CN101502880B - Method for preparing sub-nano golden cluster molecule - Google Patents
Method for preparing sub-nano golden cluster molecule Download PDFInfo
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- CN101502880B CN101502880B CN2009100964097A CN200910096409A CN101502880B CN 101502880 B CN101502880 B CN 101502880B CN 2009100964097 A CN2009100964097 A CN 2009100964097A CN 200910096409 A CN200910096409 A CN 200910096409A CN 101502880 B CN101502880 B CN 101502880B
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000010931 gold Substances 0.000 claims abstract description 73
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052737 gold Inorganic materials 0.000 claims abstract description 59
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- 239000007864 aqueous solution Substances 0.000 claims description 52
- 239000002159 nanocrystal Substances 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 34
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 27
- 239000012279 sodium borohydride Substances 0.000 claims description 22
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 22
- 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 20
- 239000006193 liquid solution Substances 0.000 claims description 14
- 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 12
- 239000001509 sodium citrate Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims description 10
- 239000011668 ascorbic acid Substances 0.000 claims description 10
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 6
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 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
- 238000002360 preparation method Methods 0.000 claims description 4
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- 108010024636 Glutathione Proteins 0.000 claims description 3
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims description 3
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 3
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 3
- 235000009582 asparagine Nutrition 0.000 claims description 3
- 229960001230 asparagine Drugs 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 claims description 3
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 3
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000018102 proteins Nutrition 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000013049 sediment Substances 0.000 description 14
- 239000000725 suspension Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000376 reactant Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- XQQSWXUDAPLMKD-UHFFFAOYSA-N N,N-dimethylheptadecan-1-amine hydrobromide Chemical compound Br.CCCCCCCCCCCCCCCCCN(C)C XQQSWXUDAPLMKD-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 208000035126 Facies Diseases 0.000 description 4
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 4
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 235000010703 Modiola caroliniana Nutrition 0.000 description 4
- 244000038561 Modiola caroliniana Species 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 octyl group amine bromides Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012984 biological imaging Methods 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 229960003180 glutathione Drugs 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a method for preparing a sub-nanometer gold cluster molecule. The purification of the prior part is complex. The method of the invention firstly uses chloroauric acid as raw material and adopts a solution method for synthesizing a gold nanometer crystal solution. Then, the gold nanometer crystal solution and amine solution with the molar concentration of 1mM-10M are mixed and react for more than 30min. After the reaction is finished, the centrifugal separation is carried out on the solution to obtain sub-nanometer gold cluster molecular solution. The sub-nanometer gold cluster molecule obtained by the method is monodispersed Au8 cluster molecule. Only common centrifugation is required for separating other impurities. The purification mode is simple.
Description
Technical field
The invention belongs to the material technology field, relate to the preparation method of sub-nano golden cluster molecule, specifically, relate to a kind of method that adopts gold nano-crystal and organic amine molecule to prepare sub-nano golden cluster molecule as reactant.
Background technology
Gold nano-crystal (gold nanocrystals) is owing to the biocompatibility of itself is being used widely in a lot of fields.Based on the character of its high electron density and surface plasma enhancing etc., collaurum or various gold nano-crystal are used to organism mark, biological detection, oncotherapy etc.But because the fermi level of metal is in the centre that can be with, common gold nano-crystal can be not luminous or luminous efficiency is very low.Recently, be that the semiconductor-quantum-point (semiconductorquantum dots) of representative has been applied on biomarker (biological labeling) and the biological image (biologicalimaging) with the chalcogenide.But these semiconductor-quantum-points have toxicity and can not bio-compatible, must be through complicated and loaded down with trivial details chemical surface treatment just can be dispersed in the aqueous solution and have biocompatibility.Though but semiconductor-quantum-point still exists potential toxicity having biocompatibility through after the chemical surface treatment to organism, makes semiconductor-quantum-point be applied to biological field challenged.And have the gold of luminosity and banking group cluster molecule (clusters) (general size is less than 1nm) owing to itself have biocompatibility, be expected to be applied to these biological nano fields.What the present invention relates to is exactly the golden cluster molecule that synthesizes highly luminescent in the aqueous solution, and synthetic method is environmentally friendly.
The method of the multiple synthetic luminous sub-nano golden cluster molecule of report nearly all is that employing is that raw material is directly synthetic under the effect of reducing agent from gold chloride at present.The product that generally obtains need just can obtain sub-nano golden cluster molecule through complicated purification, but contains the sub-nano golden cluster molecule of various gold atom numbers often.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of method of synthetic sub-nano golden cluster molecule newly is provided.
