CN103215032A - Biocompatible gold-silver mixed cluster with strong fluorescence and preparation method of cluster - Google Patents
Biocompatible gold-silver mixed cluster with strong fluorescence and preparation method of cluster Download PDFInfo
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- CN103215032A CN103215032A CN2013101437726A CN201310143772A CN103215032A CN 103215032 A CN103215032 A CN 103215032A CN 2013101437726 A CN2013101437726 A CN 2013101437726A CN 201310143772 A CN201310143772 A CN 201310143772A CN 103215032 A CN103215032 A CN 103215032A
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- cluster
- silver
- gold
- acid
- ethanol
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Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 title abstract 6
- 238000002795 fluorescence method Methods 0.000 title 1
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 239000010931 gold Substances 0.000 claims description 86
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 83
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 48
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 44
- 229910052737 gold Inorganic materials 0.000 claims description 43
- 229910052709 silver Inorganic materials 0.000 claims description 39
- 239000004332 silver Substances 0.000 claims description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 38
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 36
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 18
- 230000002829 reductive effect Effects 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- -1 alkyl sulfide Chemical compound 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- SVABQOITNJTVNJ-UHFFFAOYSA-N diphenyl-2-pyridylphosphine Chemical compound C1=CC=CC=C1P(C=1N=CC=CC=1)C1=CC=CC=C1 SVABQOITNJTVNJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 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 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 2
- 229930002839 ionone Natural products 0.000 claims description 2
- 150000002499 ionone derivatives Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004148 unit process Methods 0.000 claims description 2
- 230000005284 excitation Effects 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 description 49
- 238000005406 washing Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 238000004821 distillation Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000000090 biomarker Substances 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- AHIBWURJLGCHAY-UHFFFAOYSA-N [S].C1=CC=CC=C1 Chemical compound [S].C1=CC=CC=C1 AHIBWURJLGCHAY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 210000001082 somatic cell Anatomy 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000002626 targeted therapy Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Abstract
The invention discloses a biocompatible gold-silver mixed cluster with strong fluorescence and a preparation method of the cluster. The structure of the gold-silver mixed cluster is expressed by the following formula (1) or (2): (AuxAg25-x(R23)10(Rl)5M2)...(1) and (AuxAg25-x(R23)10(Rl)5M2)Lz...(2), wherein x ranges from 12 to 18, M is Br or Cl, and Z is 1 or 2. The gold-silver mixed cluster has the characteristics of being high in fluorescence quantum yield, good in fluorescence stability, wide in excitation range, and excellent in biocompatibility; the gold-silver mixed cluster consists of a certain structure and the water-solubility can be increased by modifying a ligand; and the gold-silver mixed cluster can be applied to cell and biological tissue imagination.
Description
One, technical field
The present invention relates to a kind of fluorescent probe and preparation method thereof, specifically a kind of biocompatibility hyperfluorescence gold and silver mixes cluster and preparation method thereof.
Two, background technology
Basic means as life science, fluorescent mark and detection technique thereof are being brought into play very important effect in the research of cell and live body level, precious metal (gold or silver) cluster fluorescence imaging technology has inborn advantage on the live body horizontal imaging, such as long fluorescence lifetime, good light stability and target.So at biomarker, bio-sensing, the targeted therapy aspect has caused people's extensive concern.Common fluorescent probe mainly contains organic molecule and semiconductor-quantum-point at present, and the former fluorescence lifetime is short, and light stability is poor; Has toxic element and contain Cd, Hg, Pb etc. in the semiconductor-quantum-point more.Fluorescence lifetime is long, good light stability, and low toxicity even nontoxic precious metal cluster are in the news, but problem such as the ubiquity fluorescence quantum yield is not high, and yield is on the low side and can't further modify has limited its application in vivo.Therefore, develop a kind of yield height, strong, the easy functionalization of fluorescence intensity, good stability and have the precious metal cluster of biocompatibility, be extremely important thereby can be applied at biological field.
