CN113351876A - Method for preparing water-soluble nano gold - Google Patents
Method for preparing water-soluble nano gold Download PDFInfo
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- CN113351876A CN113351876A CN202110428664.8A CN202110428664A CN113351876A CN 113351876 A CN113351876 A CN 113351876A CN 202110428664 A CN202110428664 A CN 202110428664A CN 113351876 A CN113351876 A CN 113351876A
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- 229910052737 gold Inorganic materials 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 60
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- 239000002253 acid Substances 0.000 claims abstract description 75
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- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 9
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 claims abstract description 8
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- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 238000003860 storage Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
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- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
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- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
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- CBMIPXHVOVTTTL-UHFFFAOYSA-N gold(3+) Chemical compound [Au+3] CBMIPXHVOVTTTL-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2202/00—Treatment under specific physical conditions
- B22F2202/11—Use of irradiation
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a method for preparing water-soluble nano gold, which comprises the following steps: mixing the solution containing chloroauric acid radical ions with micromolecular diketone to obtain a mixed solution, and standing to obtain a water-soluble nano gold solution; the solution containing chloroauric acid radical ions comprises a sodium chloroauric acid solution, a potassium chloroauric acid solution or a chloroauric acid tetrahydrate solution and the like, and the small-molecule diketone comprises 2, 3-butanedione, 2, 3-pentanedione, 2, 4-pentanedione, 2, 5-hexanedione and the like; the method is a homogeneous reaction, does not need additional surfactant and the like, is simple and convenient to operate and low in energy consumption, obtains nano gold with the particle size range of 15-45 nm, is in the form of well-dispersed nano spherical and triangular particles, has tunable Local Surface Plasmon Resonance (LSPR) and ultrahigh stability, and has a good application prospect in the fields of biomedicine and electrodes such as plasmon biosensors and the like.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a method for preparing water-soluble nano gold.
Background
In recent years, gold nanoparticles (Au NPs, nanogold) have been widely used in the fields of material science, biotechnology and organic chemistry ("anti-nanopic gold nanoparticles: A surface of complementary synthetic methods [ J ]," Jose E.Ortiz-Castillo, Roberto C.Gallo-Villanua, Marc J.Madou, et al, coded.Chem.Rev., 2020,425, 213489) due to their functions as molecular markers, diagnostic imaging and catalysis. The size of the gold nanoparticles has an important influence on the application of the gold nanoparticles, and currently, the preparation and size regulation and control technologies of the gold nanoparticles comprise the following two technologies: 1) physical methods such as pulse laser ablation and arc discharge have high energy consumption and expensive instruments and equipment, and are not suitable for popularization and application; 2) chemical methods, such as hydrothermal and solvothermal techniques, including traditional citric acid reduction, seed growth methods using ascorbic acid, and various thermochemical and photochemical techniques using thiols, amines, micelles, dendrimers, polymers and biomolecules as protecting agents to help them be stable in aqueous, organic and thin film media, with low energy consumption, are currently widely used methods. The particle size range of the spherical and triangular nano-gold synthesized by the seed-mediated method is 6-175 nm, and the particle size range of the non-seed-mediated method is 5-300 nm.
Chinese patent CN 103418800A discloses a preparation method of nano-gold, which comprises the steps of using organic solvents such as alcohol or ketone, adding polyethylene glycol, urea and polyvinylpyrrolidone as dispersing agents, regulating and controlling the pH value to be 0.8-1.3, and heating to 85-95 ℃ to prepare 5-15 nm spherical nano-gold. Tollan et al ("One-step growth of gold nanoparticles using a β -diketone reducing agent [ J)]"Christopher M. Tollan, Jon Echeberria, Rebeca Marcilla, et al, J. Nanopart. Res.,2009,11(5),1241-1245) sodium carbonate buffer (0.1M) at pH 10 was mixed with the surfactant cetyltrimethylammonium bromide (CTAB,10mL, 0.2M), and 0.1M HAuCl was added40.1mL, and 0.018mL of 0.1M silver nitrate, and finally addedBeta-diketone-acetylacetone (AcAc,0.1mL,0.35M) to prepare the nanorod with the average length of 42nm and the length-diameter ratio of 4.6. The two methods have strict reaction conditions, and the use amount of organic matters (surfactant, polymer end-capping agent, organic solvent and the like) is high, so that secondary pollution is easily caused, and the method is not biologically friendly. Kundu et al ("Shape-controlled synthesis of gold nanoparticles from gold (III) -peptides of beta-diketones [ J]Subrata Kundu, Anjali Pal, Sujit Kumar Ghosh, et al, J.Nanopart. Res.,2005,7(6), 641-containing 650) is mixed with a beta-diketone and a chloroauric acid aqueous solution, heated to 60-80 ℃ and stirred continuously to prepare the spherical, triangular and hexagonal mixed nano-gold with the particle size of 3-100 nm, and the nano-gold can be stable at room temperature for at least one month. The method uses heating and stirring, has high energy consumption, and has complex condition for controlling the synthesis of the nano particles.
