WO2018036078A1 - 一种含有配位子键结的金纳米团簇的溶液的制备方法 - Google Patents
一种含有配位子键结的金纳米团簇的溶液的制备方法 Download PDFInfo
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- WO2018036078A1 WO2018036078A1 PCT/CN2017/000411 CN2017000411W WO2018036078A1 WO 2018036078 A1 WO2018036078 A1 WO 2018036078A1 CN 2017000411 W CN2017000411 W CN 2017000411W WO 2018036078 A1 WO2018036078 A1 WO 2018036078A1
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- ligand
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- gold nanoclusters
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- 239000010931 gold Substances 0.000 title claims abstract description 85
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 28
- 239000003446 ligand Substances 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000012045 crude solution Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000000502 dialysis Methods 0.000 claims abstract description 4
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 claims description 33
- 235000019136 lipoic acid Nutrition 0.000 claims description 33
- 229960002663 thioctic acid Drugs 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 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 4
- 239000002537 cosmetic Substances 0.000 claims description 4
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- IZFHEQBZOYJLPK-SSDOTTSWSA-N (R)-dihydrolipoic acid Chemical compound OC(=O)CCCC[C@@H](S)CCS IZFHEQBZOYJLPK-SSDOTTSWSA-N 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- LLNAMUJRIZIXHF-CLFYSBASSA-N (z)-2-methyl-3-phenylprop-2-en-1-ol Chemical compound OCC(/C)=C\C1=CC=CC=C1 LLNAMUJRIZIXHF-CLFYSBASSA-N 0.000 claims description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 claims description 2
- 108010024636 Glutathione Proteins 0.000 claims description 2
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 claims description 2
- 229960003180 glutathione Drugs 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000008194 pharmaceutical composition Substances 0.000 claims description 2
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 2
- 239000001472 potassium tartrate Substances 0.000 claims description 2
- 229940111695 potassium tartrate Drugs 0.000 claims description 2
- 235000011005 potassium tartrates Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000010409 thin film Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002096 quantum dot Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
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- 238000011161 development Methods 0.000 description 3
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 239000008346 aqueous phase Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
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- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- ZFGJFDFUALJZFF-UHFFFAOYSA-K gold(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Au](Cl)Cl ZFGJFDFUALJZFF-UHFFFAOYSA-K 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 therefore Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/16—Inorganic salts, minerals or trace elements
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/24—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing atoms other than carbon, hydrogen, oxygen, halogen, nitrogen or sulfur, e.g. cyclomethicone or phospholipids
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
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- A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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Definitions
- the present invention relates to a process for the preparation of a solution containing a ligand-bonded gold nanoclustered cluster.
- the ligand comprises lipoic acid and dihydrolipoic acid.
- quantum dots have successfully overcome the bottlenecks faced by biological and medical optical probes with their excellent optical properties, and have become important nanomaterials for the design of new generation fluorescent probes.
- the traditional commercial sale of water-soluble quantum dots based on toxic heavy metal materials such as cadmium or lead the impact of its extension on the environment and human health has gradually received attention, and it is currently facing the dilemma of its biomedical applications.
- Gold is an early research nanomaterial. It is called colloidal gold in biological research and its particle size is between 1-100nm.
- Gold quantum dots have a high electron density, good contrast under an electron microscope, and have a relatively high biocompatibility, which has been shown to emit different colors of fluorescence by changing the size of their clusters.
- the present invention provides a method for preparing a solution containing a ligand-bonded gold nanocluster.
- a preparation method comprising the steps of: providing an aqueous solution containing a precursor of gold, a base and a ligand; and performing a reduction reaction to form a liquid containing the ligand-bonded gold nanoclusters under the action of a reducing agent Concentrating the liquid to a solid at 30-60 ° C; dissolving the solid into water to form a crude solution; and performing a purification procedure to pass the crude solution through a membrane or a dialysis tube to obtain the gold nanoclusters containing the ligand-bonded Solution.
- the preparation method disclosed in the present invention is a one-batch process.