Three, summary of the invention
The present invention aims to provide a kind of biocompatibility hyperfluorescence gold and silver and mixes cluster and preparation method thereof, technical problem to be solved is to improve the fluorescence intensity of precious metal cluster, solution contains the bio-toxicity problem that fluorescence quantums such as Cd, Pb, Hg bring, and improves productive rate and repeatability.
Biocompatibility hyperfluorescence gold and silver of the present invention mixes cluster, it is characterized in that its structure expressed by following general formula (1) or general formula (2):
[Au
xAg
25-x(R
2 3)
10(R
1)
5M
2]…………（1），
[Au
xAg
25-x(R
2 3)
10(R
1)
5M
2]L
Z…………（2），
X=12-18 wherein, M is Br or Cl, Z is 1 or 2;
R
1For containing the S alkyl; R
1Preferred CH
3S-, CH
3CH
2S-, HOOCCH
2CH
2S-, HOCH
2CH
2S-, (CH
3)
2NCH
2CH
2S-, (CH
3)
3N
+Br
-CH
2CH
2S-or NH
4OOCCH
2CH
2S-; R
1Middle sulphur atom one end connects carbon atom, and the other end connects gold and/or silver-colored.
R
2For single sulfonic acid between triphenylphosphine, 2-(diphenylphosphino) pyridine, methyldiphenyl base phosphine, ethyl diphenylphosphine, triphenylphosphine, triphenylphosphine trisulfonic acid sodium salt, triphenylphosphine trisulfonic acid sylvite or other contain in the phosphine organic ligand one or more; R
2Itself being compound, is not group, R
2Be that form with coordinate bond is connected the atoms metal surface;
L is selected from Cl
-, Br
-, I
-, BF
4 -, PF
6 -Or in other acid ion one or both.
Biocompatibility hyperfluorescence gold and silver of the present invention mixes the preparation method of cluster, comprises synthetic each unit process of synthetic, synthetic and target product that alkyl sulfide is silver-colored of the gold nano cluster of organic phosphine protection, it is characterized in that:
The gold nano cluster of described organic phosphine protection synthetic be with the halogen auric acid aqueous solution (in the halogen auric acid) and organic phosphine in molar ratio 1:2-5 mixed and add in the ethanol, stir and add reductive agent down, 10-30 ℃ of reaction obtained the gold nano cluster-intermediate I of organic phosphine protection in 1.5-2.5 hour, and described halogen auric acid is hydrochloro-auric acid and/or hydrobromo-auric acid;
The golden cluster of organic phosphine of the present invention protection is not limited to the size of cluster, can be the gold nano cluster of extra small organic phosphine protection, can be the gold nano cluster of the bigger organic phosphine protection of 2-50nm yet.
The synthetic of described alkyl sulfide silver is that alkyl sulfhydryl and acid binding agent are added in the polar solvent, slowly drip Silver Nitrate, obtained alkyl sulfide silver-intermediate II in 1-2 hour in 10-50 ℃ of reaction, wherein the mol ratio of alkyl sulfhydryl, acid binding agent and Silver Nitrate is 0.5-1.5:2-5:1;
Described gold and silver mixes cluster synthetic be with described intermediate I and described intermediate II in molar ratio the ratio of 1:5-10 add in the polar solvent, 10-50 ℃ down reaction obtained gold and silver in 2-5 hour and mix cluster [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2] L
2
Described organic phosphine (R
2) be selected from single sulfonic acid between triphenylphosphine, 2-(diphenylphosphino) pyridine, methyldiphenyl base phosphine, ethyl diphenylphosphine, triphenylphosphine, triphenylphosphine trisulfonic acid sodium salt, triphenylphosphine trisulfonic acid sylvite or other and contain in the phosphine organic ligand one or more;
Described reductive agent is sodium borohydride and/or POTASSIUM BOROHYDRIDE, and the mol ratio of described reductive agent and described halogen auric acid is 2-10:1;
Described alkyl sulfhydryl (R
1H) be selected from CH
3SH, CH
3CH
2SH, HOOCCH
2CH
2SH, HOCH
2CH
2SH, (CH
3)
2NCH
2CH
2SH, (CH
3)
3N
+Br
-CH
2CH
2SH or NH
4OOCCH
2CH
2SH;
Described acid binding agent is selected from one or more in triethylamine, Trimethylamine 99, sodium bicarbonate, the pyridine.