The photochemical method is a method with mild reaction conditions, easy size control and low-risk chemicals, and is generally considered as a 'green' technology and applied to the synthesis of nano-gold. The regulation and control of nanoparticle synthesis by light instead of heat has gradually become a research hotspot. Since ketone radical is very reductive, ketones, including aliphatic ketones and aromatic ketones, have been widely reported as a method for photochemical synthesis of Au and Ag NPs. Tiziana placido et al found that acetone plays a key role in The Photochemical synthesis of water-soluble gold nanorods (see literature: "Photochemical synthesis of water-soluble gold nanoparticles: The roll of silver in The experimental and experimental growth [ J)]"Tiziana Placido, Robert Comparelli, France sco Giannici, et al, chem. Mater.,2009,21, 4192-. The keto radical generated by photolysis of acetone is responsible for reduction of au (iii), however, acetone has weak light absorption, low keto yield, and lacks stabilization to the resulting NPs. Aromatic ketones, for example diaryl ketones, benzoin derivatives and heterocyclic ketones ("Photochemical Norrish type I reactions a alcohols for metallic nanoparticie synthesis: immunity of propyl coupled electron transfer [ J ]]"Juan C.Scaiano, Kevin G.Stamplecoskew, Genieee L.Hallett-Tapley, chem.Commun, 2012,48, 4798-4808) is a very strong UV absorber, effective for the synthesis of Au and Ag NPs. But instead of the other end of the tubeMost of these aromatic ketones are poorly soluble in water, including Benzophenone (BP), the most widely studied ketone. Their use in photochemical synthesis is therefore limited to organic media or micelles and generally needs to be carried out under an inert atmosphere with reaction times in the range of tens of minutes to days (30 min-88 h). Scaiano et al, 2006 ("simple photonic synthesis of unprotected aqueous gold nanoparticles [ J ]]"Katherine L, McGilvray, Matthew R.Decan, Dashan Wang, et al, J.Am.chem.Soc.,2006,128, 15980-]-1-propanone (I-2959), incorporated in the preparation of nanogold. It was found that HAuCl can be reduced by the keto radical formed by Norrish type I cleavage of I-29594Stable, unprotected, water-soluble gold nanoparticles are prepared in minutes to hours. However, polymer nanoparticles can be generated by BP and I-2959 self illumination, so that the prepared nanogold is impure, and the prepared nanogold has large particle size difference (the particle size range is 8-300 nm) and irregular appearance. Therefore, the development of a green, efficient, mild, controllable and high-purity nanogold preparation method is urgently needed.
Disclosure of Invention
Aiming at the problems that the existing preparation method needs an organic solvent which is not friendly to the environment, the operation condition is strict, and the nano gold particles are not uniform and impure, the invention aims to provide a method for preparing water-soluble nano gold, which has the advantages of greenness, high efficiency, mildness, controllability, high and stable purity and the like.
The technical scheme adopted by the invention for realizing the purpose is as follows:
first, the present application provides a method for reducing chloroauric acid (III) radical ions ([ AuCl ] using a small molecule diketone4]-) The method for preparing the water-soluble nano gold comprises the following steps:
1) will contain chloroaurate (III) ions ([ AuCl ]4]-) Uniformly mixing the solution with a small molecular diketone solution to obtain a mixed solution; standing the mixed solution for a period of time to obtain the purpleRed zero-valent water-soluble nano gold solution; the pH value of the mixed solution is preferably 2.0-5.0;
2) storing the purple-red nano gold solution obtained in the step 1) in a 4oC environment.
In the above preparation method, the gold (III) chloride radical ([ AuCl ]) is contained4]-) The solution of (a) comprises: sodium chloroaurate solution, potassium chloroaurate solution, chloroaurate tetrahydrate solution, and the like.
The small molecule diketone comprises any one of 2, 3-Butanedione (BD), 2, 3-Pentanedione (PD), 2, 4-pentanedione (AA) and 2, 5-Hexanedione (HD).
In the preparation method, the molar ratio of the small-molecule diketone to the chloroauric acid (III) is 0.5-20: 1, the nanogold can be efficiently and rapidly prepared in the range, and the reaction rate is faster as the molar ratio is higher (the content of the small-molecule diketone is more).
Further, in the preparation method, the step 1) of allowing the mixed solution to stand for a period of time means that the chloroauric acid (III) root solution and the small molecular diketone are allowed to stand in a dark environment for 10min to 5 h; the water-soluble nano-gold solution can be generated after being placed for 10min, and the nano-gold can continuously grow and mature after being continuously placed for 5 h. This shows that the small molecular diketone can rapidly reduce the chloroauric acid (III) salt in the absence of light, which indicates that the method for preparing nanogold from small molecular diketone provided by the present application has low energy consumption.