The inventive method may further comprise the steps:
Step (1). with the gold chloride is raw material, adopts the synthetic gold nanocrystals liquid solution of solution methods, and the method for this step is ripe prior art.
Step (2). with gold nanocrystals liquid solution and molar concentration is that the equivalent proportion of gold nano-crystal and organic amine molecule is 1: 1 * 10 more than the organic amine solution hybrid reaction 30min of 1mM~10M
-1~1 * 10
3
Step (3). reaction is carried out centrifugation to solution after finishing, and obtains sub-nano golden cluster molecule solution.
Described in the step (1) is raw material with the gold chloride, adopt the synthetic gold nanocrystals liquid solution of solution methods, be to add sodium citrate aqueous solution in the aqueous solution of chloraurate of boiling, stirring condition is reaction 15~30min down, obtains the aqueous solution of emboliform gold nano-crystal; The equivalent proportion of gold chloride and natrium citricum is 1: 1~5.
Described in the step (1) is raw material with the gold chloride, adopt the synthetic gold nanocrystals liquid solution of solution methods, be that aqueous solution of chloraurate is mixed with the toluene solution that contains lauryl mercaptan, under the stirring condition gold chloride is transferred to the toluene phase from water, add the toluene solution that sodium borohydride reduction obtains emboliform gold nano-crystal then; The equivalent proportion of gold chloride and lauryl mercaptan is 1: 2.5~5, and the sodium borohydride of adding and the equivalent proportion of gold chloride are 10~100: 1.
Described in the step (1) is raw material with the gold chloride, adopt the synthetic gold nanocrystals liquid solution of solution methods, be in equivalent proportion is the aqueous solution of 1: 1 gold chloride and natrium citricum, to add sodium borohydride, the golden nanometer particle that reduction obtains is as crystal seed, and the sodium borohydride of adding and the equivalent proportion of gold chloride are 40: 1; In containing the aqueous solution of softex kw, add gold chloride and ascorbic acid then, add again and leave standstill reaction 10~20 hours after crystal seed mixes, obtain the aqueous solution of bar-shaped gold nano-crystal, the equivalent proportion of crystal seed and gold chloride is 1: 400, the equivalent proportion of softex kw and gold chloride is 360: 1, and the equivalent proportion of ascorbic acid and gold chloride is 2: 1.
The hybrid reaction of gold nanocrystals liquid solution described in the step (2) and organic amine solution is the ultrasonic reaction that carries out in the ultrasonic cleaning machine.
The hybrid reaction of gold nanocrystals liquid solution described in the step (2) and organic amine solution is the stirring reaction that carries out in flask.
Organic amine molecule described in the step (2) is a kind of in the hexa, albuminous protein employed, DNA of histidine, mercaptoethylmaine, asparagine, glutamine, glutamic acid, lysine, phenylalanine, serine, tyrosine, reduced glutathione, hexa, acidifying.
The inventive method can adopt various gold nano-crystals and common organic amine molecule to comprise that biomolecule commonly used is the feedstock production sub-nano golden cluster molecule, and the sub-nano golden cluster molecule that obtains thus is monodispersed Au
8Cluster molecule, and only need common centrifugally just can separate other impurity, the purification mode is simple.
The specific embodiment
Embodiment 1
Step 1: in the 250mL round-bottomed flask, add 125mL 1mM HAuCl
4The aqueous solution is at N
2Protection is heated to boiling down, adds 12.5mL 10mM sodium citrate aqueous solution fast, continues heating 10min, removes heating jacket, continues to stir 5min, is cooled to room temperature, obtains mauve emboliform gold nanocrystals liquid solution.
Step 2:1mL 10
-3The emboliform gold nano-crystal of M reacts 30min with after 1mL 1mM histidine mixes under ultrasonic and normal temperature condition.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 2
Step 1: in the 250mL round-bottomed flask, add 125mL 1mM HAuCl
4The aqueous solution is at N
2Protection is heated to boiling down, adds 12.5mL 20mM sodium citrate aqueous solution fast, continues heating 10min, removes heating jacket, continues to stir 20min, is cooled to room temperature, obtains mauve emboliform gold nanocrystals liquid solution.
Step 2:1mL 10
-3The emboliform gold nano-crystal of M is with after 1mL 10mM mercaptoethylmaine mixes, stir and normal temperature condition under reacted 1 hour.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 3
Step 1: in the 250mL round-bottomed flask, add 125mL 1mM HAuCl
4The aqueous solution is at N
2Protection is heated to boiling down, adds 12.5mL 30mM sodium citrate aqueous solution fast, continues heating 10min, removes heating jacket, continues to stir 15min, is cooled to room temperature, obtains mauve emboliform gold nanocrystals liquid solution.
