CN111112596A - Chiral noble metal nano-particles and preparation method and application thereof - Google Patents
Chiral noble metal nano-particles and preparation method and application thereof Download PDFInfo
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- CN111112596A CN111112596A CN201811295142.XA CN201811295142A CN111112596A CN 111112596 A CN111112596 A CN 111112596A CN 201811295142 A CN201811295142 A CN 201811295142A CN 111112596 A CN111112596 A CN 111112596A
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Abstract
The invention provides a chiral noble metal nano particle and a preparation method thereof, wherein the chiral noble metal nano particle is a noble metal nano rod of which the surface of a long shaft is coated with a noble metal shell layer which is spirally arranged along a single direction; the invention can realize the generation of chiral noble metal nano particles with optical activity from bottom to top after modifying chiral sulfydryl molecules on the surface of the noble metal nano rod, the structure and the synthesis method of the structure belong to a new breakthrough in the field of nano structure regulation, the preparation method of the chiral noble metal nano particles provided by the invention can prepare the chiral noble metal nano particles with extremely high efficiency, the yield and the cost are controllable, the obtained chiral noble metal nano particles have an abnormally stable and clear microstructure, the circular dichroism signal can reach about 600 millidegree, and the chiral noble metal nano particles lead other materials with similar structures, thereby having huge application prospects in the fields of chiral catalysis, chiral separation, chiral compound detection and chiral optical devices.
Description
Technical Field
The invention relates to the field of nano composite materials, in particular to a chiral noble metal nano particle and a preparation method and application thereof.
Background
Natural biomolecules have chirality, which is almost a basic feature of living materials and may even be a necessary condition for life existence, and it is the discovery of double helix chiral structure of DNA that decouples the secret of life genetic information replication and transmission, so understanding the chirality of molecules and the selectivity of chiral enantiomers is crucial for understanding the biochemical reactions of life.
In recent years, the synthesis and biological application of chiral inorganic materials with light control capability, such as materials with characteristics of polarization control, negative refractive index or chiral sensing detection, are being developed vigorously, noble metal nano materials can generate surface plasmon resonance due to the action of noble metal nano materials with light, form "hot-spot" on the surface or inside, further generate extremely strong electromagnetic field in a local area, and are often regarded as "prisms" with light concentration and amplification effects in a nano area, and meanwhile, the noble metal nano materials have very strong biocompatibility, so the synthesis of chiral noble metal nano materials with optical activity is important for understanding and imitating biological chiral structures, and applications such as biomolecule detection, chiral catalysis and chiral separation.
At present, two methods are mainly used for preparing the noble metal nano material with the chiral structure, the first method is to construct the chiral nano structure through micromachining (photoetching, plasma etching or wet etching and the like) and a gas phase deposition method in a top-down processing mode, the method has high requirements on the precision and stability of production equipment and processing materials, the production efficiency is low, the yield is low, and the obtained product is easy to oxidize and lose efficacy in the atmosphere. The second method is to assemble a plurality of noble metal nanoparticles without chirality into a chiral spatial structure by means of biological macromolecules with chirality (such as DNA, polypeptide, amino acid and the like), and although the method is widely applied in the year, the method also has the problems that the product structure is difficult to accurately control, the yield is low, the product structure is unstable, racemization influence is easy to occur in the storage process to further apply, and the like. For example, CN103940746A discloses a method for obtaining a "shoulder-to-shoulder" chiral structure by incubating gold nanorods and thiol-containing chiral small molecules under heating, wherein a circular dichroism signal is formed by twisting between two gold nanorods, and copper ions are detected by using the circular dichroism signal; the obtained material is easily interfered by the impurity ions in the solution as the purpose of the material is, the optical performance is unstable, the maximum ellipticity is only 20 millidegrees, and the application of the material in other fields is limited.