Further, the step 1) of placing the mixed solution for a period of time means that the mixed solution is placed in an ultraviolet irradiation environment to be irradiated for 2-90 min, and then the water-soluble nano gold solution can be prepared; under the UV illumination, the chloroauric acid (III) salt begins to reduce (generate water-soluble nano gold) for 2min, and the time range of complete reduction is 4-90 min. The ultraviolet light intensity is more than 1.37mW/cm2Preferably 1.37-7.5 mW/cm2The ultraviolet light source is a medium-pressure or low-pressure mercury lamp which is conventional in the field, the medium-pressure mercury lamp is multicolor, and the characteristic emission wavelength is 365 nm; the low-pressure mercury lamp is monochromatic and emits at a wavelength of 254 nm.
According to the invention, the water-soluble colloidal nano-gold is prepared by reducing chloroauric acid (III) salt by utilizing excellent redox capability and photochemical activity of micromolecular diketone. Compared with the prior art, the beneficial effects are that:
(1) in one embodiment of the invention, the light intensity is 7.5mW/cm using the established UV/AA system2The method can generate nano gold within 2min, and photo-reduces chloroauric acid (III) salt in water to zero-valent gold within 4min, which is 13-18 times of a UV/aromatic ketone system generating strong reducing ketone radical and is about 801 times of a single UV system. The conversion rate of the chloroauric acid (III) salt is up to 100 percent, and the aims of green and high efficiency are achieved.
(2) The preparation conditions are normal temperature and normal pressure, the preparation is carried out in aqueous solution, the whole preparation process is safe and stable, the control is convenient to master, and the implementation is easy. Compared with the conventional nano-gold prepared by UV/I-2959 which is stable within six months, in one embodiment of the invention, the nano-gold prepared by the UV/AA system can still maintain ultrahigh stability after being placed for one year, and the industrial application value is high.
(3) The nano-gold prepared by the invention is a single crystal, in one embodiment of the invention, the nano-gold has small particle size, good monodispersity (15-45 nm), uniform nano-gold particles and tunable Local Surface Plasmon Resonance (LSPR), and can provide a good foundation for research and application of nano-gold in the fields of biomedicine and electrodes.
(4) The micromolecule diketone method adopted by the invention is a homogeneous reaction, in one embodiment of the invention, the applicable solution has a wide pH range (2.0-5.0), no stabilizer such as polymer, surfactant and the like is required to be additionally added, and the prepared nanogold has high purity and higher industrial application prospect.
Drawings
FIG. 1 is a transmission electron microscope image of the purple-red nano-gold obtained by dark reaction of AA in example 1 at different time points.
FIG. 2 is a transmission electron microscope, an optical photograph, a particle size distribution, a high resolution transmission electron microscope and a real-time fast Fourier transform chart of the magenta nano-gold sol obtained in example 2.
FIG. 3 is the X-ray photoelectron spectrum of the dried purple-red nanogold obtained in example 2.
FIG. 4 is the LSPR peak diagram of the mixed solution of water-soluble nanogold colloid prepared by photochemical reaction obtained in example 2.
FIG. 5 is a graph showing the change of absorbance of LSPR peak of the nano-gold prepared by UV/diketone method in example 3 with storage time.
FIG. 6 is a comparison of the effects of UV/diketone method and UV/aromatic ketone method in example 4 to prepare nanogold.
FIG. 7 is a comparative UV-Vis spectrum of the four UV/diketone systems of example 5 to produce nanogold.
FIG. 8 is a comparative schematic diagram of optical photographs of the four UV/diketone systems in example 5 to produce nanogold.
FIG. 9 is a UV-Vis spectrum of the effect of diketone concentration on the preparation of nanogold by the UV/diketone method in example 6.
FIG. 10 is an optical photograph showing the effect of diketone concentration on the preparation of nanogold by the UV/diketone method in example 6.
FIG. 11 is a histogram of particle size distribution of the effect of light intensity on the UV/diketone method for preparing nanogold in example 7.
FIG. 12 is a UV-Vis spectrum of the effect of the ionic strength on the preparation of nanogold by the UV/AA method in example 8.
FIG. 13 is an optical photograph showing the effect of ionic strength on the UV/AA method for preparing nanogold in example 8.
FIG. 14 is a UV-Vis spectrum of the effect of the pH of the solution of example 9 on the preparation of nanogold by the UV/AA method.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited thereto.
(1) The examples relate to the reagents:
the drugs used in the examples were all analytically pure and above. 2, 3-butanedione (BD, C)4H6O2) 2, 4-pentanedione (AA, C)5H8O2) 2, 5-hexanedione (HD, C)6H10O2) And sodium perchlorate (NaClO)4) 2, 3-Pentanedione (PD, C) from Nanjing chemical industries, Ltd5H8O2) Chloroauric acid tetrahydrate (HAuCl), available from Shanghai Allantin Biotechnology Ltd4·4H2O,Au≥47.8%) was purchased from limited chemical agents corporation of the national drug group. Two aromatic ketones, benzophenone (BP, C)13H10O) and 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone (I-2959, C)12H16O4) Purchased from Shanghai Bidi pharmaceutical technology, Inc.