The concentration of the described halogen auric acid aqueous solution is 0.1-0.5g/mL.
Polar solvent is selected from one or more in ethanol, methyl alcohol, water, the acetone described in the building-up process of alkyl sulfide silver;
Polar solvent is selected from one or more in methyl alcohol, ethanol, the acetone described in the building-up process of gold and silver mixing cluster, and the mol ratio of the gold nano cluster of described polar solvent and the protection of described organic phosphine is 20-40:1.
Gold and silver is mixed cluster [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2] L
2With reductive agent in molar ratio 1:1-1.05 mixed and add in the ethanol, 10-50 ℃ down reaction obtained gold and silver in 0.5-1.5 hour and mix cluster [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2] L
1Described reductive agent is selected from one or more in sodium borohydride, POTASSIUM BOROHYDRIDE, sodium hydride, hydrazine hydrate, Lithium Aluminium Hydride, the xitix.
Gold and silver is mixed cluster [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2] L
2With reductive agent in molar ratio 1:2-2.05 mixed and add in the ethanol, 10-50 ℃ down reaction obtained gold and silver in 0.5-1.5 hour and mix cluster [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2].Described reductive agent is selected from one or more in sodium borohydride, POTASSIUM BOROHYDRIDE, sodium hydride, hydrazine hydrate, Lithium Aluminium Hydride, the xitix.
Gold and silver of the present invention mixes in the cluster, organophosphorus ligand connects 10 gold atoms on the five-ring of two ends, the organosulfur part connects 10 atoms metals (gold and/or silver atoms) on two five-rings of waist, two atoms metals (gold and/or silver atoms) at two ends connect two halogens (chlorine and/or bromine), two cage shape M13 structure centre atoms are gold atom, the summit atom is a silver atoms altogether, mix cluster integral body and be with two unit positive charges, unit positive charge or neutral, concrete structure is referring to Fig. 1.Negatively charged ion is Cl
-, Br
-, I
-, BF
4 -, PF
6 -And one or both the mixture in other acid ion.
Gold and silver of the present invention mixes the excitation wavelength range of cluster at 300-670nm.
Concentration when gold and silver of the present invention mixes the biomarker of cluster is the 10-80 mcg/ml, and incubation time is 1-3 hour.When the addition of gold and silver mixing cluster was 10 mcg/ml during biomarker, best incubation time was 3 hours, 24 hours no tangible phenomena of mortality of cultivation; When the addition of gold and silver mixing cluster was 80 mcg/ml, best incubation time was 1 hour, 24 hours no tangible necrocytosis phenomenons of cultivation.
Compared with prior art, beneficial effect of the present invention is embodied in:
1, with the hydrochloro-auric acid that is easy to get and/or hydrobromo-auric acid as Jin Yuan, Silver Nitrate is as silver-colored source, raw material is easy to get; As part, raw materials cost is low with organic phosphine and mercaptan.
2, the harmful heavy metal ion such as Cd, Hg, Pb that do not induce one in the reaction, target product toxicity is low, helps biomarker.
3, have definite structure, product purity easily detects.
4, excellent in optical properties all can excite target product to produce near infrared light from the UV-light to ruddiness, and emission wavelength does not change with the change of excitation wavelength.
5, yield height of the present invention can reach more than 60% with the silver rate of collecting.Reaction at room temperature can be carried out, and good reproducibility is particularly suitable for large-scale production.
