is 0.01mol/L to 0.5mol/L;
B. the concentration of the silver ion solution is 1mmol/L to 10mmol/L;
C. the concentration of the solution containing Au ions is 1mmol/L to 50mmol/L;
D. the concentration of the hydroquinone solution is 0.1mol/L to 1mol/L;
E. the NaBH 4 The concentration of the solution is 1mmol/L to 50mmol/L;
F. the silver ion solution comprises a silver nitrate solution;
G. the Au ion-containing solution comprises HAuCl 4 A solution;
H. the acid liquid comprises hydrochloric acid;
I. in the step (3), the aqueous solution of the surfactant is mixed with silver ion solution and Au ion-containing solution, and acid liquor, hydroquinone solution and NaBH are added 4 The solution is mixed and then kept stand in a water bath at 30-40 ℃ for overnight, and the Au nano-rod is prepared.
8. Au nanorods prepared according to the method of any one of claims 5-7.
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| US8956440B2 (en) * | 2011-03-18 | 2015-02-17 | William Marsh Rice University | High-yield synthesis of gold nanorods with optical absorption at wavelengths greater than 1000nm using hydroquinone |
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