Based on the prior art, those skilled in the art need to develop a simple and easy synthesis method of chiral noble metal nanoparticles from bottom to top with high yield, so that the obtained product has both structural stability due to the "top-down" synthesis method and high yield due to the self-assembly synthesis method, thereby satisfying the increasing demand for optically active materials.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for synthesizing chiral noble metal nanoparticles from bottom to top, which is simple, convenient and feasible and has higher yield, and the chiral noble metal nanoparticles obtained by the method, so as to meet the increasing demand on optically active materials.
To achieve the above object, an object of the present invention is to provide a chiral noble metal nanoparticle, which is a noble metal nanorod having a long axis surface coated with a noble metal shell layer spirally arranged in a single direction.
The noble metal shell is spirally arranged along a single direction, which means that the crystal lattices of the noble metal nanoparticles or noble metal crystals constituting the noble metal shell are spirally arranged along a single direction.
The helical arrangement in a single direction includes an arrangement in only a left-hand helical direction and an arrangement in only a right-hand helical direction.
Preferably, the coating is such that the surface of the noble metal nanorods contains threads.
Preferably, the coating is such that the surface of the noble metal nanorods contains equally spaced threads.
Preferably, the pitch of the thread is 25 to 36nm, such as 26nm, 27nm, 28nm, 29nm, 30nm, 31nm, 32nm, 33nm, 34nm or 35 nm.
Preferably, the thread has a thread depth of 15nm or less, such as 0.5nm, 1nm, 2nm, 3nm, 5nm, 7nm, 9nm, 11nm, 12nm, 13nm, 14nm, or the like.
Under the screw pitch and the screw thread depth, the obtained chiral noble metal nano-particles have larger circular dichroism and are more suitable for being used as chiral detection materials.
Preferably, the noble metal nanorods are nanorods composed of any one noble metal or an alloy of at least two noble metals of gold, silver, platinum or palladium, and are further preferably gold nanorods.
Preferably, the length-diameter ratio of the noble metal nanorods is more than or equal to 2, such as 3, 4, 7, 10, 15, 20, 25, 30, 40 or 50.
Preferably, the noble metal shell layer is a noble metal shell layer composed of any one noble metal or an alloy of at least two noble metals of gold, silver, platinum or palladium, and more preferably a shell layer composed of gold, silver or a gold-silver alloy.
Preferably, the content of silver in the shell layer made of the gold-silver alloy is 10-80 wt%, and more preferably 35-50 wt%, and the precious metal components and the content thereof are selected to form chiral precious metal nanoparticles with the most complete helical structure, so that the chiral precious metal nanoparticles have the largest circular dichroism signals.
Preferably, chiral molecules containing sulfydryl are dispersed on the surface of the noble metal nanorod and in the noble metal shell.
Preferably, the chiral molecule containing sulfydryl is a chiral organic small molecule containing sulfydryl or a chiral polypeptide molecule containing sulfydryl.
Preferably, the thiol-containing chiral molecule is any one of L-cysteine and its enantiomer, L-glutathione and its enantiomer, and L-acetylcysteine and its enantiomer.
Preferably, the surface of the noble metal nanorod and the noble metal shell layer are also dispersed with non-chiral molecules containing sulfydryl.
Preferably, the non-chiral molecules containing sulfydryl are non-chiral molecules containing sulfydryl and benzene rings, the introduction of the non-chiral molecules containing sulfydryl and benzene rings can improve the circular dichroism signal of the chiral noble metal nanoparticles only containing chiral molecules by about 2-3 times, and the phenomenon may be caused by the limiting effect of the benzene rings.
Preferably, the non-chiral molecule containing the sulfydryl is any one or a mixture of at least two of p-aminophenol, p-hydroxyphenylthiophenol, p-mercaptobenzoic acid or p-mercaptophenylboronic acid.
