CN114957328B - Fifteen-core silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane and preparation method and application thereof - Google Patents
Fifteen-core silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane and preparation method and application thereof Download PDFInfo
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- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- 229910052946 acanthite Inorganic materials 0.000 title claims abstract description 26
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229940056910 silver sulfide Drugs 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 isopropyl silver sulfide Chemical compound 0.000 claims abstract description 46
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- PGWMQVQLSMAHHO-UHFFFAOYSA-N sulfanylidenesilver Chemical compound [Ag]=S PGWMQVQLSMAHHO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims abstract description 16
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 206010028980 Neoplasm Diseases 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- VKJKOXNPYVUXNC-UHFFFAOYSA-K trilithium;trioxido(oxo)-$l^{5}-arsane Chemical compound [Li+].[Li+].[Li+].[O-][As]([O-])([O-])=O VKJKOXNPYVUXNC-UHFFFAOYSA-K 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 13
- 239000003814 drug Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000002265 prevention Effects 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 18
- 239000004332 silver Substances 0.000 abstract description 17
- 239000003446 ligand Substances 0.000 abstract description 15
- 150000001450 anions Chemical class 0.000 abstract description 6
- 230000001093 anti-cancer Effects 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002246 antineoplastic agent Substances 0.000 abstract description 3
- 229940041181 antineoplastic drug Drugs 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 abstract 1
- 239000001294 propane Substances 0.000 abstract 1
- 230000027455 binding Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- 239000007772 electrode material Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000004364 calculation method Methods 0.000 description 7
- ONDPGJBEBGWAKI-UHFFFAOYSA-N diphenylphosphane;propane Chemical compound CCC.C=1C=CC=CC=1PC1=CC=CC=C1 ONDPGJBEBGWAKI-UHFFFAOYSA-N 0.000 description 7
- 230000003993 interaction Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 150000003378 silver Chemical class 0.000 description 4
- 208000016261 weight loss Diseases 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 108010087230 Sincalide Proteins 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000010609 cell counting kit-8 assay Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- ZMMJGEGLRURXTF-UHFFFAOYSA-N ethidium bromide Chemical compound [Br-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 ZMMJGEGLRURXTF-UHFFFAOYSA-N 0.000 description 3
- 229960005542 ethidium bromide Drugs 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 206010006187 Breast cancer Diseases 0.000 description 2
- 208000026310 Breast neoplasm Diseases 0.000 description 2
- 206010009944 Colon cancer Diseases 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 208000029742 colonic neoplasm Diseases 0.000 description 2
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- 238000000921 elemental analysis Methods 0.000 description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
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- 238000002604 ultrasonography Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910002699 Ag–S Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000004568 DNA-binding Effects 0.000 description 1
- GHASVSINZRGABV-UHFFFAOYSA-N Fluorouracil Chemical compound FC1=CNC(=O)NC1=O GHASVSINZRGABV-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229960002949 fluorouracil Drugs 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
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- 239000006174 pH buffer Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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 Table
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
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- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention provides a catalyst based on 1, 3-bis (diphenylphosphine)) Fifteen-core sulfur-silver cluster compound of propane and a preparation method and application thereof, belonging to the technical field of silver cluster compound preparation. The preparation method comprises the steps of taking ferrocenecarboxylic acid as a ligand, adding isopropyl silver sulfide and silver tetrafluoroborate, adjusting the pH of a solution by 4-dimethylaminopyridine under the guidance of an anion template method, and adding 1, 3-bis (diphenylphosphino) propane to reduce system precipitation to obtain a pentadeca-nuclear silver sulfide cluster compound (hereinafter referred to as X2) based on the 1, 3-bis (diphenylphosphino) propane. The cluster compound X2 is a 15-core sulfur silver cluster compound, and the molecular formula of X2 is [ Cl@Ag ] 15 (S i Pr) 12 (dppp) 3 ](BF 4 ) 2 It belongs to a trigonal system, and the space group is P-3. Experiments show that the prepared X2 crystal has higher purity, good thermal stability and semiconductor property, and the experiment on the tumor inhibition activity shows that the X2 has the IC on MDA-MB-231 and HCT116 50 The results are 15.68+/-2.36 and 18.69+/-3.09 respectively, which indicate that X2 has higher anticancer activity and is a potential anticancer drug.
Description
Technical Field
The invention belongs to the technical field of silver cluster compound preparation, and particularly relates to a fifteen-core sulfur silver cluster compound based on 1, 3-bis (diphenylphosphine) propane, and a preparation method and application thereof.
Background
The silver-sulfur cluster compound has been widely studied due to the advantages of various synthesis methods, rich structure, excellent photophysical properties and the like. For example, in 1981, the Dance group synthesized a series of cage-like silver cluster compounds [ Ag ] using thiophenol as a ligand 6 (SPh) 8 ] 2- 、[Ag 5 (SPh) 7 ] 2- 、[Ag 12 (SPh) 16 ] 4- And their crystal structures were measured, all of which showed Ag + Is a complex. Subsequently, dance reported for the first time in 1983 that AgSC (CH 3 )(C 2 H 5 ) 2 The compound is also a one-dimensional chain infinitely extended structure, and chains are protected by alkyl substituents so that each chain is formed independently.