Four, description of drawings
Fig. 1 is the structure iron that gold and silver of the present invention mixes cluster.That Fig. 1 represents is [Au
xAg
25-x (R
2 3)
10(R
1)
5M
2], [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2] L or [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2] L
2The core, anionicsite does not mark on Fig. 1.
Fig. 2 is the present invention [Au
12Ag
13(PPh
3)
10(PhC
2H
4S)
5Cl
2] (SbF
6)
2In [Au
12Ag
13(PPh
3)
10(PhC
2H
4S)
5Cl
2] part the crystalline structure collection of illustrative plates.
Fig. 3 is the present invention [Au
12Ag
13(PPh
3)
10(PhC
2H
4S)
5Cl
2]
2+Ultraviolet (left-hand broken line), fluorescence excitation spectrogram (left side solid line) and corresponding fluorescence emission spectrum (right figure).As can be seen from Figure 3 cluster can use wavelength to excite as the light of 300nm-670nm, and in this excites wave band, all can excite and all can obtain than hyperfluorescence, simultaneously, UV spectrum is identical with the fluorescence emission spectrum peak shape, illustrates that cluster has good optical purity.
Fig. 4 is the present invention [Au
12Ag
13(PPh
3)
10(OHC
2H
4S)
5Cl
2] Cl
2Cell imaging under different excitation wavelengths, used cell are Human cancer cells7402, and it is 650-700nm that emission wavelength is accepted scope.Wherein the excitation wavelength of figure (a) is 405nm; The excitation wavelength of figure (b) is 633nm; Figure (c) is a light field; Figure (d) reaches (c) stacking diagram of figure for (a) and (b).As can be seen from Figure 4 cluster can be applied to the mark of active somatic cell, and the light that can use multi-wavelength is as excitation light source, thus can be effectively and other commercial dyestuff use simultaneously.For example most fluorescence dye goes out the peak all below 600nm.
Five, embodiment
The present invention is further illustrated below in conjunction with embodiment, but protection scope of the present invention is not limited in this.
1, intermediate compound I-[Au
11(PPh
3)
10Cl
2] preparation of Cl
With hydrochloro-auric acid 4mL(0.2g/ml, 2.35mmol) add and be equipped with in the there-necked flask of 100mL ethanolic soln, stir and add 1.6g(6.1mmol down) triphenylphosphine, stirring at room solution is by the transparent Baise suspension liquid that becomes of glassy yellow, back adding dissolving 0.25g(6.25mmol) the 20mL ethanol of sodium borohydride continued stirring reaction 2 hours under the room temperature, and underpressure distillation removes and desolvates, and use the washing of 60mL normal hexane for several times, obtain 0.82g Vandyke brown powder after the drying and be intermediate compound I-[Au
11(PPh
3)
10Cl
2] Cl, productive rate is 80%.
2, intermediate compound I-[Au
11(PEtPh
2)
10Cl
2] preparation of Cl
With hydrochloro-auric acid 4mL(0.2g/ml, 2.35mmol) add and be equipped with in the there-necked flask of 100mL ethanolic soln, stir and add 1.5g ethyl diphenylphosphine (7mmol) down, stirring at room solution is by the transparent Baise suspension liquid that becomes of glassy yellow, back adding dissolving 0.35g(8.75mmol) the 40mL ethanol of sodium borohydride continues to stir 2 hours, and underpressure distillation removes and desolvates, and use the washing of 60mL normal hexane for several times, obtain 0.80g Vandyke brown powder after the drying and be intermediate compound I-[Au
11(PEtPh
2)
10Cl
2] Cl, productive rate is 85%.
3, intermediate compound I-[Au
11((P (p-C
6H
5SO
3H)
3)
10Cl
2] preparation of Br
With hydrobromo-auric acid 4mL(0.2g/ml, 2.35mmol) add and be equipped with in the there-necked flask of 150mL ethanolic soln, stir and add 2.5g(5mmol down) to the triphenylphosphine trisulfonic acid, stirring at room solution is by the transparent Baise suspension liquid that becomes of glassy yellow, back adding dissolving 0.61g(11.25mmol) the 40mL ethanol of POTASSIUM BOROHYDRIDE continues to stir 2 hours, and underpressure distillation removes and desolvates, and use the washing of 60mL normal hexane for several times, obtain 1.16g Vandyke brown powder after the drying and be intermediate compound I-[Au
11((P (p-C
6H
5SO
3H)
3)
10Cl
2] Br, productive rate is 75%.