Step 2:1mL 10
-3The emboliform gold nano-crystal of M is with after 1mL 100mM asparagine mixes, and reaction is 2 hours under ultrasonic and normal temperature condition.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 4
Step 1: in the 250mL round-bottomed flask, add 125mL 1mM HAuCl
4The aqueous solution is at N
2Protection is heated to boiling down, adds 12.5mL 50mM sodium citrate aqueous solution fast, continues heating 10min, removes heating jacket, continues to stir 10min, is cooled to room temperature, obtains mauve emboliform gold nanocrystals liquid solution.
Step 2:1mL 10
-3The emboliform gold nano-crystal of M is with after 1mL 10mM glutamine mixes, stir and normal temperature condition under reacted 3 hours.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 5
Step 1: the toluene solution that in the 100mL there-necked flask, adds 10mL 10mM aqueous solution of chloraurate and 10mL45mM four octyl group amine bromides (TOAB); vigorous stirring 15 minutes; the toluene solution that in flask, adds 5mL 50mM lauryl mercaptan then; the aqueous solution with the 5mL 0.2M sodium borohydride of fresh configuration adds in the constant pressure funnel simultaneously; back feeding nitrogen then is evacuated system; under protection of nitrogen gas, sodium borohydride is added in the reactant liquor fast, keep at last and stirred 3 hours.After reaction finishes,, remove water with the reactant liquor layering.Organic facies then decompression distillation adds 100mL ethanol then and removes unnecessary mercaptan to 5mL, places in refrigerator after 24 hours, centrifugally obtains bolarious powder, it is dissolved in the toluene again, obtains the toluene solution of emboliform gold nano-crystal.
Step 2:1mL 10
-3The emboliform gold nano-crystal of M is with after 1mL 10M glutamic acid mixes, and reaction is 4 hours under ultrasonic and normal temperature condition.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 6
Step 1: the toluene solution that in the 100mL there-necked flask, adds 10mL 10mM aqueous solution of chloraurate and 10mL45mM four octyl group amine bromides (TOAB); vigorous stirring 15 minutes; the toluene solution that in flask, adds 5mL 65mM lauryl mercaptan then; the aqueous solution with the 5mL 0.5M sodium borohydride of fresh configuration adds in the constant pressure funnel simultaneously; back feeding nitrogen then is evacuated system; under protection of nitrogen gas, sodium borohydride is added in the reactant liquor fast, keep at last and stirred 3 hours.After reaction finishes,, remove water with the reactant liquor layering.Organic facies then decompression distillation adds 100mL ethanol then and removes unnecessary mercaptan to 5mL, places in refrigerator after 24 hours, centrifugally obtains bolarious powder, it is dissolved in the toluene again, obtains the toluene solution of emboliform gold nano-crystal.
Step 2:1mL 10
-3The emboliform gold nano-crystal of M is with after 1mL 10M lysine mixes, stir and normal temperature condition under reacted 5 hours.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 7
Step 1: the toluene solution that in the 100mL there-necked flask, adds 10mL 10mM aqueous solution of chloraurate and 10mL45mM four octyl group amine bromides (TOAB); vigorous stirring 15 minutes; the toluene solution that in flask, adds 5mL 80mM lauryl mercaptan then; the aqueous solution with the 5mL 1M sodium borohydride of fresh configuration adds in the constant pressure funnel simultaneously; back feeding nitrogen then is evacuated system; under protection of nitrogen gas, sodium borohydride is added in the reactant liquor fast, keep at last and stirred 3 hours.After reaction finishes,, remove water with the reactant liquor layering.Organic facies then decompression distillation adds 100mL ethanol then and removes unnecessary mercaptan to 5mL, places in refrigerator after 24 hours, centrifugally obtains bolarious powder, it is dissolved in the toluene again, obtains the toluene solution of emboliform gold nano-crystal.
Step 2:1mL 10
-3The emboliform gold nano-crystal of M is with after 1mL 1M phenylalanine mixes, stir and normal temperature condition under reacted 6 hours.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 8
Step 1: the toluene solution that in the 100mL there-necked flask, adds 10mL 10mM aqueous solution of chloraurate and 10mL45mM four octyl group amine bromides (TOAB); vigorous stirring 15 minutes; the toluene solution that in flask, adds 5mL 100mM lauryl mercaptan then; the aqueous solution with the 5mL 2M sodium borohydride of fresh configuration adds in the constant pressure funnel simultaneously; back feeding nitrogen then is evacuated system; under protection of nitrogen gas, sodium borohydride is added in the reactant liquor fast, keep at last and stirred 3 hours.After reaction finishes,, remove water with the reactant liquor layering.Organic facies then decompression distillation adds 100mL ethanol then and removes unnecessary mercaptan to 5mL, places in refrigerator after 24 hours, centrifugally obtains bolarious powder, it is dissolved in the toluene again, obtains the toluene solution of emboliform gold nano-crystal.