In recent years, more and more researches are focused on synthesizing high-nuclear silver-sulfur cluster compounds, and in 2004-2009, the Fenske subject group performs some precursor work on the synthesis of silver-sulfur nanoclusters. They utilize silver tert-butyl mercaptide and a silver-SiMe-containing 3 Highly reactive sulfur sources of radicals (e.g.S (SiMe 3 ) 2 、RSSiMe 3 ) A series of high-nuclear silver-sulfur cluster compounds are synthesized by reaction at low temperature,silver sulfur nanoclusters with a core number exceeding 100 include: ag (silver) 123 S 35 (S t Bu) 50 、Ag 188 S 124 (S t Bu) 96 、Ag 352 S 128 (S t C 5 H 11 ) And Ag 490 S 188 (S t C 5 H 11 ) 114 While Ag 490 S 188 (S t C 5 H 11 ) 114 Is the silver-sulfur cluster compound with the highest nuclear number at present. In 2010, the university of mansion, wang Quanming subject group, agBF 4 、NH 2 NH 2 And AgSBu t Adding into methanol, heating at 65deg.C to obtain high-symmetry silver-sulfur nanocluster [ Ag ] 62 S 13 (SBu t ) 32 ](BF 4 ) 4 Analysis of the single crystal structure shows that the cluster compound is a cation cluster with a core-shell structure and contains Ag 14 S 13 Nuclear layer and Ag 48 (SBu t ) 32 A shell layer. The group of Sun subject of Shandong university selects anionic silver polymer with chain structure { [ HNEt ] 3 ] 2 [Ag 10 (SC 6 H 4 Bu t ) 12 ]} n For reaction of raw materials and CF 3 COOAg synthesizes a 37-core silver-sulfur cluster compound by a one-pot method: { (HNEt) 3 )[Ag 37 S 4 (SC 6 H 4 Bu t ) 24 (CF 3 COO) 6 (H 2 O) 12 ]}. The cluster compound is an anion cluster, and the inside is an AgS 4 The tetrahedron is formed, and the whole anion cluster is of a spherical structure with high symmetry.
In recent years, a series of silver-sulfur clusters with different structures are designed and synthesized, but the research on the performances of the silver-sulfur clusters is focused on optical performances and semiconductor performances, and the biopharmaceutical performances of the silver-sulfur clusters are freshly reported.
Disclosure of Invention
Based on the above, the invention provides a fifteen-core sulfur-silver cluster compound based on 1, 3-bis (diphenylphosphine) propane, which can be applied to tumor prevention and treatment, and fills the blank of the silver-sulfur cluster compound in the tumor prevention and treatment direction.
The invention also provides a preparation method of the pentadeca-core silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane, so as to prepare the pentadeca-core silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane with an accurate structure.
The invention also provides application of the pentadecanuclear silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane in preparing medicines for preventing and treating tumors.
The technical scheme for solving the technical problems is as follows:
fifteen-core sulfur silver cluster compound based on 1, 3-bis (diphenylphosphine) propane and with molecular formula of [ Cl@Ag ] 15 (S i Pr) 12 (dppp) 3 ](BF 4 ) 2 Belongs to a trigonal system, the space group is P-3, and the unit cell parameters are as follows:c＝21.7218(8)；α＝90°，β＝90°，γ＝120°。
a method for preparing fifteen-core silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane, which comprises the following steps:
s01, adding silver tetrafluoroborate and silver isopropylsulfate into a mixed solution of acetonitrile and methanol to dissolve the silver tetrafluoroborate and the silver isopropylsulfate, so as to obtain a white clear solution A;
s02, adding a lithium arsenate solution into the solution A to uniformly disperse the solution A to obtain a solution B;
s03, adding ferrocenecarboxylic acid into the solution B to completely dissolve the ferrocenecarboxylic acid, thereby obtaining orange clear solution C;
s04, adding 4-dimethylaminopyridine into the solution C to generate a large amount of yellow precipitate to obtain suspension D;
s05, adding 3-bis (diphenylphosphine) propane (dppp) into the suspension D, dissolving the suspension D, and reducing yellow precipitation to obtain a suspension E;
s06, heating the suspension E at a first temperature for a first period of time to obtain orange-yellow solution F;
s07, cooling the solution F to room temperature, filtering, volatilizing the filtrate at a second temperature, and obtaining white polyhedral crystals after a second time, namely the pentadecanuclear silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane.
Preferably, in step S01, the ratio of the amounts of the substances of the silver tetrafluoroborate and the silver isopropylsulfate is 1:1.
Preferably, in step S02, the ratio of the amount of the lithium arsenate to the amount of the silver tetrafluoroborate is (1-2): 30, and the lithium arsenate solution is a methanol solution of lithium arsenate.
Preferably, in step S03, the ratio of the amounts of the ferrocenecarboxylic acid and the silver isopropylsulfate substance is 1:1.
Preferably, in step S04, the ratio of the amounts of the 4-dimethylaminopyridine and the silver isopropylsulfate substance is 1:1.
Preferably, in step S05, the ratio of the amounts of the 3-bis (diphenylphosphine) propane and the silver isopropylsulfide is 1:1.
Preferably, in step S06, the first temperature is 70±5 ℃, and the first duration is 20h±5h.
Preferably, in step S07, the second temperature is 10±5 ℃, and the second time period is 7d±2d.
The application of the pentadeca-nuclear silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane in preparing medicines for preventing and treating tumors.