4, the preparation of intermediate II-alkyl sulfide silver
In the 250mL there-necked flask, add 100mL ethanol successively, 4g(64.5mmol) sulfur alcohol and 10g(99mmol) triethylamine, stir slowly to drip down and contain 5g(29.4mmol) the 50ml ethanolic soln of Silver Nitrate, reaction is thermopositive reaction, maintain about 10 ℃, continue to stir 2 hours, underpressure distillation removes and desolvates, and use the 60mL absolute ethanol washing for several times, and vacuum-drying obtains 4.72g(27.93mmol) intermediate II-C
2H
5SAg, productive rate 95%.
5, the preparation of intermediate II-alkyl sulfide silver
In the 250mL there-necked flask, add 100mL ethanol successively, 4g(51.9mmol) 2-aminoothyl mercaptan and 15g(148.5mmol) triethylamine, stir slowly to drip down and contain 10g(58.82mmol) the 50ml ethanolic soln of Silver Nitrate, reaction is thermopositive reaction, maintain about 10 ℃, continue to stir 2 hours, underpressure distillation removes and desolvates, and use the 80mL absolute ethanol washing for several times, and vacuum-drying obtains 10.87g(54.7mmol) intermediate II-NH
2C
2H
4SAg, productive rate 93%.
6, the preparation of intermediate II-alkyl sulfide silver
In the 250mL there-necked flask, add 100mL ethanol successively, 8g(57.97mmol) benzene sulfur alcohol and 10g(99mmol) triethylamine, stir slowly to drip down and contain 5g(29.4mmol) the 50ml ethanolic soln of Silver Nitrate, reaction is thermopositive reaction, maintain about 20 ℃, continue to stir 2 hours, underpressure distillation removes and desolvates, and use the 20mL absolute ethanol washing for several times, and vacuum-drying obtains 7.06g(28.81mmol) intermediate II-PhC
2H
4SAg, productive rate 98%.
7, target product [Au
12Ag
13(PPh
3)
10(PhC
2H
4S)
5Cl
2] Cl
2Synthetic
In 100ml single port flask, add 4g(0.82mmol successively) intermediate compound I-[Au
11(PPh
3)
10Cl
2] Cl, add 3g(12.24mmol after the ethanol 50ml stirring and dissolving) intermediate II-[PhC
2H
4SAg], stirred under the room temperature 4 hours, centrifugally remove black precipitate, the upper strata stillness of night uses underpressure distillation to remove and desolvates, 20mL ethanol: normal hexane=1:3(V/V) washing uses ethanol and methylene dichloride mixed solvent recrystallization to obtain target product 4.71g(0.66mmol for several times), productive rate 70%.
8, target product-[Au
12Ag
13(PPh
3)
10(OHC
2H
4S)
5Cl
2] (SbF
6)
2Synthetic
In 100ml single port flask, add 4g(0.82mmol successively) intermediate compound I-[Au
11(PPh
3)
10Cl
2] Cl, add 2.5g(13.5mmol after the ethanol 50ml stirring and dissolving) mesosome II-[OHC
2H
4SAg], stirred under the room temperature 4 hours, centrifugally remove black precipitate, the upper strata stillness of night uses underpressure distillation to remove and desolvates 20mL ethanol: normal hexane=1:3(V/V) wash for several times, and dissolve with ethanol is used in the back, add the 5ml ethanol that is dissolved with the 1g sodium hexafluoroantimonate, stirred 15 minutes, back centrifuging and taking precipitation part.Use ethanol and methylene dichloride mixed solvent recrystallization to obtain target product 4.48g(0.62mmol), productive rate 60%.