- a key technical feature of the present invention is that the preparation method provided by the present invention is to prepare an aqueous solution for synthesizing gold nanoclusters containing a ligand-bonded bond in an aqueous phase.
- the manufacturing process of the present invention is a green manufacturing process, and the aqueous solution containing the ligand-bonded gold nanoclusters prepared according to the present invention does not contain Harmful substances or solvents such as toluene and dimethylformamide, therefore, aqueous solutions containing ligand-bonded gold nanoclusters prepared according to the process of the present invention are particularly suitable for use in the cosmetic and biomedical industries.
- Fig. 1 is a TEM image of a solution of a gold nanoclusters containing a lipoic acid ligand-bonded bond according to an experimental example of the present invention.
- FIG. 2 is a TEM image of a single cluster of gold nanoclusters containing lipoic acid ligand-bonded bonds according to an experimental example of the present invention.
- FIG. 3 is a core size distribution diagram of a solution of a gold nanoclusters containing lipoic acid ligand-bonded bonds according to an experimental example of the present invention; this FIG. 3 is drawn based on the software calculation results of FIG. 2.
- Figure 4 is a graph showing the dynamic light scattering number size distribution of a solution of a gold nanoclusters containing lipoic acid ligand-bonded bonds as described in the experiments of the present invention.
- Figure 5 is a graph showing the dynamic light scattering volume size distribution of a solution of a gold nanoclusters containing lipoic acid ligand-bonded bonds as described in the experiments of the present invention.
- Figure 6 is a photoelectronogram of a solution of a gold nanoclusters containing lipoic acid ligand-bonded bonds according to an experimental example of the present invention.
- Fig. 7 is a graph showing the thermogravimetric analysis of a solution of a gold nanoclustered group containing lipoic acid ligand-bonded according to an experimental example of the present invention.
- Figure 8 is a Fourier infrared spectrum of a solution of a gold nanoclusters containing lipoic acid ligand-bonded bonds according to an experimental example of the present invention.
- Fig. 9 is an X-ray diffraction diagram of a solution of a gold nanoclustered group containing a lipoic acid ligand-bonded according to an experimental example of the present invention.
- Figure 10 is a graph showing the relationship between the fluorescence intensity and the heat treatment temperature of a solution of a gold nanoclusters containing lipoic acid ligand-bonded bonds according to the present invention.
- Figure 11 is a graph showing the relationship between the fluorescence intensity of a solution containing a lipoic acid ligand-bonded gold nanoclusters and a UV treatment procedure according to the present invention.
- Figure 12 is a graph showing the relationship between the fluorescence intensity of a solution containing a lipoic acid ligand-bonded gold nanoclusters of the present invention and its concentration.
- the present invention provides a method for preparing a solution containing a ligand-bonded gold nanocluster, the method comprising the steps of: providing a gold-containing precursor, a base, and a ligand An aqueous solution; performing a reduction reaction to form a liquid containing the ligand-bonded gold nanoclusters under the action of a reducing agent; concentrating the liquid to a solid at 30-60 ° C; dissolving the solid into water to form a crude solution; A purification procedure is performed to obtain a solution of the ligand-bonded gold nanoclusters by passing the crude solution through a membrane or a dialysis tube.
- the method for preparing a solution of the above-described ligand-bonded gold nanoclusters further comprises a heating program and/or a UV treatment program to increase the gold nanoclusters containing the ligand-bonded bonds.
- the fluorescence intensity of the solution is not limited to a heating program and/or a UV treatment program.
- the heating procedure is performed between 30-150 °C.
- the UV processing procedure is performed between wavelengths of 300-400 nm.
- the gold precursor comprises trivalent gold Au(III) ions.
- the ligand comprises lipoic acid and dihydrolipoic acid.
- the base comprises sodium hydroxide and potassium hydroxide.
- the reducing agent comprises sodium borohydride, sodium citrate, potassium tartrate, dithiothreitol, tris(2-carboxyethyl)phosphine, tetrabutyl Ammonium nitrate, ascorbic acid and glutathione.
- the reduction reaction is carried out between 5 and 40 °C.