Compared with the prior art, the invention has at least the following advantages:
the preparation method comprises the steps of taking ferrocenecarboxylic acid as a ligand, adding isopropyl silver sulfide and silver tetrafluoroborate, adjusting the pH of a solution by 4-dimethylaminopyridine under the guidance of an anion template method, and adding 1, 3-bis (diphenylphosphino) propane to reduce system precipitation to obtain a pentadeca-nuclear silver sulfide cluster compound (hereinafter referred to as X2) based on the 1, 3-bis (diphenylphosphino) propane. The cluster compound X2 is a 15-core sulfur silver cluster compound, and the molecular formula of X2 is [ Cl@Ag ] 15 (S i Pr) 12 (dppp) 3 ](BF 4 ) 2 It belongs to a trigonal system, and the space group is P-3. Asymmetric structural unit [ Cl@Ag ] of X2 15 (S i Pr) 12 (dppp) 3 ]Is prepared from 15 silver atoms, chloride ions as template, and 12 isopropyl mercaptan ligandsAnd 31, 3-bis (diphenylphosphine) propane ligands, and the silver cage cores are disordered.
Experiments show that the prepared X2 crystal has higher purity, good thermal stability and semiconductor property, and the binding mode with ct-DNA can be electrostatic binding, and the binding constant is K b Is 3.6X10 3 L·mol -1 Binding constant K is 1.14X10 4 L·mol -1 . The tumor inhibition activity experiment shows that the X2 has the IC on MDA-MB-231 (human breast cancer cells) and HCT116 (human colon cancer cells) 50 The results are 15.68+/-2.36 and 18.69+/-3.09 respectively, which indicate that X2 has higher anticancer activity and is a potential anticancer drug.
Drawings
Fig. 1 is a molecular structure diagram of a silver cluster of X2. Disordered moieties and counterions are deleted.
Fig. 2 is a graph comparing powder XRD experimental data of X2 with simulated data.
FIG. 3 is an infrared absorption spectrum of X2.
FIG. 4 is a general view of X2X-ray photoelectron spectroscopy.
Fig. 5 is an enlarged detail view of Ag3d of X2.
FIG. 6 is a thermogravimetric analysis of X2.
FIG. 7 is a solid ultraviolet absorption spectrum of X2.
FIG. 8 is a solid ultraviolet diffuse reflectance spectrum of X2.
Fig. 9 is a CV curve of X2 at different scan speeds.
Fig. 10 shows the charge and discharge curves of X2 at different current densities.
Fig. 11 shows the specific capacitance of X2 at different current densities.
FIG. 12 is a Ragone curve for X2.
FIG. 13 is an ultraviolet spectrum of X2 and ct-DNA interactions at pH=6.2.
FIG. 14 is an ultraviolet spectrum of X2 and ct-DNA interactions at pH=7.2.
FIG. 15 is an ultraviolet spectrum of X2 and ct-DNA interactions at pH=8.2.
FIG. 16 shows fluorescence spectra of EB-ctDNA at different concentrations of X2.
FIG. 17 is a Stern-Volmer diagram of the interaction of X2 with EB-ctDNA.
Fig. 18 is a bipartite graph of X2.
FIG. 19 is a CV curve of a bare gold electrode and a ct-DNA/Au electrode as working electrodes.
FIG. 20 is Fe (CN) 6 3-/4- Cyclic voltammograms at different rates.
Fig. 21 is a relationship between the oxidation peak current and the scanning rate.
FIG. 22 is Fe (CN) 6 3-/4- Cyclic voltammograms of X2 at different concentrations.
Fig. 23 shows an isothermal adsorption process of X2.
FIG. 24 is a flow chart of the process for preparing X2 in one embodiment.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The technical solution of the present invention will be further described below with reference to the accompanying drawings of the embodiments of the present invention, and the present invention is not limited to the following specific embodiments.
In one embodiment, a pentadecanuclear silver sulfide cluster compound (hereinafter referred to as X2) based on 1, 3-bis (diphenylphosphine) propane has a molecular formula of [ Cl@Ag 15 (S i Pr) 12 (dppp) 3 ](BF 4 ) 2 Belongs to a trigonal system, the space group is P-3, and the unit cell parameters are as follows:c＝21.7218(8)；α＝90°，β＝90°，γ＝120°。
referring to FIG. 1, the single crystal diffraction result shows that the cluster compound X2 is a 15-core silver sulfide cluster compound with the molecular formula of [ Cl@Ag 15 (S i Pr) 12 (dppp) 3 ](BF 4 ) 2 It belongs to a trigonal system, and the space group is P-3. Asymmetric structural unit [ Cl@Ag ] of X2 15 (S i Pr) 12 (dppp) 3 ]Is prepared from 15 silver atoms and chlorine ions as template anions and 12 isopropyl sulfideThe alcohol ligand and 31, 3-bis (diphenylphosphine) propane ligands are combined, and the silver cage core region is disordered.
Note that, [ cl@ag ] 15 (S i Pr) 12 (dppp) 3 ](BF 4 ) 2 The chlorine ions mainly come from small amounts of residual chlorine ions in 3-bis (diphenylphosphine) propane (dppp).