The preparation method of the chloroauric acid stock solution comprises the following steps: 1g of HAuCl was weighed4·4H2O to 200mL of ultrapure water, a 12mM chloroauric acid stock solution was prepared.
The preparation method of the diketone stock solution comprises the following steps: 128.6 μ L of AA/108.7 μ L of BD/128.6 μ L of PD/64.3 μ L of HD to 250mL of ultrapure water were taken respectively and prepared into 5mM of AA/BD/PD/HD stock solution.
The preparation method of the aromatic ketone stock solution comprises the following steps: 0.2278g BP to 250mL 50% (v/v) acetonitrile water solution is taken, 0.2803g I-2959 to 250mL ultra-pure water is taken, and 10mM BP or I-2959 stock solution is prepared.
Na2SO4The preparation method of the stock solution comprises the following steps: 0.0355g of Na was weighed2SO4To 25mL of ultrapure water, prepared as 10mM Na2SO4And (4) stock solution.
Ultrapure water (18.25M Ω · cm) manufactured by an ultrapure water machine (shanghai poppy industries ltd) was used for preparing the sample solution.
(2) Reaction device
The photoreaction device is provided by Nanjing Haoben technologies, Inc., and has a structure and documents as follows: the same apparatus as that disclosed in 167-.
(3) Method for detecting content of chloroauric acid (III) salt
The gold content of the solution was measured by inductively coupled plasma emission spectroscopy (ICP-OES, iCAP7400, siemer feishell science, usa) and all samples were filtered through a 0.22 μm water-based filter and acidified with 2% nitric acid before analytical testing, and the samples were analyzed within 24 h.
Example 1 dark reaction preparation of water-soluble nanogold
Mixing chloroauric acid (HAuCl)4·4H2The molar ratio of O) to AA is set to 1:10, 0.0625mL of 12mM chloroauric acid stock solution and 1.5mL of 5mMAA solution are taken and added into a glass colorimetric tube with the volume of 25mL, ultrapure water is added to dilute the mixture to the scale, and the mixture is uniformly oscillated to obtain 0.03mM chloroauric acid and 0.3 mMAA. Then, tinfoil paper is used for wrapping the colorimetric tube to ensure a dark environment, and the mixture is placed for a period of time to prepare uniform mauve gold colloid mixed liquid.
FIG. 1 is the transmission electron microscope (TEM, JEM-100S, Japan) images of the magenta nano-gold prepared in this example at different time points. It can be found that the AA system can be placed for 10min under the condition of no light to prepare the nano-gold, the grain diameter of the nano-gold is gradually increased along with the increase of the placing time, the irregular nano-gold seeds grow into regular spheres after 3h and are accompanied with the generation of some triangular nano-gold gradually at 10min, and some hexagonal nano-gold is generated after 5h, which corresponds to the nucleation and growth processes of the nano-gold.
EXAMPLE 2 photochemical reaction preparation of Water-soluble Nanogold
Setting the molar ratio of chloroauric acid to AA (or BD, BP, I-2959) at 1:3.3, adding 12mM chloroauric acid 0.625mL and 5mL of 5mM AA (or BD, BP, I-2959) solution into a glass colorimetric tube with the volume of 25mL, adding ultrapure water to dilute to the scale, and uniformly oscillating to obtain the chloroauric acid 0.3mM, AA or BD, BP, I-2959.
Then poured into a 25mL quartz photoreaction tube, and finally the reaction tubes were placed in the photoreactor in sequence. Using a medium-pressure mercury lamp with a light intensity of 7.5mW/cm2Respectively illuminating corresponding AA solution and BD, BP and I-2959 solutions for 4min to obtain simple substance gold colloid mixed solution.
Mixing the claret glueCentrifuging the mixed solution (10000-15000 rpm, 10-30 min), removing the supernatant, adding ultrapure water, washing, centrifuging again, repeating the steps for three times, and freeze-drying the obtained colloidal nanogold (step 1)
2.5L Labconco, USA (-50oC, 0.120mBar, dried for 2h) and then examined the solid material for X-ray photoelectron spectroscopy (XPS, PHI5000 Versa Probe, Japan) to characterize the composition of the nanogold.
Fig. 2 is a transmission electron microscope (TEM, FEI, TF20, usa) image and a particle size distribution diagram of the magenta nanogold prepared in this example. Wherein, (a) is TEM image and optical photograph of nano-gold prepared by UV/AA system and diameter distribution diagram of nano-gold particles prepared by the system; (b) a TEM image and an optical photograph of the nano-gold prepared by the UV/BD system, and a diameter distribution schematic diagram of nano-gold particles prepared by the system; (c) high Resolution Transmission Electron Microscopy (HRTEM) and real-time fast fourier transform (live FFT) images of nanogold prepared for UV/AA systems, and (d) HRTEM and live FFT images of nanogold prepared for UV/BD systems. (e) Is TEM image of BP nanoparticles prepared by illumination under the coexistence condition of (w /) chloroauric acid, and (f) is TEM image of I-2959 nanoparticles prepared by illumination under the coexistence condition of chloroauric acid.