The second purpose of the present invention is to provide a preparation method of the chiral noble metal nanoparticles, which comprises the following steps:
dispersing water-soluble noble metal nanorods in water, adding a chiral molecule containing sulfydryl or a mixture of the chiral molecule containing sulfydryl and an achiral molecule containing sulfydryl into the water, and incubating the mixture to obtain a noble metal nanorod solution with the chiral molecule containing sulfydryl adsorbed on the surface;
and (2) adding soluble noble metal salt and a reducing agent into the noble metal nanorod solution with the surface adsorbed with the chiral molecules containing sulfydryl obtained in the step (1), uniformly mixing to obtain a mixed solution, and after the soluble noble metal salt in the mixed solution is subjected to reduction treatment, forming a noble metal shell layer spirally arranged along a single direction on the surface of the long axis of the noble metal nanorod to obtain the chiral noble metal nanoparticles.
Preferably, the incubation temperature in step (1) is 25-60 ℃, such as 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or 55 ℃.
Preferably, the incubation time in step (1) is 0.5-24 h, such as 1h, 2h, 4h, 6h, 8h, 10h, 13h, 15h, 17h, 20h, 22h or 23 h.
Preferably, the incubation treatment is performed under the condition of standing or uniform stirring.
Preferably, the concentration of the noble metal atoms in the noble metal nanorods described in step (1) in the solution is 0.02 to 0.5mmol/L, such as 0.03mmol/L, 0.05mmol/L, 0.08mmol/L, 0.10mmol/L, 0.15mmol/L, 0.20mmol/L, 0.25mmol/L, 0.30mmol/L, 0.35mmol/L, 0.40mmol/L, 0.45mmol/L, or 0.48mmol/L, etc., calculated on the amount of the substance in which the noble metal atoms are contained.
Preferably, the concentration of the thiol-group containing chiral molecule in the solution in step (1) is 20-200. mu. mol/L, such as 25. mu. mol/L, 30. mu. mol/L, 40. mu. mol/L, 50. mu. mol/L, 60. mu. mol/L, 70. mu. mol/L, 80. mu. mol/L, 90. mu. mol/L, 100. mu. mol/L, 110. mu. mol/L, 130. mu. mol/L, 150. mu. mol/L, 170. mu. mol/L or 190. mu. mol/L.
Preferably, the concentration of the thiol-group containing achiral molecule in the solution in step (1) is 0-150. mu. mol/L, such as 5. mu. mol/L, 15. mu. mol/L, 25. mu. mol/L, 35. mu. mol/L, 45. mu. mol/L, 55. mu. mol/L, 65. mu. mol/L, 75. mu. mol/L, 85. mu. mol/L, 95. mu. mol/L, 105. mu. mol/L, 115. mu. mol/L, 125. mu. mol/L, 135. mu. mol/L or 145. mu. mol/L.
Preferably, after the water-soluble noble metal nanorods are dispersed in water, a surfactant is added to promote the dispersion.
Preferably, the concentration of the surfactant is 5 to 20mmol/L, for example, 6mmol/L, 7mmol/L, 8mmol/L, 9mmol/L, 10mmol/L, 11mmol/L, 12mmol/L, 13mmol/L, 14mmol/L, 15mmol/L, 16mmol/L, 17mmol/L, 18mmol/L or 19 mmol/L.
Preferably, the surfactant is cetyltrimethylammonium bromide.
Preferably, the temperature of the reduction treatment in step (2) is 30 to 80 ℃, for example, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or 75 ℃.
Preferably, the time of the reduction treatment in the step (2) is 20-120 min, such as 25min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 115 min.
Preferably, the concentration of the soluble noble metal salt in the solution in step (2) is 0.025 to 0.4mmol/L, for example, 0.03mmol/L, 0.05mmol/L, 0.08mmol/L, 0.10mmol/L, 0.13mmol/L, 0.15mmol/L, 0.20mmol/L, 0.25mmol/L, 0.30mmol/L, 0.33mmol/L, 0.36mmol/L or 0.39 mmol/L.
Preferably, the reducing agent in step (2) is ascorbic acid.
Preferably, the concentration ratio of the ascorbic acid to the soluble noble metal salt is 1: 1.5-5, such as 1:1.6, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1: 4.8.