In the silver cage skeleton, the distance between Ag and Ag bonds is betweenTo->Is smaller than the sum of Van der Waals radii of two Ag atoms>This therefore indicates the presence of Ag … Ag metal-metal interactions. Isopropyl mercaptan coordinates with silver clusters in a mu 4 or mu 3 coordination mode respectively, and the bond length of Ag-S bonds is as followsTo->Between them. The 1, 3-bis (diphenylphosphine) propane ligand is directly connected with silver atom, and the bond length of Ag-P bond is +.>To->Between them. Together, these ligands make the silver cluster structure more stable.
A white polyhedral X2 crystal with the size of 0.13mm multiplied by 0.12mm multiplied by 0.10mm and regular shape is selected at 100K for single crystal diffraction test. The main crystallographic parameters of cluster X2 are shown in table 1. The partial bond lengths and bond angles of X2 are shown in Table 2.[ Cl@Ag 15 (S i Pr) 12 (dppp) 3 ](BF 4 ) 2
TABLE 1 Crystal parameter Table of Cluster X2
a R 1 ＝[Σabs(abs(Fo)-abs(Fc))]/[Σabs(Fo)]. b wR 2 ＝[Σ(w(Fo 2 -Fc 2 ) 2 )/Σ[w(Fo 2 ) 2 ] 0.5 。
TABLE 2 partial bond lengths of cluster X2And bond angle [ °]
The nature of X2 produced in the present invention is further illustrated by the experimental procedure below.
1. X-ray powder diffraction analysis
To verify the purity of the clusters, X2 was subjected to an X-ray powder diffraction test. As shown in FIG. 2, the diffraction peak of the cluster compound X2 is basically consistent with the peak position of the fitting peak simulated by the single crystal, which shows that all the crystals precipitated by the scheme are X2, and the purity of the cluster compound X2 crystals is higher.
2. Infrared spectroscopic analysis
Infrared analysis was performed on cluster X2 as shown in fig. 3. At 3054cm -1 、2953cm -1 、2906cm -1 、2852cm -1 The absorption peak at the position is the expansion vibration of the relevant C-H in X2; at 1481cm -1 The vibration absorption of benzene ring connected with P; at 1435cm -1 At CH 2 -deformation vibration absorption of P; at 1037cm -1 The peak at the position is the absorption peak of tetrafluoroborate ions; at 1360cm -1 Splitting into two peaks with almost equal intensity, i-propyl; at 511cm -1 The vibration absorption of the benzene ring skeleton is shown. The presence of these characteristic absorption peaks is a sufficient evidence of the presence of the relevant ligand in cluster X2.
3. X-ray photoelectron spectroscopy of X2
The elemental composition and valence state associated with cluster X2 were further confirmed by X-ray photoelectron spectroscopy (XPS). As shown in FIG. 4, XPS full spectrum of cluster X2 shows the elements contained in X2, wherein Ag: C: S: cl: F=9.49%: 76.48%:3.04%:2.63%:0.46%:4.31%, theoretical value Ag: C: P: S: cl: F=5.83%: 80.81%:4.14%:3.22%:0.4%:3.72%. FIG. 5 is an enlarged view of the energy level of the Ag3d orbit in FIG. 4, showing that the energy level spectrum of the Ag3d core orbit splits into two different peaks at 374.5eV and 368.5eV, respectively, corresponding to 3d 3/2 And 3d 5/2 Energy level. Referring to the literature, it was found that cluster X1 exhibited binding energies higher than elemental silver (374.3 and 368.3 eV) but similar to that of the Ag (I) compounds (374.8 and 368.8 eV) in comparison to the two peaks of Ag3d, thus indicating that the silver atom in X2 is also positive monovalent silver. The XPS test gave results consistent with the structure of cluster X2.
4. Thermogravimetric analysis
And carrying out TGA test analysis at the temperature of 30-700 ℃ under the whole protection of nitrogen so as to determine the molecular structure and the thermal stability of the nitrogen. The results of the thermal analysis of the complex are consistent with the results of the elemental analysis. Fig. 6 is a graph of TG and DTG of cluster X2, and analysis of the graph shows that the decomposition of cluster X2 is mainly divided into three stages. The first stage of weight loss occurs in the range of 208.0 ℃ to 210.3 ℃ and is about 2.5% weight loss, presumably losing free BF 4 - The theoretical value is 2.3%. The second stage then takes place at a temperature of between 210.3℃and 279.4℃and a weight loss of about 15.6%, possibly losing the peripheral isopropyl group, which is 14.4% of theory. The final stage may be decomposition of silver shell and 1, 3-bis (diphenylphosphine) propane at 279.4-387.2 deg.c, with a weight loss of about 37.83% and a theoretical value of 42.76%. The final residue may be Ag 2 O/Ag mixture. The corresponding temperatures with the maximum change of the weightlessness rate according to the DTG curve are 215.5 ℃, 233.1 ℃ and 367.6 ℃ respectively, which shows that X2 has good thermal stability。
5. X2 solid ultraviolet absorption spectroscopy
And (3) carrying out solid ultraviolet absorption spectrum detection on the cluster compound X2. As shown in fig. 7 and 8, a maximum absorption of X2 at a wavelength of 281nm in the solid uv absorption spectrum is observed, which is attributed to pi→pi X electron transfer of the 1, 3-bis (diphenylphosphine) propane ligand; the absorption at 447nm is then the result of a charge transfer of the ligand to the metal (LMCT). The forbidden band width eg=3.0 eV of X2 is calculated, which coincides with the color white exhibited by the crystal, and it is also explained that the cluster compound X2 has semiconductor properties.
