CN103011121A - Five-vacancy manganese di-hepta-tungsten phosphorus oxygen cluster compound and preparation method thereof - Google Patents

Five-vacancy manganese di-hepta-tungsten phosphorus oxygen cluster compound and preparation method thereof Download PDF

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CN103011121A
CN103011121A CN2012105685909A CN201210568590A CN103011121A CN 103011121 A CN103011121 A CN 103011121A CN 2012105685909 A CN2012105685909 A CN 2012105685909A CN 201210568590 A CN201210568590 A CN 201210568590A CN 103011121 A CN103011121 A CN 103011121A
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manganese
vacant
phosphorus oxygen
tungsten phosphorus
oxygen cluster
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张必松
殷之武
吴昌胜
裘建平
施存元
李云霞
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ZHEJIANG JIAFENG PHARMACEUTICAL CO Ltd
Jinhua Polytechnic
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Jinhua Polytechnic
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Abstract

The invention belongs to the field of inorganic material chemistry, inorganic drug chemistry and crystal engineering, and particularly relates to a five-vacancy manganese di-hepta-tungsten phosphorus oxygen cluster compound and a preparation method thereof. The five-vacancy manganese di-hepta-tungsten phosphorus oxygen cluster compound is provided with an anionic compound unit, and a chemical formula of the anionic compound unit is [Mn(HPW7O28)2]<14->. The compound has the advantages that the compound has potential anti-tumor and anti-viral activity, and potential application in a catalyst, molecular-based optical, electric and magnetic materials, and other aspects.