9, target product-[Au
12Ag
13(P (p-Ph
2C
6H
4SO
3H)
3)
10(OHC
2H
4S)
5Cl
2] Cl
2Synthetic
In 100ml single port flask, add 6g(0.83mmol successively) intermediate compound I-[Au
11(P (p-Ph
2C
6H
4SO
3H)
3)
10Cl
2] Br, add 2.5g(13.5mmol after the deionized water 50ml stirring and dissolving) intermediate II-[OHC
2H
4SAg], stirred under the room temperature 4 hours, centrifugally remove black precipitate, the upper strata stillness of night uses underpressure distillation to remove and desolvates, the 20mL washing with alcohol uses ethanol and water mixed solvent recrystallization to obtain target product product 6.52g(0.68mmol for several times), productive rate 65%.
10, target product-[Au
12Ag
13(PPh
2C
6H
4SO
3H)
10(C
2H
5S)
5Cl
2] Cl
2Synthetic
In 100ml single port flask, add 6g(0.83mmol successively) intermediate compound I-[Au
11(PPh
2C
6H
4SO
3H)
10Cl
2] Cl, add 2.1g(12.45mmol after the deionized water 50ml stirring and dissolving) intermediate II-[C
2H
5SAg], stirred under the room temperature 4 hours, centrifugally remove black precipitate, the upper strata stillness of night uses underpressure distillation to remove and desolvates, the 20mL washing with alcohol uses ethanol and water mixed solvent recrystallization to obtain target product productive rate 5.4g(0.59mmol for several times), 62%.
11, target product-[Au
12Ag
13(PPh
3)
10(PhC
2H
4S)
5Cl
2] synthetic
In 100ml single port flask, add 4g(0.82mmol successively) intermediate compound I-[Au
11(PPh
3)
10Cl
2] Cl, add 3g(12.24mmol after the ethanol 50ml stirring and dissolving) intermediate II-[PhC
2H
4SAg], stirred under the room temperature 4 hours, centrifugally remove black precipitate, the upper strata stillness of night uses underpressure distillation to remove and desolvates 20mL ethanol: normal hexane=1:3(V/V) washing uses ethanol and methylene dichloride mixed solvent recrystallization to obtain [Au for several times
12Ag
13(PPh
3)
10(PhC
2H
4S)
5Cl
2] Cl
24.71g(0.66mmol), then be dissolved in the 50ml ethanol, add sodium borohydride 0.049g(1.32mmol), stirred 1 hour under the room temperature, the back adds 200ml water, and centrifuging and taking lower floor solid is with 20ml water washing 3 times, 35 ℃ of following drying under reduced pressure obtain target product 4.5g, productive rate 66.8%.
12, target product-[Au
12Ag
13(PPh
3)
10(PhC
2H
4S)
5Cl
2] Cl synthetic
In 100ml single port flask, add 4g(0.82mmol successively) intermediate compound I-[Au
11(PPh
3)
10Cl
2] Cl, add 3g(12.24mmol after the ethanol 50ml stirring and dissolving) intermediate II-[PhC
2H
4SAg], stirred under the room temperature 4 hours, centrifugally remove black precipitate, the upper strata stillness of night uses underpressure distillation to remove and desolvates 20mL ethanol: normal hexane=1:3(V/V) washing uses ethanol and methylene dichloride mixed solvent recrystallization to obtain [Au for several times
12Ag
13(PPh
3)
10(PhC
2H
4S)
5Cl
2] Cl
24.71g(0.66mmol), then be dissolved in the 50ml ethanol, add sodium borohydride 0.025g(0.66mmol), stirred 1 hour under the room temperature, the back adds 200ml water, and centrifuging and taking lower floor solid is with 20ml water washing 3 times, 35 ℃ of following drying under reduced pressure obtain target product 4.5g, productive rate 66.8%.