6. X2 cyclic voltammetry analysis (CV)
The cluster X2 was subjected to cyclic voltammetry. CV testing of X2 was performed at a potential ranging from 0.15 to +0.45V and at different scan rates of 5 to 1000 mV/s. As shown in FIG. 9, the CV plot shows a pair of distinct redox peaks, at a sweep rate of 100mV/s, with oxidation peaks at about 0.32V and reduction peaks at about 0.18V, the formation of which is primarily related to the Faraday silver oxidation state in alkaline electrolyte, and also indicates that the electrode material is a pseudocapacitive electrode material. From the point of view of peak current intensity and potential moving distance, the current intensity of oxidation peak and reduction peak is basically the same, and the potential moving distance is smaller, thus showing that the cycling reversibility of the super capacitor electrode material is good. With the increase of the scanning rate, the oxidation-reduction potential of X2 moves to the positive and negative directions due to the influence of the internal resistance of the electrode. The current increases with the increase of the sweeping speed, and the current generated is increased due to the fact that more and more electrode materials undergo oxidation-reduction reaction with the increase of the sweeping speed.
7. X2 constant current charge-discharge test analysis (GCD)
In order to further clarify the advantages and disadvantages of X2 as an electrode material of the super capacitor, constant current charge and discharge tests are carried out on the super capacitor. As shown in fig. 10, it can be seen first that the GCD curve shape is a non-isosceles triangle shape, i.e., non-linear, thus illustrating its pseudocapacitance, rather than the double layer capacitance, which is consistent with CV test results. In addition, X2 was observed to exhibit charge-discharge characteristics in the range of 0 to 0.38V, which at a current density of 0.1A/g, exhibited a charge plateau at 0.27V, a discharge plateau at 0.22V, the plateau appearance in the curve all resulted from the redox reaction of the electrode material, and the charge-discharge plateau in the GCD curve corresponded to the redox peak in the CV curve. When the current densities were 1A/g, the discharge times of X2 were 6 seconds, and the discharge times were relatively short.
The specific capacity, power density and energy density of the X2 electrode material were calculated using the results of the constant current charge-discharge curve obtained, and the calculation results are shown in Table 3.
Some of the supercapacitor parameters of Table 3 X2
According to Table 3, the specific capacitance of X2 was 8.05F/g,7.30F/g,7.00F/g and 6.37F/g,6.00F/g,5.81F/g,5.31F/g when the current density was 0.1A/g,0.2A/g,0.3A/g,0.5A/g,0.8A/g,1A/g,2A/g, respectively. As shown in fig. 11, a graph of the specific capacitance on the abscissa and the specific capacitance on the ordinate reveals the relationship between the specific capacitance of the X2 electrode material and the current density.
As can be seen from fig. 11, the specific capacitance of the X2 super electrode material decreases with increasing current density. With X2, when the current density was 2A/g, the specific capacitance was only 5.31F/g, and excellent charge-discharge characteristics were not exhibited.
As shown in fig. 12, a Ragone curve is made with the energy density as the abscissa and the power density as the ordinate, which shows the rapid charge and discharge performance of two electrode materials.
As can be seen from fig. 12, the power density of the X2 super electrode material decreases with an increase in energy density, and the energy density decreases to a relatively large extent. That is, it means that the energy density of the electrode material is too different in the case of an increase in power density, so that the characteristic of rapid charge and discharge in a short time cannot be achieved.
By combining the X2 cyclic voltammetry test analysis and the constant current charge-discharge test analysis with the alternating current impedance test analysis, the charge-discharge time of the X2 is found to be extremely short and the X2 can not be rapidly subjected to the charge-discharge in a short time, and the superelectric performance of the X2 is also not ideal. Nevertheless, it is still expected that X2 can be applied as a semiconductor material while conforming to its electrochemical properties.
8. Determination of binding Property of X2 and ct-DNA by ultraviolet-visible Spectrometry
0.007g of cluster X2 was dissolved in a mixed solution of DMSO: PBS (pH 6.2) =9:1, and the volume was fixed in a 25mL volumetric flask to prepare 0.1mmol/L of X2 solution. Taking 2mL of cluster compound solution, respectively adding 0-1 mL of ct-DNA solution with 0.5mg/mL prepared by PBS with pH of 6.2, and fixing the volume to 10mL by the PBS with pH of 6.2 to obtain the solution to be tested with pH of 6.2. The concentration of ct-DNA in the liquid to be measured is 0-0.05 mg/mL. X2 test solutions with pH values of 7.2 and 8.2 were still prepared as described above. Ultraviolet spectroscopy testing was then performed.
As shown in fig. 13 to 15, in the case of the fixation of the X2 concentration, the amount of ct-DNA was gradually increased, and the ultraviolet absorption intensity was changed, and high colorability was also exhibited. It was also found that the position of the maximum absorption peak was also shifted in the short wave direction. These results indicate that the material may undergo a non-intercalating DNA binding mode, and the binding constant K at different pH values is determined by calculation of the change in UV spectral absorption intensity in the range 230-325 nm b Values.
Finally, by calculation, the binding constant K of the interaction of X2 and ct-DNA in different pH buffers is obtained b The values are respectively: (a) 1.04×10 3 L·mol -1 ；(b)4.12×10 3 L·mol -1 ；(c)2.24×10 3 L·mol -1 . The results show that X2 binds to ct-DNA more strongly than to acidic and basic under neutral conditions. The binding mode of X2 and ct-DNA may be electrostatic binding.