The nano gold prepared by the UV/diketone system has smaller particle size, the particle size distribution range is 15-45 nm, and the nano gold is uniform. The nanogold prepared by the UV/AA system has regular spherical and triangular shapes, good overall dispersion and no agglomeration phenomenon, which is probably attributed to the property of the beta-diketone that has a surfactant (see the literature: Synthesis of high molecular biological iron nanoparticles with surfactant property [ J ] "Dale L.Huber, et al.J.Magn.Mat.2004, 278(3): 311-316). In contrast, the UV/BD system produces dendritic gold nanostructures.
The above examples demonstrate that the UV/diketone method does not require addition of a large amount of surfactant, and greatly reduces environmental pollution caused by use of chemical reagents. In addition, the nano-gold prepared by the UV/diketone system belongs to a face-centered cubic structure and has two crystal faces of (110) and (111).
As shown in FIGS. 2e and 2f, the conventional two UV/aromatic ketone systems (UV/BP and UV/I-2959) become cloudy in their own illumination solution, resulting in larger polymer nanoparticles; the nano gold prepared by illumination in coexistence with chloroauric acid has smaller size, and two kinds of nano particles with greatly different sizes are formed. This indicates that the nanogold prepared from the two aromatic ketones is not pure, is a compound of nanogold and polymer nanoparticles, and cannot be separated out.
Fig. 3 shows XPS of the dried purple-red nanogold obtained in this example. (a) In the figure, 80.9 percent of the mauve substance prepared by the UV/AA system is zero-valent gold, and 19.1 percent of the mauve substance is positive-valent gold; (b) in the figure, the UV/BD system prepares the mauve substance with 87.8 percent of zero-valent gold and 12.2 percent of positive-valent gold. The UV/diketone method is proved to have high efficiency in reducing the chloroauric acid and higher purity of the prepared nano gold.
Fig. 4 is a LSPR peak diagram of the mixed purple water-soluble nanogold colloid in this example. Detection was performed using a 1cm stone p cuvette placed in a single channel uv-vis spectrophotometer (Cary 60, agilent, usa). The nano-gold prepared by the UV/diketone method has a strong LSPR peak, and the result proves that the purple red nano-gold with great application potential in the fields of biomedicine such as plasmon biosensors and electrodes is prepared by the embodiment.
EXAMPLE 3 stability of Nanogold prepared by UV/diketone method
Setting the molar ratio of the chloroauric acid to the AA (or BD) at 1:2, adding 0.208mL and 1mL of 12mM chloroauric acid and 5mM AA (or BD) into a glass colorimetric tube with the volume of 25mL, adding ultrapure water to dilute the mixture to the scale, and uniformly oscillating to obtain a mixed solution of 0.1mM chloroauric acid and 0.2mM AA (or BD). The pH of the solution was adjusted to 3.3 with 0.1M perchloric acid and sodium hydroxide. Then poured into a 25mL quartz photoreaction tube, and finally the reaction tubes were placed in the photoreactor in sequence. Irradiating for 30min by using a low-pressure mercury lamp, wherein the light intensity of the reaction is 1.4mW/cm2And storing the prepared nano gold colloid mixed solution in a refrigerator at 4 ℃. The uv-vis spectra of the solutions were measured at intervals.
FIG. 5 is a graph showing the change of absorbance of LSPR peak of the nanogold in this example with storage time. It can be seen that the absorbance of the LSPR peak (530nm) of the water-soluble nanogold prepared by the UV/AA system after being placed for one year is basically coincident with that of the initial peak, which shows that the nanogold prepared by the UV/AA system still keeps ultrahigh stability after being placed for one year.
Example 4 comparison of the effects of UV/diketone and UV/aromatic ketone methods on the preparation of nanogold
Setting the molar concentration of the ketone (AA/BD/BP/I-2959) to be 1.0mM and the molar concentration of the chloroauric acid to be 0.3mM, respectively taking 0.625mL of 12mM chloroauric acid and 5mL of 5mM ketone solution, adding the solutions into a glass colorimetric tube with the volume of 25mL, adding ultrapure water to dilute the solutions to the scale, and uniformly oscillating the solutions to obtain 0.3mM chloroauric acid (III) salt solution and 1.0mM ketone mixed solution respectively. The pH of the solution was adjusted to 3.3 with 0.1M perchloric acid and sodium hydroxide. In the experiment, BP was dissolved in 50% (v: v) acetonitrile aqueous solution to prepare a stock solution, because BP has poor water solubility. Then poured into a 25mL quartz photoreaction tube, and finally the reaction tubes were placed in the photoreactor in sequence. The light intensity of the medium-pressure mercury lamp is 7.5mW/cm2The illumination reaction is carried out for 60min, the concentration of the chloroauric acid is detected by sampling every 2min for the first 10min, and the sampling time interval of the later period is increased to 10min and 30 min.