- the purification procedure is to maintain the molecular weight of the gold nanoclusters containing the ligand linkage between 10-100 kDa.
- the Fourier infrared spectrum of the gold nanoclusters containing the ligand linkages comprises the following peaks: 3261, 2920, 2852, 1560 and 1401 cm -1 .
- the X-ray diffraction spectrum of the gold nanoclusters containing the ligand linkages comprises the following peaks: 38.5° (111), 44.6° (200), 64.8° (220), 77.8°. (311) 2-theta degree.
- the gold nanoclusters containing the ligand-bonded bonds have a hydraulic mean diameter of from 1 to 4 nm.
- the weight ratio of the gold containing the ligand-bonded gold nanoclusters to the ligand is 0.5-10.
- the gold nanoclusters containing the ligand linkages are part of a composition comprising a cosmetic composition, a food composition, and a pharmaceutical composition.
- the preparation method of the solution containing the ligand-bonded gold nanoclusters disclosed in the present invention is a one-batch process.
- a key technical feature of the present invention is that the preparation method provided by the present invention is to prepare an aqueous solution for synthesizing gold nanoclusters containing a ligand-bonded bond in an aqueous phase.
- the manufacturing process of the present invention is a green manufacturing process, and the aqueous solution containing the ligand-bonded gold nanoclusters prepared according to the present invention does not contain Any harmful substance or solvent such as toluene and dimethylformamide, therefore, an aqueous solution containing the ligand-bonded gold nanoclusters prepared according to the method of the present invention is particularly suitable for use in the cosmetics and biomedical industries.
- TEM Transmission electron microscopy
- DLS dynamic light scattering
- XPS X-ray photoelectron spectroscopy
- TGA thermogravimetric analysis
- FTIR Fourier transform infrared spectrometer
- XRD X-ray pyroelectric
- TEM analysis shows that the size of the gold nanoclusters containing the lipoic acid ligand-bonded bond of the present invention is less than 10 nm, and the gold nanoclusters bonded by the lipoic acid ligand are uniformly dispersed.
- the average core diameter of the gold nanoclusters containing the lipoic acid ligand-bonded in the present invention is 1.45 ⁇ 0.34 nm.
- DLS analysis showed that the number distribution of gold batches of three batches of lipoic acid ligand-bonded gold nanoclusters prepared according to the method of the present invention was 1.82 nm (standard deviation was 0.56 nm), 2.28, respectively. Nm (standard deviation is 0.60 nm) and 2.71 nm (standard deviation is 0.89 nm).
- the X-ray photoelectron spectrum shows that the atomic percentages of C, O, S, Na, N and Au are 73.9%, 17.0%, 4.4%, 2.7%, 1.3% and 0.6%, respectively.
- thermogravimetric analysis showed that the weight percentages of gold and ligand were 67.39% and 32.61%, respectively.
- the Fourier transform infrared spectrum showed peaks at the following positions: 3261, 2920, 2852, 1560 and 1401 cm -1 .
- the X-ray diffraction pattern shows the four characteristic peak positions as follows: 38.5° (111), 44.6° (200), 64.8° (220), and 77.8° (311).
- WG represents the manufacturing process of the present invention in which the concentration step is omitted
- IWG-55C, IWG-80C, and IWG-90C respectively represent the manufacture of the concentration step and the heating step (55 ° C, 80 ° C, and 90 ° C), respectively.
- Process, according to Figure 10 the fluorescence intensity of the liquid containing the lipoic acid ligand-bonded gold nanoclusters prepared by the manufacturing process of the concentration step and the heating step (55 ° C, 80 ° C and 90 ° C) 700nm) a significant increase.
- WG represents the manufacturing process of the present invention in which the concentration step is omitted
- IWG-UV represents a manufacturing process of performing a concentration step and treatment with UV light (wavelength 365 nm), according to FIG. 11, while taking a concentration step and UV light
- the fluorescence intensity (wavelength 700 nm) of the liquid having the lipoic acid ligand-bonded gold nanoclusters prepared by the manufacturing process of the wavelength of 365 nm) was greatly increased.