Preferably, the preparation method comprises the following steps:
dispersing water-soluble noble metal nanorods in water to ensure that the concentration of noble metal atoms in the water is 0.02-0.5 mmol/L, adding surfactant cetyl trimethyl ammonium bromide, sulfydryl-containing chiral molecules or a mixture of the sulfydryl-containing chiral molecules and sulfydryl-containing achiral molecules into the water to ensure that the concentration of the cetyl trimethyl ammonium bromide is 5-20 mmol/L, the concentration of the sulfydryl-containing chiral molecules is 20-200 mu mol/L, the concentration of the sulfydryl-containing achiral molecules is 0-150 mu mol/L, and incubating the mixture at 25-60 ℃ for 0.5-24 hours to obtain a noble metal nanorod solution with the sulfydryl-containing chiral molecules adsorbed on the surface;
and (2) adding soluble noble metal salt and a reducing agent ascorbic acid into the noble metal nanorod solution with the surface adsorbed with the chiral molecules containing sulfydryl, which is obtained in the step (1), so that the concentration of the soluble noble metal salt in the solution is 0.025-0.4 mmol/L, the concentration ratio of the ascorbic acid to the soluble noble metal salt is 1: 1.5-5, uniformly mixing to obtain a mixed solution, and after the soluble noble metal salt in the mixed solution is subjected to reduction treatment at 30-80 ℃ for 20-120 min, forming a noble metal shell layer spirally growing along a single direction on the surface of a long axis of the noble metal nanorod to obtain the chiral noble metal nanoparticle.
The third purpose of the present invention is to provide a use of the chiral noble metal nanoparticles, that is, the chiral noble metal nanoparticles have excellent optical stability and strong optical rotation ability, and can be used for chiral catalysis, chiral separation or detection of chiral compounds, and for manufacturing chiral optical devices or polarizers.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) after the surface of the noble metal nanorod is modified with chiral sulfydryl molecules, the water-soluble noble metal salt is introduced into the system and the reduction process of the water-soluble noble metal salt is regulated, so that a noble metal shell layer spirally arranged along a single direction is coated on the surface of a long shaft of the surface of the noble metal nanorod, and chiral noble metal nano particles with optical activity are generated from bottom to top.
(2) The preparation method of the chiral noble metal nano-particles provided by the invention can be used for preparing the chiral noble metal nano-particles with extremely high efficiency, the yield and the cost are controllable, the obtained chiral noble metal nano-particles have an abnormal stable and clear microstructure, the circular dichroism signal can reach about 600 milli-DEG, the chiral noble metal nano-particles lead other materials with similar structures, and the preparation method has huge application prospects in the fields of chiral catalysis, chiral separation, detection of chiral compounds and chiral optical devices.
Drawings
Fig. 1 is a scanning electron micrograph of the chiral noble metal nanoparticle 1 obtained in example 1 according to the present invention.
Fig. 2 is a scanning electron micrograph of the chiral noble metal nanoparticle 2 obtained in example 2 of the present invention.
Fig. 3 is a scanning electron micrograph of the chiral noble metal nanoparticles 3 obtained in example 3 of the present invention.
Fig. 4 is a circular dichroism spectrum of the chiral noble metal nanoparticle 1 obtained in example 1 according to the present invention.
Fig. 5 is a circular dichroism spectrum of the chiral noble metal nanoparticle 2 obtained in example 2 of the present invention.
Fig. 6 is a circular dichroism spectrum of chiral noble metal nanoparticles 3 obtained in example 3 of the present invention.
Fig. 7 is a circular dichroism spectrum of chiral noble metal nanoparticles 4 obtained in example 4 of the present invention.