FIG. 6 is a schematic diagram showing the change of the concentration of chloroauric acid in this embodiment. It can be seen that the complete reduction of chloroauric acid can be achieved by the UV/AA system at 4min, and the reaction rate is 801 times that of the UV/BD system alone, 13.5 times that of the UV/BD system, 13.1 times that of the UV/BP system, and 18.0 times that of the UV/I-2959 system. Both the UV/BD system and the UV/I-2959 system achieved almost complete reduction of chloroauric acid at 60min (ln (C/C)0)＝-4, C/C01.83%), whereas the conversion of chloroauric acid by the UV/BP system stayed around 10min with a conversion of around 55%. Thus, the UV/diketone method is a photochemical method for efficiently reducing chloroauric acid.
Example 5 UV-Vis spectral comparison of four UV/diketone systems to produce nanogold
Setting the molar ratio of chloroauric acid to AA (or BD, PD, HD) at 1:10, taking 0.208 and 5mL of each of 12mM chloroauric acid and 5mM AA (or BD, PD, HD) solution, adding into a solution with a volume of 25And (3) adding ultrapure water into the mL glass colorimetric tube to dilute the glass colorimetric tube to the scale, and uniformly oscillating the glass colorimetric tube to obtain 0.1mM chloroauric acid, 1.0mM AA or BD, HD and PD. The pH of the solution was adjusted to 3.3 with 0.1M perchloric acid and sodium hydroxide. Then poured into a 25mL quartz photoreaction tube, and finally the reaction tubes were placed in the photoreactor in sequence. The light intensity of the medium-pressure mercury lamp is 6.8mW/cm2Respectively illuminating corresponding solutions containing AA or BD, PD and HD, sampling every 5 or 10min, and detecting the ultraviolet-visible spectrum of the solution.
Fig. 7 and 8 are a uv-vis spectrum and an optical photograph of the nanogold in this example, respectively. In fig. 7, (a) to (d) are the results of uv-vis spectrum detection of solutions containing AA or BD, PD, and HD in order. As shown in the figure, the new absorption value in the visible light region after light irradiation is the absorption for producing nanogold, and the higher the absorption value at the same time point represents the higher the amount of nanogold. In FIG. 8, (a) to (d) represent solutions irradiated with light for 0, 5, 10 and 20min, respectively, and darker solution color represents more nanogold. In summary, the reaction speed sequence for producing the nanogold of the four diketone systems is as follows: UV/AA > UV/HD > UV/PD > UV/BD.
Example 6 influence of diketone concentration on preparation of nanogold by UV/diketone method
Setting the molar concentration of the chloroauric acid to be 0.1mM, setting the molar ratio of the chloroauric acid to the AA or BD to be 1:0.5, 1:2, 1:10 and 1:20, adding 0.208mL of 12mM chloroauric acid solution and 0.25, 1, 5 or 10mL of 5mMAA (or BD) solution into a glass colorimetric tube with the volume of 25mL, adding ultrapure water to dilute the solution to a scale, and uniformly shaking to obtain mixed solutions of 0.1mM chloroauric acid and 0.05, 0.2, 1.0 and 2.0mMAA or BD respectively. The pH of the solution was adjusted to 3.3 with 0.1M perchloric acid and sodium hydroxide. Then poured into a 25mL quartz photoreaction tube, and finally the reaction tubes were placed in the photoreactor in sequence. The light intensity of the medium-pressure mercury lamp is 6.8mW/cm2And (3) carrying out illumination reaction for 90min, and sampling at intervals to detect the ultraviolet-visible spectrum of the solution.
FIGS. 9 and 10 are a UV-Vis spectrum and an optical photograph of the solution of this example. In FIG. 9, (a) is a UV-visible spectrum of the UV/AA system after mixing AA and chloroauric acid at different concentrations, and (b) is a UV/BD system. In FIG. 10, (a) to (d) represent solutions irradiated with light for 0, 5, 20 and 90min, respectively. As can be seen from the absorbance of the ultraviolet-visible spectrum in the visible light region and the color change of the solution, under the same condition, the conversion effect sequence of different photochemical processes on 0.1mM chloroauric acid is as follows: UV/AA > UV/BD. The higher the concentration of the diketone, the faster the rate of conversion to chloroauric acid. The LSPR peak value of the nano-gold generated by 0.2mM mixed solution of AA and chloroauric acid ([ AA ]/[ chloroauric acid ] ═ 2) under illumination for 5min can reach the maximum value; the maximum LSPR peak of nanogold formed in a 2.0mM BD and chloroauric acid mixed solution ([ BD ]/[ chloroauric acid ] ═ 20) was reached after 10min of light irradiation. Therefore, the UV/AA system can reduce chloroauric acid very efficiently.