- WG represents the manufacturing process of the present invention in which the concentration step is omitted
- IWG-50X, IWG-100X, IWG-200X, IWG-250X, and IWG-300X respectively represent performing the concentration step to the lipoic acid-containing ligand bond.
- the concentration of the knotted gold nanoclusters is 50 times, 100 times, 200 times, 250 times and 300 times the original concentration.
- the fluorescence intensity is also increased, in order to achieve the maximum fluorescence intensity of the gold nanoclusters containing the lipoic acid ligand-bonded bonds.
- the key to the concentration step in the method of the present invention is to concentrate the liquid nano-cluster containing the lipoic acid ligand-bonded to a solid state, and then dissolve the solid into water to carry out a purification procedure to obtain the present invention.
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Abstract
一种含有配位子键结的金纳米团簇的溶液的制备方法，该方法包含以下步骤：提供含有金的前驱物、碱和配位子的水溶液；进行还原反应使上述的水溶液在还原剂作用下形成含有配位子键结的金纳米团簇的液体；浓缩该液体至固体；溶解该固体至水中形成粗溶液；和进行纯化程序，使该粗溶液通过薄膜或透析管而得到该含有配位子键结的金纳米团簇的溶液。
Description
本发明是关于一种含有配位子键结的金纳米团簇的溶液的制备方法。特别是该配位子包含硫辛酸和二氢硫辛酸。
传统的有机染料分子的性质在高解析的生物影像应用上受到了限制，但是量子点相较于传统的有机染料分子具有荧光亮度强、光稳定性佳、以及用单一波长的激光便可以激发出多种不同波长的发射波的特性。发射波是狭窄且对称的波形，且可重复激发，因此荧光时效可以持久。这些特性吸引科学家的重视，纳米量子点的应用也越来越多样性，深具取代传统染剂的潜力，因此，在生医工程应用方面，更有令人期待的发展性。
近年来量子点以其优异的光学特性，已成功地克服过去生物及医学光学探针所面临的瓶颈，成为新一代荧光探针设计的重要纳米材料。从细胞立体影像、活细胞监控、单分子胞内追踪、长效型光学感测器研制、癌症诊断与治疗皆有突破性进展，加上量子点快速产业化及其上亿商机，已成纳米生物技术极为成功应用的典范。然而传统市售以镉或铅等有毒重金属材料为主的水溶性量子点，其延伸对环境及人体健康可能带来的冲击逐渐受到重视，是目前全面开拓其生医应用所面临的窘境。
金是研究较早的一种纳米材料，在生物学研究中被称为胶体金，粒子尺寸在1-100nm之间。金量子点具有很高的电子密度，在电子显微镜下有很好的衬度，并且具有相当高的生物相容性，其已被证实经由改变其原子团簇的大小即可发出不同颜色的荧光，能够应用在多元的生医标定或光学元件的制作上，但由于制造过程相当不易，合成时需要利用昂贵的树状聚合物(dendrimer)作为金量子点的包覆材料，耗时且不易大量生产，故限制其广大生医应用的开发。因此，开发出简易并可大量生产制造的金量子点形成技术是产业界亟欲发展的重点。
鉴于上述发明背景中，为了符合产业上的要求，本发明提供一种含有配位子键结的金纳米团簇的溶液的制备方法。
发明内容