Fig. 8 is a circular dichroism spectrum of chiral noble metal nanoparticles 5 obtained in example 5 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
Chiral noble metal nanoparticles 1 were prepared by the following steps:
dispersing water-soluble gold nanorods (with the length-diameter ratio of 7) in water to enable the concentration of gold atoms in the water to be 0.05mmol/L, adding surfactants Cetyl Trimethyl Ammonium Bromide (CTAB) and L-cysteine (L-Cys) into the water to enable the concentration of CATB to be 10mmol/L and the concentration of L-Cys to be 60 mu mol/L, and incubating the solution at 30 ℃ for 2.5 hours to obtain a gold nanorod solution with L-Cys adsorbed on the surface;
step (2), adding 20 μ L of silver nitrate solution with concentration of 10mmol/L, 8.11 μ L of chloroauric acid solution with concentration of 24.29mmol (i.e. the amount of silver atom substance accounts for 50% of the total amount of gold and silver atoms) and 32 μ L of ascorbic acid solution with concentration of 20mmol into 2mL of gold nanorod solution with L-Cys adsorbed on the surface obtained in step (1), so that the total concentration of the soluble noble metal salt in the solution is 0.2mmol/L and the concentration ratio of the ascorbic acid to the soluble noble metal salt is 1:1.6, uniformly mixing to obtain a mixed solution, after the soluble noble metal salt in the mixed solution is subjected to reduction treatment in a water bath at 70 ℃ for 30min, and forming a gold-silver alloy shell layer spirally growing along a single direction on the surface of the long axis of the gold nanorod, and carrying out centrifugal treatment on the mixed solution at the rotating speed of 6000 rpm for 5min to obtain a precipitate, namely the chiral noble metal nanoparticle 1.
Example 2
Chiral noble metal nanoparticles 2 were prepared by the following steps:
the only difference from example 1 is that p-aminophenol (4-ATP) was added to the aqueous solution in step (1) in addition to CTAB and L-Cys, and the concentration of 4-ATP in water was 40. mu. mol/L.
Example 2 chiral noble metal nanoparticles 2 were obtained.
Example 3
Chiral noble metal nanoparticles 3 were prepared by the following steps:
the only difference from example 2 is that the L-cysteine (L-Cys) in step (1) is replaced by the same molar amount of its enantiomer, D-cysteine (D-Cys).
Example 3 chiral noble metal nanoparticles 3 were obtained.
Example 4
Chiral noble metal nanoparticles 4 are prepared by the following steps:
the only difference from example 2 is that 10. mu.L of silver nitrate solution with a concentration of 10mmol/L and 12.16. mu.L of chloroauric acid solution with a concentration of 24.29mmol (i.e., the amount of silver atom in the shell layer is 25.3% of the total amount of silver atom in the shell layer) are added in step (2).
Example 4 gives chiral noble metal nanoparticles 4.
Example 5
Chiral noble metal nanoparticles 5 were prepared by the following steps:
the only difference from example 2 is that in step (2), 14. mu.L of silver nitrate solution with a concentration of 10mmol/L and 10.54. mu.L of chloroauric acid solution with a concentration of 24.29mmol (i.e., the amount of silver atom in the shell layer is 35% of the total amount of silver atom in the shell layer) are added.
Example 5 gives chiral noble metal nanoparticles 5.
Example 6
Chiral noble metal nanoparticles 6 were prepared by the following steps:
dispersing water-soluble platinum nanorods (with the length-diameter ratio of 4) in water to enable the concentration of platinum atoms in the water to be 0.05mmol/L, adding surfactants Cetyl Trimethyl Ammonium Bromide (CTAB) and L-cysteine (L-Cys) into the water to enable the concentration of CATB to be 10mmol/L and the concentration of L-Cys to be 60 mu mol/L, and incubating the solution at 30 ℃ for 2.5 hours to obtain a platinum nanorod solution with L-Cys adsorbed on the surface;
step (2), adding 20 μ L of silver nitrate solution with concentration of 10mmol/L, 8.11 μ L of chloroauric acid solution with concentration of 24.29mmol (namely, the amount of silver atom substance accounts for 50% of the total amount of gold and silver atoms) and 32 μ L of ascorbic acid solution with concentration of 20mmol into the platinum nanorod solution with L-Cys adsorbed on the surface obtained in step (1), so that the concentration of the soluble noble metal salt in the solution is 0.025-0.4 mmol/L and the concentration ratio of the ascorbic acid to the soluble noble metal salt is 1:1.6, uniformly mixing to obtain a mixed solution, after the soluble noble metal salt in the mixed solution is subjected to reduction treatment in a water bath at 70 ℃ for 90min, and forming a gold-silver alloy shell layer spirally growing along a single direction on the surface of the long axis of the platinum nanorod, and carrying out centrifugal treatment on the mixed solution at the rotating speed of 6000 rpm for 5min to obtain a precipitate, namely the chiral noble metal nanoparticles 6.