9. Fluorescence spectrometry analysis of binding properties of X2 and ct-DNA
0.014g of cluster X2 was dissolved in DMSO solution, and the volume was set to a 10mL volumetric flask to prepare 0.5mmol/L of X2 solution. 0.002g of Ethidium Bromide (EB) and 0.008g of ct-DNA are weighed, dissolved in PBS solution with pH of 7.2, fixed to a 50mL volumetric flask, and kept stand for balancing for 30 minutes to form a stable EB-ctDNA system. Taking 2mLEB-ctDNA solution (15 mu MEB-15 mu Mct-DNA), respectively adding 0-0.8 mL of the prepared X2 solution (0-40 mu M), and fixing the volume to 10mL by using PBS solution with pH of 7.2 to obtain a group of solutions to be tested. Fluorescence spectroscopy was performed after 10 minutes of equilibration.
In the 500-800nm range, as shown in FIG. 16, the fluorescence intensity of the system was observed to decrease with increasing concentration of X2, and the emission intensity of the EB-ctDNA complex at 606nm was decreased upon addition of X2, and quenching of this emission intensity could be attributed to binding of X2 to ct-DNA, or decreased availability of EB-ctDNA binding sites. According to the Stokes-Volmer equation, calculate the K of X2 sv The value was 3.65X10 4 L·mol -1 。
Evaluating the quenching mechanism of X2 quenching ethidium bromide emission to calculate K q The value was 1.59X10 12 L·mol -1 ·s -1 The results indicate that quenching of X2 is also caused by a static quenching mechanism, and therefore the complex formed between X2 and EB-ctDNA molecules is stable in the ground state. Further calculations showed that the number of binding sites for X2 to ct-DNA was 0.82, approximately equal to 1, indicating that X2 was bound to a reactive site on ct-DNA, binding constant K b Is 3.6X10 3 L·mol -1 。
10. Electrochemical method for testing binding property of X2 and ct-DNA
10mL of a 0.4mmol/L X2 solution was prepared from a mixture of DMSO: PBS (pH 7.2) =9:1. Then, 10mL of a potassium ferricyanide solution containing 0.1mol/L potassium chloride as a supporting electrolyte and 5mmol/L potassium ferricyanide solution as an electrolyte was prepared with a PBS solution having a pH of 7.2. And adopting a three-electrode system to perform cyclic voltammetry test.
As shown in FIG. 19, under the condition that the scanning rate is 100mV/s, compared with the CT-DNA modified working electrode and the bare gold electrode, the oxidation-reduction peak current of the CT-DNA modified working electrode is obviously reduced, and the reduction peak potential is obviously positively moved. At different scan rates, as shown in FIG. 20 and FIG. 21, the peak current of the ct-DNA modified working electrode increases with increasing scan rate, and is in a linear relationship with the square root of the corresponding scan rate. Thus, the voltammetric response meter of the ct-DNA modified working electrode and the bare gold electrodeThe reaction on the gold electrode is mainly composed of Fe (CN) in solution 6 3-/4- Controlling the diffusion process to the electrode surface; fe (CN) is hindered on the electrode due to the modification of ct-DNA 6 3-/4- Diffusion towards the electrode surface causes its current to reduce the voltage to move forward. Thus, the ct-DNA is successfully modified to the surface of the gold electrode, and the experimental requirement is met.
FIG. 22 shows CV diagrams of various concentrations of X2 (0.10 mmol/L-0.45 mmol/L) added. It can be seen that the redox peak current decreases with the addition of X2, indicating the interaction of the two. And the reduction peak potential moves toward a low electrochemical potential, thereby indicating that cluster X2 and ct-DNA are electrostatically bound.
As the concentration of X2 increases, the redox peak current gradually decreases and tends to equilibrate, which process may be similar to langmuir adsorption process (e.g., 23). According to literature reports, X2 and ct-DNA can be assumed as a system to generate a complex DNA DRUG m . Then, the binding constant of X2 and ct-DNA is calculated by applying the Langmuir isothermal equation formula.
Wherein DeltaI P,max The difference represented is the maximum oxidation peak current subtracted from the peak current before drug addition; [ DRUG ]]Representing the concentration of drug added to the solution under different experimental conditions; by calculation, the binding constant K of X2 and ct-DNA is 1.14X10 4 L·mol -1 。
11. Investigation of anticancer Activity of X2
The anticancer activity of X2 is measured by CCK-8 method, and the half inhibition concentration (IC 50) of MDA-MB-231 (human breast cancer cell) and HCT116 (human colon cancer cell) is measured at a concentration of 1 mu M-100 mu M for 24h, so as to investigate the relationship between the structure and effect. Calculation of IC based on CCK-8 results by GraphPadprism software 50 (. Mu.M) and the calculation results are shown in Table 4.
TABLE 4 IC calculated by GraphPadprism software based on CCK-8 results 50 Results (mu M)
The results are shown in Table 2, and from the results of Table 2, the anticancer effect of X2 on two cancer cells is equivalent to that of 5-fluorouracil, indicating that X2 is a potential anticancer drug.