鉴于上述的发明背景，为了符合产业上的要求，本发明的目的在于提供一种含有配位子键结的金纳米团簇的溶液的制备方法。
本发明的一目的在于提供一种含有配位子键结的金纳米团簇的溶液的
制备方法，该方法包含以下步骤：提供含有金的前驱物、碱和配位子的水溶液；进行还原反应使上述的水溶液在还原剂作用下形成含有配位子键结的金纳米团簇的液体；在30-60℃浓缩该液体至固体；溶解该固体至水中形成粗溶液；和进行纯化程序，使该粗溶液通过薄膜或透析管而得到该含有配位子键结的金纳米团簇的溶液。
综上所述，本发明所揭露的制备方法是一步法(one-batch process)。本发明的关键技术特征是本发明所提供的制备方法是在水相中制备合成含有配位子键结的金纳米团簇的水溶液。再者，由于制备过程中是使用水作为溶剂，因此本发明所述的制造过程是绿色环保制造过程，根据本发明所制备得到的含有配位子键结的金纳米团簇的水溶液不会含有有害性物质或溶剂，如甲苯和二甲基甲酰胺，因此，根据本发明的方法所制备得到的含有配位子键结的金纳米团簇的水溶液特别适合应用在化妆品和生医产业。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，而可依照说明书的内容予以实施，并且为了让本发明的上述和其他目的、特征和优点能够更明显易懂，以下特举较佳实施例，并配合附图，详细说明如下。
附图的简要说明
图1是本发明实验例所述的含有硫辛酸配位子键结的金纳米团簇的溶液的TEM影像图。
图2是本发明实验例所述的含有硫辛酸配位子键结的金纳米团簇的单颗团簇的TEM影像图。
图3是本发明实验例所述的含有硫辛酸配位子键结的金纳米团簇的溶液的核心尺寸分布图；该图3是根据图2的软件计算结果所绘制。
图4是本发明实验所述的含有硫辛酸配位子键结的金纳米团簇的溶液的动态光散射数目尺寸分布图。
图5是本发明实验所述的含有硫辛酸配位子键结的金纳米团簇的溶液的动态光散射体积尺寸分布图。
图6是本发明实验例所述的含有硫辛酸配位子键结的金纳米团簇的溶液的光电子图谱。
图7是本发明实验例所述的含有硫辛酸配位子键结的金纳米团簇的溶液的热失重分析图。
图8是本发明实验例所述的含有硫辛酸配位子键结的金纳米团簇的溶液的傅立叶红外光谱图。
图9是本发明实验例所述的含有硫辛酸配位子键结的金纳米团簇的溶液的X光绕射图。
图10是本发明所述的含有硫辛酸配位子键结的金纳米团簇的溶液的荧光强度和热处理温度的关系图。
图11是本发明所述的含有硫辛酸配位子键结的金纳米团簇的溶液的荧光强度和UV处理程序的关系图。
图12是本发明所述的含有硫辛酸配位子键结的金纳米团簇的溶液的荧光强度和其浓度的关系图。
实现发明的最佳方式
有关本发明之前述及其他技术内容、特点与功效，在以下配合参考图式的一较佳实施例的详细说明中，将可清楚的呈现。为了能彻底地了解本发明，将在下列的描述中提出详尽的步骤及其组成。显然地，本发明的施行并未限定于该领域的技艺者所熟习的特殊细节。另一方面，众所周知的组成或步骤并未描述于细节中，以避免造成本发明不必要的限制。本发明的较佳实施例会详细描述如下，然而除了这些详细描述之外，本发明还可以广泛地施行在其他的实施例中，且本发明的范围不受限定，其以本申请所要保护的专利范围为准。
根据本发明的一代表实施例，本发明提供一种含有配位子键结的金纳米团簇的溶液的制备方法，该方法包含以下步骤：提供含有金的前驱物、碱和配位子的水溶液；进行还原反应使上述的水溶液在还原剂作用下形成含有配位子键结的金纳米团簇的液体；在30-60℃浓缩该液体至固体；溶解该固体至水中形成粗溶液；和进行纯化程序，使该粗溶液通过薄膜或透析管而得到该含有配位子键结的金纳米团簇的溶液。
在一较佳具体范例，其中上述的含有配位子键结的金纳米团簇的溶液的制备方法还包含加热程序和/或UV处理程序以增加该含有配位子键结的金纳米团簇的溶液的荧光强度。
在一具体范例，该加热程序是在30-150℃之间执行。
在一具体范例，该UV处理程序是在波长300-400nm之间执行。
在一较佳具体范例，该金的前驱物包含三价金Au(III)离子。
在一较佳具体范例，其中上述的金的前驱物对于配位子的摩尔比例是小于10，且该配位子包含硫辛酸(lipoic acid)和二氢硫辛酸(dihydrolipoic acid)。
在一具体范例，该碱包含氢氧化钠和氢氧化钾。