Step 2:1mL 10
-3The emboliform gold nano-crystal of M is with after 1mL 100mM serine mixes, stir and normal temperature condition under reacted 7 hours.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 9
Add 0.5mL 10mM HAuCl in the step 1:50mL flask
4The aqueous solution, 0.5mL 10mM sodium citrate aqueous solution 18.4mL deionized water, mixing and stirring.In above solution, add the freshly prepared sodium borohydride aqueous solution of 0.6mL 0.1M rapidly again, stop simultaneously stirring.React and obtain crystal seed after 1 hour.Then in a clean test tube, the cetyl trimethyl ammonia bromide (CTAB) of 9mL 0.1M and the HAuCl of 0.25mL 0.01M
4Mix, add the ascorbic acid of the fresh configuration of 0.05mL 0.1M again.Then, the crystal seed of 0.025mL joins in the above mixed solution.Leave standstill after 10 hours and obtain bar-shaped gold nano-crystal.
Step 2:1mL10
-3The bar-shaped gold nano-crystal of M is with after 1mL 10mM tyrosine mixes, and reaction is 8 hours under ultrasonic and normal temperature condition.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 10
Add 0.5mL 10mM HAuCl in the step 1:50mL flask
4The aqueous solution, 0.5mL 10mM sodium citrate aqueous solution 18.4mL deionized water, mixing and stirring.In above solution, add the freshly prepared sodium borohydride aqueous solution of 0.6mL 0.1M rapidly again, stop simultaneously stirring.React and obtain crystal seed after 1 hour.Then in a clean test tube, the cetyl trimethyl ammonia bromide (CTAB) of 9mL 0.1M and the HAuCl of 0.25mL 0.01M
4Mix, add the ascorbic acid of the fresh configuration of 0.05mL 0.1M again.Then, the crystal seed of 0.025mL joins in the above mixed solution.Leave standstill after 15 hours and obtain bar-shaped gold nano-crystal.
Step 2:1mL10
-3The bar-shaped gold nano-crystal of M is with after 1mL 1mM reduction glutathione mixes, stir and normal temperature condition under reacted 9 hours.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 11
Add 0.5mL 10mM HAuCl in the step 1:50mL flask
4The aqueous solution, 0.5mL 10mM sodium citrate aqueous solution 18.4mL deionized water, mixing and stirring.In above solution, add the freshly prepared sodium borohydride aqueous solution of 0.6mL 0.1M rapidly again, stop simultaneously stirring.React and obtain crystal seed after 1 hour.Then in a clean test tube, the cetyl trimethyl ammonia bromide (CTAB) of 9mL 0.1M and the HAuCl of 0.25mL 0.01M
4Mix, add the ascorbic acid of the fresh configuration of 0.05mL 0.1M again.Then, the crystal seed of 0.025mL joins in the above mixed solution.Leave standstill after 20 hours and obtain bar-shaped gold nano-crystal.
Step 2:1mL10
-3The bar-shaped gold nano-crystal of M is with after 1mL 10mM hexa mixes, and reaction is 8 hours under ultrasonic and normal temperature condition.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 12
Add 0.5mL 10mM HAuCl in the step 1:50mL flask
4The aqueous solution, 0.5mL 10mM sodium citrate aqueous solution 18.4mL deionized water, mixing and stirring.In above solution, add the freshly prepared sodium borohydride aqueous solution of 0.6mL 0.1M rapidly again, stop simultaneously stirring.React and obtain crystal seed after 1 hour.Then in a clean test tube, the cetyl trimethyl ammonia bromide (CTAB) of 9mL 0.1M and the HAuCl of 0.25mL 0.01M
4Mix, add the ascorbic acid of the fresh configuration of 0.05mL 0.1M again.Then, the crystal seed of 0.025mL joins in the above mixed solution.Leave standstill after 12 hours and obtain bar-shaped gold nano-crystal.