In yet another embodiment of the present invention, a method for preparing a fifteen-core silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane, comprises the steps of:
s01, adding silver tetrafluoroborate and silver isopropylsulfate into a mixed solution of acetonitrile and methanol to dissolve the silver tetrafluoroborate and the silver isopropylsulfate, and obtaining a white clear solution A.
Preferably, silver tetrafluoroborate (AgBF 4 ) And silver isopropylsulfate (AgS) i Pr) is 1:1. Acetonitrile (CH) 3 CN) and methanol (CH) 3 OH) is mixed with acetonitrile and methanol in a volume ratio of 1:1. The addition amount of the mixed solution of acetonitrile and methanol to be able to dissolve AgBF 4 And AgS i Pr is the same.
In one embodiment, agS i Pr is configured by: adding an ethanol solution of 2-propyl mercaptan into a nitrate aqueous solution to generate a large amount of yellow precipitate, continuously stirring, adding triethylamine, carrying out suction filtration after the mixture is fully stirred, washing the mixture with water, ethanol and diethyl ether respectively, and naturally airing the mixture to obtain yellow solid powder, namely the isopropyl silver sulfide compound.
For example, 3.38g (0.02 mol) AgNO was weighed out 3 Dissolve in 100mL of water in a 250mL round bottom flask. 1.8mL (0.0195 mol) of 2-propylmercaptan was added to a beaker containing 5mL of ethanol, which was quickly added to AgNO 3 A large amount of yellow precipitate is generated immediately in the aqueous solution, stirring is continued for 15 minutes, then 2.71mL (0.0195 mol) of triethylamine is added into the system, after the triethylamine is fully stirred, suction filtration is carried out, water, ethanol and diethyl ether are sequentially used for respectively washing for 2-3 times, and then the yellow solid powder is obtained after natural airing, namely the isopropyl silver sulfide compound. Yield rate>90％。
S02, adding the lithium arsenate solution into the solution A to uniformly disperse the lithium arsenate solution to obtain a solution B.
Preferably, the lithium arsenate solution is a methanol solution of lithium nitrate. In one embodiment, the lithium arsenate solution is configured by: dissolving lithium arsenate solid in absolute methanol, adding nitric acid, and oscillating until the lithium arsenate is completely dissolved to obtain a white clear solution.
For example, 0.3195g (0.002 mol) of lithium arsenate solid was weighed and dissolved in 20mL of anhydrous methanol, then 0.5mL of nitric acid was added, and ultrasound was applied until the lithium arsenate was completely dissolved to obtain a white clear solution, i.e., a 0.1mol/L solution of lithium arsenate.
Preferably, the lithium nitrate solution is added in an amount such that the ratio of the amount of lithium arsenate to the amount of the silver tetrafluoroborate is (1-2): 30.
S03, adding ferrocenecarboxylic acid into the solution B to completely dissolve the ferrocenecarboxylic acid, thereby obtaining orange-yellow clear solution C.
Preferably, the ratio of the amounts of the ferrocenecarboxylic acid and the isopropyl silver sulfide substance is 1:1.
S04, adding 4-dimethylaminopyridine into the solution C to generate a large amount of yellow precipitate, and obtaining suspension D.
Preferably, the ratio of the amounts of the 4-dimethylaminopyridine and the silver isopropylsulfanile substance is 1:1.
S05, adding 3-bis (diphenylphosphine) propane (dppp) into the suspension D, dissolving the mixture, and reducing yellow precipitation to obtain a suspension E.
Preferably, the ratio of the amounts of the 3-bis (diphenylphosphine) propane and the silver isopropylsulfide material is 1:1.
S06, heating the suspension E at a first temperature for a first period of time to obtain orange-yellow solution F.
Preferably, the first temperature is 70 ℃ +/-5 ℃ and the first time period is 20 hours+/-5 hours.
S07, cooling the solution F to room temperature, filtering, volatilizing the filtrate at a second temperature, and obtaining white polyhedral crystals after a second time, namely the pentadecanuclear silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane.
Preferably, the second temperature is 10 ℃ ± 5 ℃ and the second time period is 7d±2d.
Specifically, referring to FIG. 24, 0.0584g (0.3 mmol) of silver tetrafluoroborate and 0.055g (0.3 mmol) of silver isopropylsulfate were added to a mixed solution of 3ml of acetonitrile and 3ml of methanol, and dissolved by ultrasonic wave to obtain a white clear solution. Then 100 mu L of 0.1mol/L of lithium arsenate solution is added, and the solution is uniformly dispersed by ultrasonic treatment, so that the color is not obviously changed. Then 0.069g (0.3 mmol) ferrocenecarboxylic acid was added, and the mixture was completely dissolved by ultrasonic treatment to obtain an orange-yellow clear solution. A further addition of 0.0367g (0.3 mmol) of 4-Dimethylaminopyridine (DMAP) resulted in a large yellow precipitate immediately after sonication. Finally 0.1237g (0.3 mmol) of 1, 3-bis (diphenylphosphino) propane (dppp) were added and after dissolution by ultrasound, the precipitation was largely reduced, but a small amount of yellow precipitate remained. Heating the solution at a constant temperature of 70 ℃ for 20 hours to obtain an orange-yellow solution. Cooling, filtering, volatilizing at low temperature for about one week to obtain white polyhedral crystal.