在一具体范例，该还原剂包含硼氢化钠、柠檬酸钠、酒石酸钾、二硫苏糖醇(Dithiothreitol)、三(2-羧乙基)膦(Tris(2-carboxyethyl)phosphine)、四丁基硝酸铵、抗坏血酸和谷胱甘肽。
在一具体范例，该还原反应是在5-40℃之间执行。
在一具体范例，该纯化程序是维持该含有配位子键结的金纳米团簇的分子量在10-100kDa之间。
在一较佳具体范例，该含有配位子键结的金纳米团簇的傅立叶红外光谱包含以下波峰：3261，2920，2852，1560和1401cm-1。
在一较佳具体范例，该含有配位子键结的金纳米团簇的X-ray绕射谱包含以下波峰：38.5°(111)，44.6°(200)，64.8°(220)，77.8° (311) 2-theta degree。
在一较佳具体范例，该含有配位子键结的金纳米团簇的水力平均直径是1-4nm。
在一较佳具体范例，该含有配位子键结的金纳米团簇的金对于该配位子的重量比例是0.5-10。
在一具体范例，该含有配位子键结的金纳米团簇是组成物的一部份，该组成物包含化妆品组成物、食品组成物和医药组成物。
根据上述，本发明所揭露的含有配位子键结的金纳米团簇的溶液的制备方法是一步法(one-batch process)。本发明的关键技术特征是本发明所提供的制备方法是在水相中制备合成含有配位子键结的金纳米团簇的水溶液。再者，由于制备过程中是使用水作为溶剂，因此本发明所述的制造过程是绿色环保制造过程，根据本发明所制备得到的含有配位子键结的金纳米团簇的水溶液不会含有任何有害性物质或溶剂，如甲苯和二甲基甲酰胺，因此，根据本发明的方法所制备得到的含有配位子键结的金纳米团簇的水溶液特别适合应用在化妆品和生医产业。
以下以具体实验例说明本发明的内容和技术特征，但并不因此限定本发明的范围。
实验例：制备合成含有硫辛酸配位子键结的金纳米团簇的水溶液
30μmol的硫辛酸溶于含有氢氧化钠的去离子水中，加入10μmol的gold(III)chloride trihydrate。.室温下持续搅拌并且加入硼氢化纳(Sodium borohydride)再搅拌反应15分钟后，直接在55℃浓缩上述的反应混合物至固体，然后再加入去离子水溶解该固体形成粗溶液(crude solution)，最后以10kDa的薄膜进行纯化程序得到本发明所述的含有硫辛酸配位子键结的金纳米团簇的水溶液。
上述实验例所制备得到的含有硫辛酸配位子键结的金纳米团簇的水溶液以下述仪器进行各项分析鉴定：透射电子显微镜(Transmission electron microscopy(TEM))、动态光散射仪(dynamic light scattering(DLS))、光电子扫描仪(X-ray photoelectron spectroscopy(XPS))、热失重分析仪(thermogravimetric analysis(TGA))、傅立叶红外光谱仪(Fourier transform infrared spectrometer(FTIR))和X光热射仪(X-ray
diffraction(XRD))。
本发明实验例所述的含有硫辛酸配位子键结的金纳米团簇的水溶液的特性分析和鉴定如表一所示。
表一
如图1和图2所示，TEM分析显示本发明的含有硫辛酸配位子键结的金纳米团簇的尺寸小于10nm，且该硫辛酸配位子键结的金纳米团簇是均匀分散在水溶液之中；根据图3所示，本发明的含有硫辛酸配位子键结的金纳米团簇的平均核心直径(average core diameter)是1.45±0.34nm。
如图4所示，DLS分析显示根据本发明的方法所制备的3批次的硫辛酸配位子键结的金纳米团簇的数量尺寸分布分别是1.82nm(标准差是0.56nm)、2.28nm(标准差是0.60nm)和2.71nm(标准差是0.89nm)。
如图5所示，DLS分析显示根据本发明的方法所制备的3批次的硫辛酸配位子键结的金纳米团簇的体积尺寸分布分别是2.56nm(标准差是1.44nm)、2.80nm(标准差是0.96nm)和4.00nm(标准差是2.16nm)。
如图6所示，X光电子图谱显示C，O，S，Na，N和Au的原子百分比分别是73.9％，17.0％，4.4％，2.7％，1.3％和0.6％。
如图7所示，热重量分析显示金和配位子的重量百分比分别是67.39％和32.61％。
如图8所示，傅立叶红外光谱显示以下位置的波峰：3261，2920，2852，1560和1401cm-1。