Example 7
The chiral noble metal nanoparticles 7 are prepared by the following steps:
the only difference from example 1 is that L-Cys was not added to the aqueous solution in step (1), but L-glutathione was added at the same concentration.
Example 7 gives chiral noble metal nanoparticles 7.
Example 8
The chiral noble metal nanoparticles 8 are prepared by the following steps:
the only difference from example 1 is that the incubation treatment in step (1) was carried out at a temperature of 60 ℃ for a period of 1 hour.
Example 8 chiral noble metal nanoparticles 8 were obtained.
Example 9
Chiral noble metal nanoparticles 9 were prepared by the following steps:
the only difference from example 2 is that the concentration of L-Cys in step (1) was 180. mu. mol/L and the concentration of 4-ATP was 150. mu. mol/L
Example 9 gives chiral noble metal nanoparticles 9.
Example 10
The chiral noble metal nanoparticles 10 are prepared by the following steps:
the only difference from example 1 is that in step (2), ascorbic acid was added in such an amount that the ratio of the ascorbic acid to the concentration of the soluble noble metal salt was 1:5, and the temperature of the reduction treatment was 30 ℃ and the time of the reduction treatment was 120 min.
Example 10 results in chiral noble metal nanoparticles 10.
The chiral noble metal nanoparticles 1 to 10 obtained in examples 1 to 10 were subjected to the following characterization test.
(1) Topography testing
The morphology of the chiral noble metal nanoparticles 1-10 was tested using a JC-Merlin Scanning Electron Microscope (SEM) produced by Zeiss, with the test parameters being voltage: 5 kv.
(2) Circular dichroism testing
The optical rotation characteristics of the chiral noble metal nanoparticles 1-10 are tested by using a J-1500 type Circular Dichroism (CD) manufactured by JASCO company, the circular dichroism of the chiral noble metal nanoparticles is represented by ellipticity theta, the circular dichroism of the chiral noble metal nanoparticles 1-10, which changes along with incident wavelength, is obtained, and the test parameters are as follows: the sweep rate was 500nm/min with 1nm intervals.
The chiral noble metal nano-particles obtained by the method are coated with noble metal shells which are spirally arranged along a single direction, so that the surfaces of the noble metal nano-rods contain equally spaced threads, the thread pitch of the threads is 25-36 nm, and the thread depth of the threads is less than or equal to 15 nm.
FIGS. 1 to 3 are scanning electron micrographs of the chiral noble metal nanoparticles 1 to 3 obtained in examples 1 to 3, respectively, and FIGS. 4 to 8 are circular dichromatic views of the chiral noble metal nanoparticles 1 to 5 obtained in examples 1 to 5, respectively.
It is apparent from the comparison between fig. 1 and fig. 2 that, after the thiol-containing achiral molecule is introduced into the system, the obtained chiral noble metal nanoparticle has a more regular morphology, and the surface of the chiral noble metal nanoparticle has a thread with a larger thread depth, and from the comparison between fig. 4 and fig. 5, the obtained chiral noble metal nanoparticle has a larger circular dichroism signal at the absorption peak after the thiol-containing achiral molecule is introduced, the intensity can reach about 600 milli-degree (ellipticity), which is 3 times that of example 1 without the thiol-containing achiral molecule, and the above characterization tests show that the introduction of the thiol-containing achiral molecule can obtain the chiral noble metal nanoparticle with a more regular morphology and a stronger optical rotation capability.