Step 2:1mL10
-3The bar-shaped gold nano-crystal of M is with after the hexa of 1mL 100mM acidifying mixes, stir and normal temperature condition under reacted 10 hours.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 13
Add 0.5mL 10mM HAuCl in the step 1:50mL flask
4The aqueous solution, 0.5mL 10mM sodium citrate aqueous solution 18.4mL deionized water, mixing and stirring.In above solution, add the freshly prepared sodium borohydride aqueous solution of 0.6mL 0.1M rapidly again, stop simultaneously stirring.React and obtain crystal seed after 1 hour.Then in a clean test tube, the cetyl trimethyl ammonia bromide (CTAB) of 9mL 0.1M and the HAuCl of 0.25mL 0.01M
4Mix, add the ascorbic acid of the fresh configuration of 0.05mL 0.1M again.Then, the crystal seed of 0.025mL joins in the above mixed solution.Leave standstill after 12 hours and obtain bar-shaped gold nano-crystal.
Step 2:1mL10
-3The bar-shaped gold nano-crystal of M is with after 1mL 1M albuminous protein employed mixes, and reaction is 12 hours under ultrasonic and normal temperature condition.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Embodiment 14
Add 0.5mL 10mM HAuCl in the step 1:50mL flask
4The aqueous solution, 0.5mL 10mM sodium citrate aqueous solution 18.4mL deionized water, mixing and stirring.In above solution, add the freshly prepared sodium borohydride aqueous solution of 0.6mL 0.1M rapidly again, stop simultaneously stirring.React and obtain crystal seed after 1 hour.Then in a clean test tube, the cetyl trimethyl ammonia bromide (CTAB) of 9mL 0.1M and the HAuCl of 0.25mL 0.01M
4Mix, add the ascorbic acid of the fresh configuration of 0.05mL 0.1M again.Then, the crystal seed of 0.025mL joins in the above mixed solution.Leave standstill after 12 hours and obtain bar-shaped gold nano-crystal.
Step 2:1mL10
-3The bar-shaped gold nano-crystal of M is with after 1mL 10M DNA (DNA) mixes, stir and normal temperature condition under reacted 24 hours.
Step 3: after reaction finished, centrifugal suspension and the sediment removed collected settled solution, promptly obtains sub-nano golden cluster molecule Au
8
Claims (2)
1. the preparation method of sub-nano golden cluster molecule is characterized in that the concrete steps of this method are:
Step (1). with the gold chloride is raw material, adopts the synthetic gold nanocrystals liquid solution of solution methods;
Described is raw material with the gold chloride, and the concrete grammar that adopts the synthetic gold nanocrystals liquid solution of solution methods is a kind of in the following method:
A. add sodium citrate aqueous solution in the aqueous solution of chloraurate of boiling, stirring condition is reaction 15~30min down, obtains the aqueous solution of emboliform gold nano-crystal; The equivalent proportion of gold chloride and natrium citricum is 1: 1~5;
B. aqueous solution of chloraurate is mixed with the toluene solution that contains lauryl mercaptan, under the stirring condition gold chloride is transferred to the toluene phase from water, add the toluene solution that sodium borohydride reduction obtains emboliform gold nano-crystal then; The equivalent proportion of gold chloride and lauryl mercaptan is 1: 2.5~5, and the sodium borohydride of adding and the equivalent proportion of gold chloride are 10~100: 1;
C. add sodium borohydride in equivalent proportion is the aqueous solution of 1: 1 gold chloride and natrium citricum, the golden nanometer particle that reduction obtains is as crystal seed, and the sodium borohydride of adding and the equivalent proportion of the gold chloride in the aqueous solution are 40: 1; In containing the aqueous solution of softex kw, add gold chloride and ascorbic acid then, add again and leave standstill reaction 10~20 hours after crystal seed mixes, obtain the aqueous solution of bar-shaped gold nano-crystal, the equivalent proportion of the crystal seed that adds and the gold chloride of adding is 1: 400, the equivalent proportion of the softex kw in the aqueous solution and the gold chloride of adding is 360: 1, and the equivalent proportion of the ascorbic acid of adding and the gold chloride of adding is 2: 1;
Step (2). with gold nanocrystals liquid solution and molar concentration is that the organic amine solution of 1mM~10M carries out ultrasonic reaction or carries out in flask more than the stirring reaction 30min in the ultrasonic cleaning machine, and the equivalent proportion of gold nano-crystal and organic amine molecule is 1: 1 * 10
-1~1 * 10
3
Step (3). reaction is carried out centrifugation to solution after finishing, and obtains sub-nano golden cluster molecule solution.
2. the preparation method of sub-nano golden cluster molecule as claimed in claim 1 is characterized in that: the organic amine molecule described in the step (2) is a kind of in the hexa, albuminous protein employed, DNA of histidine, mercaptoethylmaine, asparagine, glutamine, glutamic acid, lysine, phenylalanine, serine, tyrosine, reduced glutathione, hexa, acidifying.
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