The molecular formula of the cluster compound X2 is [ Ag ] 15 (S i Pr) 13 (dppp) 3 ](BF 4 ) 2 Yield: 35.2%. Compound C 117 H 157 Ag 15 B 2 F 8 P 6 S 13 Elemental analysis of (a), experimental value (%): c,35.58; h,2.89; theoretical value (%): c,35.52; h,3.97.FT-IR (KBr pellet): 3054 2953, 2906, 2852cm -1 (ν C-H )，1037cm -1 (ν B-F )。
In the process of preparing X2, the selection of the template, the reaction temperature, the solvent, the silver salt raw material, the ligand and the like affect the synthesis of the final product. As shown in Table 5, the inventors explored a combination of various ligands, templates, solvents and silver salts, and finally, after ferrocenecarboxylic acid as the ligand, adding isopropyl silver sulfide and silver tetrafluoroborate, adjusting the pH of the solution with 4-dimethylaminopyridine under the guidance of an anion template method, adding phosphine ligand to reduce the condition of system precipitation, and condensing at a reaction temperature of 70 ℃ for a long time at low temperature, X2 was obtained. It will be appreciated by those skilled in the art that the above experimental conditions will have a limited effect on the results of the present invention within the allowable error range.
TABLE 5 preparation process exploration of X2
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Note that: in the above table,/indicates "or", i.e. it indicates that a plurality of sets of parallel schemes (the same applies below) are included.
X2 precipitation provides a new research idea for synthesizing dppp series sulfur-silver cluster compounds. The experimental phenomenon is better in the preparation process, the solution is clear and bright in color, and unfortunately, related crystals are not precipitated.
TABLE 6 preparation of dppp series of silver sulfide clusters
In one embodiment of the invention, the use of a pentadecanuclear silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane as described above for preparing a medicament for preventing and treating tumors.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Fifteen-core sulfur silver cluster compound based on 1, 3-bis (diphenylphosphine) propane, which is characterized by having a molecular formula of [ Cl@Ag15 (Si Pr) 12 (dppp) 3] (BF 4) 2, belonging to a trigonal system, wherein the space group is P-3, and the unit cell parameters are as follows: α=90°, β=90°, γ=120°, wherein dppp represents 1, 3-bis (diphenylphosphine) propane.
2. A method for preparing fifteen-core silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane, which is characterized by comprising the following steps:
s01, adding silver tetrafluoroborate and silver isopropylsulfate into a mixed solution of acetonitrile and methanol to dissolve the silver tetrafluoroborate and the silver isopropylsulfate, so as to obtain a white clear solution A;
s02, adding a lithium arsenate solution into the solution A to uniformly disperse the solution A to obtain a solution B;
s03, adding ferrocenecarboxylic acid into the solution B to completely dissolve the ferrocenecarboxylic acid, thereby obtaining orange clear solution C;
s04, adding 4-dimethylaminopyridine into the solution C to generate a large amount of yellow precipitate to obtain suspension D;
s05, adding 1, 3-bis (diphenylphosphine) propane into the suspension D, and reducing yellow precipitation after dissolving to obtain a suspension E;
s06, heating the suspension E at a first temperature for a first period of time to obtain orange-yellow solution F;
s07, cooling the solution F to room temperature, filtering, volatilizing the filtrate at a second temperature, and obtaining white polyhedral crystals after a second time, namely the pentadecanuclear silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane.
3. The method for preparing a pentadecanuclear silver sulfide cluster based on 1, 3-bis (diphenylphosphine) propane according to claim 2, wherein the ratio of the amounts of the materials of the silver tetrafluoroborate and the silver isopropylsulfide in step S01 is 1:1.
4. The method for producing a pentadecanuclear silver sulfide cluster based on 1, 3-bis (diphenylphosphine) propane according to claim 2, wherein the ratio of the amount of the lithium arsenate to the amount of the silver tetrafluoroborate is (1-2): 30 in step S02, and the lithium arsenate solution is a methanol solution of lithium arsenate.
5. The method for preparing a pentadecanuclear silver sulfide cluster based on 1, 3-bis (diphenylphosphine) propane according to claim 2, wherein the ratio of the amounts of the ferrocenecarboxylic acid and the isopropyl silver sulfide is 1:1 in step S03.
6. The method for preparing a pentadecanuclear silver sulfide cluster based on 1, 3-bis (diphenylphosphine) propane according to claim 2, wherein the ratio of the amounts of the 4-dimethylaminopyridine and the isopropylsilver sulfide is 1:1 in step S04.
7. The method for producing a pentadecanuclear silver sulfide cluster based on 1, 3-bis (diphenylphosphine) propane according to claim 2, wherein the ratio of the amounts of the 1, 3-bis (diphenylphosphine) propane and the isopropylsilver sulfide is 1:1 in step S05.
8. The method for preparing a pentadecanuclear silver sulfide cluster compound based on 1, 3-bis (diphenylphosphine) propane according to claim 2, wherein in the step S06, the first temperature is 70 ℃ ± 5 ℃ and the first time period is 20h ± 5h.
9. The method for preparing a pentadecanuclear silver sulfide cluster based on 1, 3-bis (diphenylphosphine) propane according to claim 2, wherein in step S07, the second temperature is 10 ℃ ± 5 ℃ and the second time period is 7d±2d.
10. Use of a pentadecanuclear silver sulfide cluster based on 1, 3-bis (diphenylphosphine) propane according to claim 1 for the preparation of a medicament for the prevention and treatment of tumors.
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