Furthermore, the LSPR wavelength of nanogold prepared with the UV/AA system red-shifted from 530nm to 548nm as the AA concentration increased from 0.2mM to 2.0 mM. However, the UV/BD system only showed a significant LSPR peak in the visible region at a BD concentration of 2.0 mM. The LSPR wavelength is positively correlated with the size of the nanogold (molecular detection and application [ J ] ", Yaocui Nuo, Wangmeng, Wangjing, Zhangxi. laser biology report 2015,24(04): 303-313). Therefore, the higher the concentration ratio of AA to chloroauric acid, the larger the size of the prepared nanogold. In practical application, the concentration ratio of AA to chloroauric acid is recommended to be 2-20, and the concentration ratio of BD to chloroauric acid is recommended to be 10-20.
Example 7 Effect of light intensity on the preparation of Nanogold by the UV/diketone method
Setting the molar ratio of chloroauric acid to AA at 1:10, adding 12mM chloroauric acid (III) salt 0.0625mL, 5mM AA or BD solution 1.5mL into a glass colorimetric tube with the volume of 25mL, adding ultrapure water to dilute to the scale, and uniformly oscillating to obtain 0.03mM chloroauric acid (III) salt and 0.3mM AA or BD. The pH of the solution was adjusted to 3.3 with 0.1M perchloric acid and sodium hydroxide. Then poured into a 25mL quartz photoreaction tube, and finally the reaction tubes were placed in the photoreactor in sequence. When the medium-pressure mercury lamp is used, the light intensity is shielded by wrapping one or two layers of copper nets around the ultraviolet lamp to realize the light intensity control of three gradients, which are respectively 4.93 mW/cm, 3.33 mW/cm and 1.37mW/cm2Irradiating the solution for 60min, sampling at intervals, and detecting the ultraviolet-visible spectrum of the solution。
FIG. 11 is a distribution diagram of the particle size of the nano-gold in this embodiment. Wherein (a) is a diameter distribution schematic diagram of nano gold particles obtained under three light intensities of a UV/AA system; (b) the diameter distribution of the nano-gold particles obtained under three light intensities of the UV/BD system is shown schematically. It can be seen that under the condition of gradually increasing light intensity, the particle size of the nanogold gradually increases: the average particle size of the nano-gold of the UV/AA system is increased from 12nm to 30nm, and the average particle size of the nano-gold of the UV/BD system is increased from 11nm to 36 nm. In the photochemical method, the particle size of the nanogold is regulated and controlled by controlling the light intensity, so that the method is a convenient and effective method. In a specific application, light intensity of more than 1.37mW/cm is recommended2。
Example 8 Effect of ion Strength on the preparation of Nanogold by UV/AA method
The molar ratio of chloroauric acid to AA was set at 1:2, 12mM chloroauric acid 0.208mL and 5mM AA solution 1mL were added to a glass cuvette having a volume of 25mL, and 0.25, 1.25 or 6.25mL 10mM Na was added to the cuvette2SO4Diluting the stock solution with ultrapure water to scale, and shaking to obtain 0.1mM chloroauric acid, 0.2mM AA, and Na+The concentrations were 0.2, 1.0 and 5.0mM, respectively. The pH of the solution was adjusted to 3.3 with 0.1M perchloric acid and sodium hydroxide. Then poured into a 25mL quartz photoreaction tube, and finally the reaction tubes are sequentially put into a photoreactor. The light intensity of the medium-pressure mercury lamp is 6.8mW/cm2The solution is illuminated for 30min, and the ultraviolet-visible spectrum of the solution is detected by sampling at intervals.
Fig. 12 and 13 are the uv-vis spectrum and optical photograph of the nanogold in this example. In FIG. 12, (a) is Na+UV-VIS spectrum of 0.2mM system, (b) Na+UV-VIS spectrum obtained from 1.0mM system, and Na in (c)+UV-Vis spectra obtained for the 5.0mM system.
With Na+When the concentration is increased from 0.2mM to 1.0mM, the LSPR peak of the nano-gold is narrowed, which shows that the particle size distribution of the nano-gold is narrowed and the particle size is more uniform. Na (Na)+As the concentration continued to rise to 5mM, the LSPR peak red-shifted, indicating that the nanogold size is increasing. Drawing (A)In 13, (a) to (d) represent solutions irradiated with light for 0, 5, 10 and 20min, respectively. It can be seen that the higher the ionic strength, the darker the solution color at the same illumination time. In general, the increase of the ionic strength is beneficial to the grain growth and the grain size homogenization of the nano-gold.
As can be seen from this example, the ionic strength is advantageous for the preparation of nanogold, so other common chloroauric acid (III) salts in the art, such as chloroauric acid tetrahydrate, potassium chloroauric acid, or sodium chloroauric acid, can be used in the implementation.