13, target product-[Au
12Ag
13(PPh
3)
10(PhC
2H
4S)
5Cl
2] synthetic
In 100ml single port flask, add 4g(0.82mmol successively) intermediate compound I-[Au
11(PPh
3)
10Cl
2] Cl, add 1.5g(6.12mmol after the ethanol 50ml stirring and dissolving) intermediate II-[PhC
2H
4SAg], stirred under the room temperature 4 hours, centrifugally remove black precipitate, the upper strata stillness of night uses underpressure distillation to remove and desolvates 20mL ethanol: normal hexane=1:3(V/V) washing uses ethanol and methylene dichloride mixed solvent recrystallization to obtain [Au for several times
12Ag
13(PPh
3)
10(PhC
2H
4S)
5Cl
2] Cl
24.71g(0.66mmol), then be dissolved in the 50ml ethanol, add sodium borohydride 0.050g(1.32mmol), stirred 1 hour under the room temperature, the back adds 200ml water, and centrifuging and taking lower floor solid is with 20ml water washing 3 times, 35 ℃ of following drying under reduced pressure obtain target product 4.5g, productive rate 66.8%.
Claims (9)
1. a biocompatibility hyperfluorescence gold and silver mixes cluster, it is characterized in that its structure expressed by following general formula (1) or general formula (2):
[Au
xAg
25-x(R
2 3)
10(R
1)
5M
2]…………（1），
[Au
xAg
25-x(R
2 3)
10(R
1)
5M
2]L
Z…………（2），
X=12-18 wherein, M is Br or Cl, Z is 1 or 2;
R
1For containing the S alkyl;
R
2For single sulfonic acid between triphenylphosphine, 2-(diphenylphosphino) pyridine, methyldiphenyl base phosphine, ethyl diphenylphosphine, triphenylphosphine, triphenylphosphine trisulfonic acid sodium salt, triphenylphosphine trisulfonic acid sylvite or other contain in the phosphine organic ligand one or more;
L is selected from Cl
-, Br
-, I
-, BF
4 -, PF
6 -Or in other acid ion one or both.
2. biocompatibility hyperfluorescence gold and silver according to claim 1 mixes cluster, it is characterized in that:
R
1Be selected from CH
3S-, CH
3CH
2S-, HOOCCH
2CH
2S-, HOCH
2CH
2S-, (CH
3)
2NCH
2CH
2S-, (CH
3)
3N
+Br
-CH
2CH
2S-or NH
4OOCCH
2CH
2S-.
3. the described biocompatibility hyperfluorescence of claim 1 gold and silver mixes the preparation method of cluster, comprises synthetic each unit process of synthetic, synthetic and target product that alkyl sulfide is silver-colored of the gold nano cluster of organic phosphine protection, it is characterized in that:
The gold nano cluster of described organic phosphine protection synthetic be with the halogen auric acid aqueous solution and organic phosphine in molar ratio 1:2-5 mixed and add in the ethanol, stir and add reductive agent down, 10-30 ℃ of reaction obtained the gold nano cluster-intermediate I of organic phosphine protection in 1.5-2.5 hour, and described halogen auric acid is hydrochloro-auric acid and/or hydrobromo-auric acid;
The synthetic of described alkyl sulfide silver is that alkyl sulfhydryl and acid binding agent are added in the polar solvent, slowly drip Silver Nitrate, obtained alkyl sulfide silver-intermediate II in 1-2 hour in 10-50 ℃ of reaction, wherein the mol ratio of alkyl sulfhydryl, acid binding agent and Silver Nitrate is 0.5-1.5:2-5:1;
Described gold and silver mixes cluster synthetic be with described intermediate I and described intermediate II in molar ratio the ratio of 1:5-10 add in the polar solvent, 10-50 ℃ down reaction obtained gold and silver in 2-5 hour and mix cluster [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2] L
2
4. preparation method according to claim 3 is characterized in that:
Described organic phosphine is selected from single sulfonic acid between triphenylphosphine, 2-(diphenylphosphino) pyridine, methyldiphenyl base phosphine, ethyl diphenylphosphine, triphenylphosphine, triphenylphosphine trisulfonic acid sodium salt, triphenylphosphine trisulfonic acid sylvite or other and contains in the phosphine organic ligand one or more;
Described reductive agent is sodium borohydride and/or POTASSIUM BOROHYDRIDE, and the mol ratio of described reductive agent and described halogen auric acid is 2-10:1;
Described alkyl sulfhydryl is selected from CH
3SH, CH
3CH
2SH, HOOCCH
2CH
2SH, HOCH
2CH
2SH, (CH
3)
2NCH
2CH
2SH, (CH
3)
3N
+Br
-CH
2CH
2SH or NH
4OOCCH
2CH
2SH;
Described acid binding agent is selected from one or more in triethylamine, Trimethylamine 99, sodium bicarbonate, the pyridine.