As can be seen from the comparison between fig. 2 and 3 and fig. 5 and 6, after the thiol-containing chiral molecule in the system is replaced by its enantiomer, the resulting noble metal shell layer on the surface of the chiral noble metal nanoparticle has an opposite helical direction, and the corresponding optical rotation performance is also reversed.
As can be seen from the comparison between fig. 5 and fig. 7 and 8, the components of the noble metal shell layer coated on the surface of the chiral noble metal nanoparticle also have a certain influence on the optical rotation performance of the chiral noble metal nanoparticle, and if the gold-silver alloy is used as the material of the noble metal shell layer coated on the surface of the chiral noble metal nanoparticle, when the content of silver in the gold-silver alloy is 35 to 50 wt%, the optical rotation performance of the obtained chiral noble metal nanoparticle is relatively strong.
In summary, after the surface of the noble metal nanorod is modified with chiral mercapto molecules, the water-soluble noble metal salt is introduced into the system and the reduction process is regulated, so that the surface of the long axis of the surface of the noble metal nanorod is coated with a noble metal shell which is spirally arranged along a single direction, and chiral noble metal nanoparticles with optical activity are generated from bottom to top. The preparation method of the chiral noble metal nano-particles provided by the invention can be used for preparing the chiral noble metal nano-particles with extremely high efficiency, the yield and the cost are controllable, the obtained chiral noble metal nano-particles have an abnormal stable and clear microstructure, the circular dichroism signal can reach about 600 milli-DEG, the chiral noble metal nano-particles lead other materials with similar structures, and the preparation method has huge application prospects in the fields of chiral catalysis, chiral separation, detection of chiral compounds and chiral optical devices.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The chiral noble metal nano-particles are characterized in that the chiral noble metal nano-particles are noble metal nano-rods of which the surfaces of long shafts are coated with noble metal shells which are spirally arranged along a single direction.
2. The chiral noble metal nanoparticle of claim 1, wherein the coating provides noble metal nanorod surfaces with threads;
preferably, the coating enables the surface of the noble metal nanorod to contain equally spaced threads;
preferably, the thread pitch of the thread is 25-36 nm;
preferably, the thread depth of the thread is less than or equal to 15 nm.
3. The chiral noble metal nanoparticle of claim 1 or 2, wherein the noble metal nanorods are nanorods composed of any one noble metal or an alloy of at least two noble metals of gold, silver, platinum or palladium, preferably gold nanorods;
preferably, the length-diameter ratio of the noble metal nanorods is more than or equal to 2.
4. The chiral noble metal nanoparticle as claimed in any one of claims 1 to 3, wherein the noble metal shell is a noble metal shell composed of any one noble metal of gold, silver, platinum or palladium or an alloy of at least two noble metals, preferably a shell composed of gold, silver or a gold-silver alloy;
preferably, the silver content in the shell layer made of the gold-silver alloy is 10-80 wt%, and more preferably 35-50 wt%.
5. The chiral noble metal nanoparticle of any one of claims 1 to 4, wherein chiral molecules containing mercapto groups are dispersed on the surface of the noble metal nanorods and in the noble metal shell layer;
preferably, the chiral molecule containing sulfydryl is a chiral organic small molecule containing sulfydryl or a chiral polypeptide molecule containing sulfydryl;
preferably, the thiol-containing chiral molecule is any one of L-cysteine and its enantiomer or L-acetylcysteine and its enantiomer.
6. The chiral noble metal nanoparticle of claim 5, wherein the noble metal nanorod surface and the noble metal shell layer further have dispersed therein non-chiral molecules containing thiol groups;
preferably, the non-chiral molecule containing sulfydryl is a non-chiral molecule containing sulfydryl and a benzene ring;
preferably, the non-chiral molecule containing the sulfydryl is any one or a mixture of at least two of p-aminophenol, p-hydroxyphenylthiophenol, p-mercaptobenzoic acid or p-mercaptophenylboronic acid.