如图9所示，X光绕射图谱显示4个特征波峰位置如下：38.5°(111)，
44.6°(200)，64.8°(220)，和77.8°(311)。
制造过程参数和含有硫辛酸配位子键结的金纳米团簇的液体的荧光强度的关系
如图10所示，WG代表省略浓缩步骤的本发明的制造过程，IWG-55C、IWG-80C和IWG-90C分别代表同时执行浓缩步骤和加热步骤(55℃、80℃和90℃)的制造过程，根据图10，同时以浓缩步骤和加热步骤(55℃、80℃和90℃)的制造过程所制备得到的含有硫辛酸配位子键结的金纳米团簇的液体的荧光强度(波长700nm)显著的增加。
如图11所示，WG代表省略浓缩步骤的本发明的制造过程，IWG-UV代表执行浓缩步骤和以UV光(波长365nm)处理的制造过程，根据图11，同时以浓缩步骤和UV光(波长365nm)处理的制造过程所制备得到的有硫辛酸配位子键结的金纳米团簇的液体的荧光强度(波长700nm)大幅度的增加。
如图12所示，WG代表省略浓缩步骤的本发明的制造过程，IWG-50X、IWG-100X、IWG-200X、IWG-250X和IWG-300X分别代表执行浓缩步骤至含有硫辛酸配位子键结的金纳米团簇的浓度为原始浓度的50倍、100倍、200倍、250倍和300倍。根据图12，当含有硫辛酸配位子键结的金纳米团簇的浓度增加时，荧光强度亦增加，为了达到含有硫辛酸配位子键结的金纳米团簇具有最大的荧光强度的目的，本发明的方法中的浓缩步骤的关键是浓缩含有硫辛酸配位子键结的金纳米团簇的液体至固体状态，然后再回溶该固体至水中进行纯化程序后得到本发明所述的含有硫辛酸配位子键结的金纳米团簇的溶液。
以上所述，仅是本发明的较佳实施例而已，并非对本发明做任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容做出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。
Claims (15)
- 一种含有配位子键结的金纳米团簇的溶液的制备方法，其特征在于，该方法包含以下步骤：提供含有金的前驱物、碱和配位子的水溶液；进行还原反应使上述的水溶液在还原剂作用下形成含有配位子键结的金纳米团簇的液体；在30-60℃浓缩该液体至固体；溶解该固体至水中形成粗溶液；和进行纯化程序，使该粗溶液通过薄膜或透析管而得到该含有配位子键结的金纳米团簇的溶液。
- 根据权利要求1所述的制备方法，其特征在于：还包含加热程序和/或UV处理程序以增加该含有配位子键结的金纳米团簇的溶液的荧光强度。
- 根据权利要求2所述的制备方法，其特征在于：该加热程序是在30-150℃之间执行。
- 根据权利要求2所述的制备方法，其特征在于：该UV处理程序是在波长300-400nm之间执行。
- 根据权利要求1所述的制备方法，其特征在于：该金的前驱物包含三价金Au(III)离子。
- 根据权利要求1所述的制备方法，其特征在于：其中上述的金的前驱物对于配位子的摩尔比例是小于10，且该配位子包含硫辛酸和二氢硫辛酸。
- 根据权利要求1所述的制备方法，其特征在于：该碱包含氢氧化钠和氢氧化钾。
- 根据权利要求1所述的制备方法，其特征在于：该还原剂包含硼氢化钠、柠檬酸钠、酒石酸钾、二硫苏糖醇、三(2-羧乙基)膦、四丁基硝酸铵、抗坏血酸和谷胱甘肽。
- 根据权利要求1所述的制备方法，其特征在于：该还原反应是在5-40℃之间执行。
- 根据权利要求1所述的制备方法，其特征在于：该纯化程序是维 持该含有配位子键结的金纳米团簇的分子量在10-100kDa之间。
- 根据权利要求1所述的制备方法，其特征在于：该含有配位子键结的金纳米团簇的傅立叶红外光谱包含以下波峰：3261，2920，2852，1560和1401cm-1。
- 根据权利要求1所述的制备方法，其特征在于：该含有配位子键结的金纳米团簇的X-ray绕射图谱包含以下波峰：38.5。（111)，44.6°(200)，64.8°(220)，和77.8°(311) 2-theta degree。
- 根据权利要求1所述的制备方法，其特征在于：该含有配位子键结的金纳米团簇的水力平均直径是1-4nm。
- 根据权利要求1所述的制备方法，其特征在于：该含有配位子键结的金纳米团簇的金对于该配位子的重量比例是0.5-10。