5. preparation method according to claim 3 is characterized in that:
The concentration of the described halogen auric acid aqueous solution is 0.1-0.5g/mL.
6. preparation method according to claim 3 is characterized in that:
Polar solvent is selected from one or more in ethanol, methyl alcohol, water, the acetone described in the building-up process of alkyl sulfide silver;
Polar solvent is selected from one or more in methyl alcohol, ethanol, the acetone described in the building-up process of gold and silver mixing cluster, and the mol ratio of the gold nano cluster of described polar solvent and the protection of described organic phosphine is 20-40:1.
7. according to claim 3,4,5 or 6 described preparation methods, it is characterized in that:
Gold and silver is mixed cluster [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2] L
2With reductive agent in molar ratio 1:1-1.05 mixed and add in the ethanol, 10-50 ℃ down reaction obtained gold and silver in 0.5-1.5 hour and mix cluster [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2] L
1
8. according to claim 3,4,5 or 6 described preparation methods, it is characterized in that:
Gold and silver is mixed cluster [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2] L
2With reductive agent in molar ratio 1:2-2.05 mixed and add in the ethanol, 10-50 ℃ down reaction obtained gold and silver in 0.5-1.5 hour and mix cluster [Au
xAg
25-x(R
2 3)
10(R
1)
5M
2].
9. according to claim 7 or 8 described preparation methods, it is characterized in that:
Described reductive agent is selected from one or more in sodium borohydride, POTASSIUM BOROHYDRIDE, sodium hydride, hydrazine hydrate, Lithium Aluminium Hydride, the xitix.
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|---|---|---|---|
| CN201310143772.6A CN103215032B (en) | 2013-04-24 | 2013-04-24 | Biocompatible gold-silver mixed cluster with strong fluorescence and preparation method of cluster |
| PCT/CN2013/001438 WO2014172819A1 (en) | 2013-04-24 | 2013-11-25 | Biocompatible strong-fluorescence mixed gold-silver cluster, preparation method and use thereof |
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|---|---|---|---|
| CN201310143772.6A CN103215032B (en) | 2013-04-24 | 2013-04-24 | Biocompatible gold-silver mixed cluster with strong fluorescence and preparation method of cluster |
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| CN103215032B CN103215032B (en) | 2015-02-11 |
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| WO (1) | WO2014172819A1 (en) |
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| CN103408592A (en) * | 2013-08-26 | 2013-11-27 | 厦门大学 | Nine-core gold cluster compound and synthesis method thereof |
| CN103626124A (en) * | 2013-12-11 | 2014-03-12 | 湖南科技大学 | Method for preparing compound silver and gold sulfide/ silver sulfide nano cluster and application thereof |
| CN105499599A (en) * | 2015-12-15 | 2016-04-20 | 安徽大学 | Preparation method for small-size gold nano-clusters, and gold nano-clusters |
| CN106862583A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of preparation method of the controllable gold nanoclusters of atom number |
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| Publication number | Publication date |
|---|---|
| WO2014172819A1 (en) | 2014-10-30 |
| CN103215032B (en) | 2015-02-11 |
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