EXAMPLE 9 Effect of solution pH on the preparation of Nanogold by UV/AA method
Setting the molar ratio of the chloroauric acid to the AA at 1:2, adding 0.208mL and 1mL of 12mM chloroauric acid and 5mM AA respectively into a glass colorimetric tube with the volume of 25mL, adding ultrapure water to dilute to the scale, and uniformly oscillating to obtain a mixed solution of 0.1mM chloroauric acid and 0.2mM AA. In view of the ease of hydrolysis of Au (III), the pH of the solution was adjusted in the acidic range with 0.1M perchloric acid and sodium hydroxide, pH values of 2.0, 4.0 and 5.0 in this order. Then poured into a 25mL quartz photoreaction tube, and finally the reaction tubes were placed in the photoreactor in sequence. The light intensity of the medium-pressure mercury lamp is 6.8mW/cm2And (3) carrying out illumination reaction for 20min, and sampling every 2 or 10min to detect the ultraviolet-visible spectrum of the solution.
FIG. 14 is a diagram of UV-Vis spectra of the solution of the present example and corresponding TEM images, wherein (a) is a diagram of UV-Vis spectra under conditions of pH 2.0, 4.0 and 5.0, respectively, from top to bottom, and (b) is a diagram of TEM spectra under conditions of pH 2.0, 4.0 and 5.0, respectively, from top to bottom. In half an hour after the pH adjustment, the solution reacted to a purple-red color, indicating that AA reduced the chloroauric acid (III) salt in the absence of UV light. And UV illumination accelerates this process. And the higher the pH, the longer the time to reach the highest LSPR peak, indicating that an increase in pH results in a decrease in the reduction rate of chloroauric acid. With the increase of pH from 2.0 to 5.0, the LSPR peak of the nano-gold blue-shifts from 563nm to 540nm, and from the corresponding TEM image, it is obvious that the particle size of the nano-gold is significantly reduced from about 100nm to about 60nm to about 20 nm. Therefore, the particle size of the nanogold and the LSPR can be easily tuned by adjusting the solution pH: the pH range is 2.0-5.0, and the higher the pH value is, the smaller the particle size is.
The above-mentioned examples only express embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for the person skilled in the art, several modifications can be made without departing from the inventive concept, and these modifications are within the scope of the present invention.
Claims (9)
1. A method for preparing water-soluble nano gold is characterized by comprising the following steps: and mixing the solution containing the chloroauric acid radical ions with the micromolecular diketone to obtain a mixed solution, and standing to obtain the water-soluble nano gold solution.
2. The method for preparing water-soluble nanogold according to claim 1, wherein the solution containing the chloroauric acid radical ions comprises at least one of a sodium chloroaurate solution, a potassium chloroaurate solution, or a chloroaurate tetrahydrate solution.
3. The method for preparing water-soluble nanogold according to claim 2, wherein the small molecule diketone comprises at least one of 2, 3-butanedione, 2, 3-pentanedione, 2, 4-pentanedione, and 2, 5-hexanedione.
4. The method for preparing water-soluble nanogold according to claim 2, wherein the pH value of the mixed solution is 2.0 to 5.0.
5. The method for preparing water-soluble nano gold according to claim 3, wherein the molar ratio of the small molecular diketone to the chloroaurate is 0.5-20: 1.
6. The method for preparing water-soluble nanogold according to any one of claims 1 to 5, wherein the standing is performed in a dark environment.
7. The method for preparing water-soluble nanogold according to any one of claims 1 to 5, wherein the standing is performed under an ultraviolet irradiation environment.
8. The method for preparing water-soluble nanogold according to claim 7, wherein the ultraviolet irradiation environment is that the ultraviolet intensity is greater than 1.37mW/cm2The environment of (2).
9. The method for preparing water-soluble nanogold according to claim 8, wherein the ultraviolet illumination environment is that the ultraviolet intensity is 1.37-7.5 mW/cm2The environment of (2).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1663714A (en) * | 2004-12-02 | 2005-09-07 | 黄德欢 | Method for preparing nano gold solution |
| WO2015125980A1 (en) * | 2014-02-21 | 2015-08-27 | Kim Il Sung University | Nanogold injection and its manufacturing method |
| CN105731587A (en) * | 2015-12-18 | 2016-07-06 | 南京大学 | Method for reducing hexavalent chromium through micromolecular diketone-ultraviolet light |
| CN110395700A (en) * | 2019-07-29 | 2019-11-01 | 南京大学 | A kind of method of photochemistry preparation nanometer selenium |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1663714A (en) * | 2004-12-02 | 2005-09-07 | 黄德欢 | Method for preparing nano gold solution |
| WO2015125980A1 (en) * | 2014-02-21 | 2015-08-27 | Kim Il Sung University | Nanogold injection and its manufacturing method |
| CN105731587A (en) * | 2015-12-18 | 2016-07-06 | 南京大学 | Method for reducing hexavalent chromium through micromolecular diketone-ultraviolet light |
| CN110395700A (en) * | 2019-07-29 | 2019-11-01 | 南京大学 | A kind of method of photochemistry preparation nanometer selenium |
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