- 根据权利要求1所述的制备方法，其特征在于：该含有配位子键结的金纳米团簇是组成物的一部份，该组成物包含化妆品组成物、食品组成物和医药组成物。
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| EP17842504.7A EP3508291A4 (en) | 2016-08-23 | 2017-07-25 | METHOD FOR PRODUCING A SOLUTION WITH LIGAND-TIED GOLD NANO CLUSTERS |
| JP2019531504A JP6810268B2 (ja) | 2016-08-23 | 2017-07-25 | リガンドが結合した金ナノクラスターを含む溶液の製造方法 |
| KR1020197008587A KR20190042668A (ko) | 2016-08-23 | 2017-07-25 | 리간드가 결합된 금 나노클러스터를 함유하는 용액의 제조 방법 |
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| KR20190142814A (ko) * | 2018-06-19 | 2019-12-30 | 경희대학교 산학협력단 | 전기화학발광 금 나노클러스터 수용액 및 그 제조방법 |
| CN110772432A (zh) * | 2019-11-05 | 2020-02-11 | 北京科技大学 | 一种长效金纳米簇荧光染发剂及染发方法 |
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| US10752834B2 (en) * | 2018-05-17 | 2020-08-25 | Chung Yuan Christian University | Composite fluorescent gold nanoclusters with high quantum yield and method for manufacturing the same |
| US10756243B1 (en) * | 2019-03-04 | 2020-08-25 | Chung Yuan Christian University | Light-emitting diode package structure and method for manufacturing the same |
| CN110724156B (zh) * | 2019-10-22 | 2022-03-15 | 安徽大学 | 一种增强铜纳米团簇荧光强度的方法 |
| CN113061261A (zh) * | 2021-03-30 | 2021-07-02 | 深圳第三代半导体研究院 | 一种铜纳米簇荧光粉及其制备方法 |
| CN113333772B (zh) * | 2021-06-18 | 2023-01-03 | 南昌大学 | 金纳米簇的制备方法及其在2,4,6-三硝基苯酚检测的应用 |
| KR102636435B1 (ko) | 2021-09-14 | 2024-02-14 | 건국대학교 산학협력단 | 칼슘 나노클러스터의 제조방법, 및 이에 따라 제조된 칼슘 나노클러스터를 유효성분으로 포함하는 화장료용 형광 소재 |
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| US20180055083A1 (en) | 2018-03-01 |
| EP3508291A1 (en) | 2019-07-10 |
| EP3508291A4 (en) | 2020-03-11 |
| CN109689256A (zh) | 2019-04-26 |
| JP6810268B2 (ja) | 2021-01-06 |
| KR20190042668A (ko) | 2019-04-24 |
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| JP2019528381A (ja) | 2019-10-10 |
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