7. A method for preparing chiral noble metal nanoparticles according to any one of claims 1 to 6, comprising the following steps:
dispersing water-soluble noble metal nanorods in water, adding a chiral molecule containing sulfydryl or a mixture of the chiral molecule containing sulfydryl and an achiral molecule containing sulfydryl into the water, and incubating the mixture to obtain a noble metal nanorod solution with the chiral molecule containing sulfydryl adsorbed on the surface;
and (2) adding soluble noble metal salt and a reducing agent into the noble metal nanorod solution with the surface adsorbed with the chiral molecules containing sulfydryl obtained in the step (1), uniformly mixing to obtain a mixed solution, and after the soluble noble metal salt in the mixed solution is subjected to reduction treatment, forming a noble metal shell layer spirally arranged along a single direction on the surface of the long axis of the noble metal nanorod to obtain the chiral noble metal nanoparticles.
8. The method according to claim 7, wherein the incubation temperature in step (1) is 25-60 ℃;
preferably, the incubation treatment time in the step (1) is 0.5-24 h;
preferably, the concentration of the noble metal atoms in the noble metal nanorods in the step (1) in the solution is 0.02-0.5 mmol/L calculated by the amount of the noble metal atoms contained in the material;
preferably, the concentration of the chiral molecule containing sulfydryl in the solution in the step (1) is 20-200 mu mol/L;
preferably, the concentration of the thiol-group-containing achiral molecule in the solution in the step (1) is 0-150 μmol/L;
preferably, after the water-soluble noble metal nanorods are dispersed in water, a surfactant is added to promote the dispersion;
preferably, the concentration of the surfactant is 5-20 mmol/L;
preferably, the surfactant is cetyltrimethylammonium bromide;
preferably, the temperature of the reduction treatment in the step (2) is 30-80 ℃;
preferably, the time of the reduction treatment in the step (2) is 20-120 min;
preferably, the concentration of the soluble noble metal salt in the solution in the step (2) is 0.025-0.4 mmol/L;
preferably, the reducing agent in step (2) is ascorbic acid;
preferably, the concentration ratio of the ascorbic acid to the soluble noble metal salt is 1: 1.5-5.
9. The method according to claim 7 or 8, characterized in that it comprises the steps of:
dispersing water-soluble noble metal nanorods in water to ensure that the concentration of noble metal atoms in the water is 0.02-0.5 mmol/L, adding surfactant cetyl trimethyl ammonium bromide, sulfydryl-containing chiral molecules or a mixture of the sulfydryl-containing chiral molecules and sulfydryl-containing achiral molecules into the water to ensure that the concentration of the cetyl trimethyl ammonium bromide is 5-20 mmol/L, the concentration of the sulfydryl-containing chiral molecules is 20-200 mu mol/L, the concentration of the sulfydryl-containing achiral molecules is 0-150 mu mol/L, and incubating the mixture at 25-60 ℃ for 0.5-24 hours to obtain a noble metal nanorod solution with the sulfydryl-containing chiral molecules adsorbed on the surface;
and (2) adding soluble noble metal salt and a reducing agent ascorbic acid into the noble metal nanorod solution with the surface adsorbed with the chiral molecules containing sulfydryl, which is obtained in the step (1), so that the concentration of the soluble noble metal salt in the solution is 0.025-0.4 mmol/L, the concentration ratio of the ascorbic acid to the soluble noble metal salt is 1: 1.5-5, uniformly mixing to obtain a mixed solution, and after the soluble noble metal salt in the mixed solution is subjected to reduction treatment at 30-80 ℃ for 20-120 min, forming a noble metal shell layer spirally growing along a single direction on the surface of a long axis of the noble metal nanorod to obtain the chiral noble metal nanoparticle.
10. Use of chiral noble metal nanoparticles according to claims 1 to 6 for chiral catalysis, chiral separation, detection of chiral compounds or for the production of chiral optical devices or polarizers.
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