Description

Two seven tungsten phosphorus oxygen cluster compounds of five vacant manganese and preparation method thereof
Technical field
The invention belongs to inorganic material chemistry, inorganic pharmacochemistry and crystal engineering field, relate in particular to two seven tungsten phosphorus oxygen cluster compounds of five vacant manganese and preparation method thereof.
Background technology
Polyoxometallate (POMS) is with its colourful structure and the good molecular characterization of himself, comprise polarity, redox potential, surface charge distribution, form and acidity, make it in a lot of fields, especially the aspects such as material, catalysis, medicine are with a wide range of applications.Polyacid medicine (document [1] .Bernold Hasenknopf, Polyoxometalates:Introduction to a class of inorganic compounds and their biomedical applications, Frontiers in Bioscience, 2005,10:275-287. document [2] .Jeffrey T.Rhule, Craig L.Hill, and Deborah A.Judd, Polyoxometalates in Medicine[J], Chem.Rev.1998,98:327-357.) because of a great variety, structure is adjustable, character is variable, cheap, the tempting prospects such as market is huge cause that increasing scientist pays close attention in the world.
The reported first such as Raynaud in 1971 heteropolyanion [SiW 12O 40] 4-Antiviral activity, started the pharmaceutical chemistry of polyacid.Yamase PM-8((NH 3Pr) 6[Mo 7O 24] 3H 2O) carry out antineoplastic research, not only drawn " Mo 7O 24Skeleton construction has a decisive role for antitumor " conclusion, and a unique so far polyacid antineoplastic oxidation one reduction mechanism hypothesis has been proposed
[Mo 7O 24] 6-+e -+H +→[Mo 7O 23（OH）] 6-。
The heteropolyacid that metal replaces has significant biological activity.
Such as document [4] (Hu D H, Shao C, Guan W, et al.Studies on the interactions of Ti-containing polyoxometalates(POMs) with SARS-CoV 3CL ProBy molecular modeling[J], J Inorg Biochem, 2007,101:89-94.) five kinds of heteropolyacid salt isomer [α-PTiW of open titanium replacement 10O 40] 7-Carry out the analog calculation research of anti-SARS virus, the result shows, this type of heteropolyacid can with the key protein enzyme 3CL that affects SARS virus and copy ProForm stable compound, thereby suppress SARS virus.
Such as document [5] (Jianxin Li, Rongxin Tan, Rui Li, Xiaohong Wang, et al.Syntheses, properties and biological activity of organogermanium substituted heterpolytungstates[J], Inorganic Chemistry Communications, 2007,10:216-219.), document [6] Jianxin Li, Fengying Zhai, Xiaohong Wang, et al.Synthesis and biological activity oftriorganogermanium substituted heteropolytungstates[J], Polyhedron, 2008,27:1150-1154.) open organic germanium replaces assorted poly-tungstate at (HOOCCH 2CH 2Ge) 3(PW 9) 2When consumption was about 52.20 μ g/mL, its activity was than Na 8H[PW 9O 34] height.
Such as document [7] (Fengying Zhai, Xiaohong Wang, Dongliu Li, et al.Synthesis and biological evaluation of decavanadate Na 4Co(H 2O) 6V 10O 2818H 2O[J], Biomedicine ﹠amp; Pharmacotherapy, 2009,63:51-55.) open cobalt replaces hetero-vanadate (Na 4Co(H 2O) 6V 10O 2818H 2O), be abbreviated as (CoV 10) to suppressing people's liver cancer (SMMC-7721) cell, ovarian cancer (SK-OV-3) cell, confirmed effectively by external experiment (mtt assay), and IC 50Be worth less.CoV 10Anti-knurl effect to SMMC-7721 is compared the effective of SK-OV-3, the activity of SMMC-7721 just is equivalent to the 5-Fu(5-fluorouracil of 25 μ g/mL when 1.5625 μ g/mL, 5 FU 5 fluorouracil).CoV 10Also be proved suppressing the Hep-A-22(liver cancer in the mouse body) effectively.King En Bo study group has obtained a large amount of innovative research achievements having done the active research work of a large amount of screenings and antiviral (anti-HIV) aspect the polyacid drug research.1998, Rhule, Hill etc. should be used as detailed summary to polyacid aspect medical.
In addition, document [8] (A.Ogata, S.Mitsui, H.Yanagie, et al.A novel anti-tumor agent, polyoxomolybdate induces apoptotic cell death in AsPC-1 human pancteatic cancer cells[J], Biomedicine ﹠amp; Pharmacotherapy, 2005,59:240-244.), document [9] (Xiaohong Wang, Jingfu Liu, Jianxin Li, et al.Synthesis and antitumor activity of cyclopentadienyltitanium substituted polyoxotungstate[CoW 11O 39(CpTi)] 7-(Cp=η 5-C 5H 5) [J], Journal of Inorganic Biochemistry, 2003,94:279-284.), document [10] (XiaohongWang, Feng Li, Shuxia Liu and M.T.Pope, New liposome-encapsulated-polyoxometalates:synthesis and antitumoral activity[J], Journal of Inorganic Biochemistry, 2005,99:452-457), document [11] (Fengying Zhai, Dongliu Li, Chunli Zhang, Xiaohong Wang, Rui Li, Synthesis and characterization of polyoxometalates loaded startch nanocomplex and its antitumoral activity[J], European Journal of Medicinal Chemistry, 2008,43:1911-1917), document [12] (Xiao-Hong Wang, JingFu Liu, Ya-Guang Chen, Qun Liu, Ju-Tao Liu and M.T.Pope, Synthesis, characterization and biological activeity of organotitanium substituted heteropolytungstates, J.Chem.Soc., DaltonTrans., 2000,1139-1141), document [13] (Liu Hong, the coordination assembling of the assorted poly-tungstate of three vacant Keggin types and transition metal, crystalline structure and magnetic research [D], Changchun: Northeast Normal University, 2007.) etc. the metal oxygen cluster compound is also disclosed.According to incompletely statistics, find that existing nearly 200 kinds and nearly 20 kinds of metal oxygen cluster compounds are had antiviral, antitumous effect by experiment conclusive evidence in external, the body respectively, and toxicity is lower.Wherein the overwhelming majority is assorted many tungsten bunch, particularly assorted many tungsten of vacant, sandwich structure bunch.Metal current oxygen bunch pharmaceutical chemical main direction of studying, the one, in metal oxygen cluster, introduce rare earth element; The 2nd, the research of single omission, many omissions and mixed type metal oxygen bunch; The 3rd, introduce organic group on the extraneous or interior boundary of metal oxygen cluster, all these work can both improve the biological activity of metal oxygen cluster effectively.
Summary of the invention
An object of the present invention is to provide the two seven tungsten phosphorus oxygen cluster compounds of five vacant manganese, this compound has potential antitumor, antiviral activity.Simultaneously, this compound also has potential application at aspects such as catalyzer and molecular based light, electricity, magneticsubstances.
Another object of the present invention provides the preparation method of the two seven tungsten phosphorus oxygen cluster compounds of a kind of above-mentioned five vacant manganese.
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
The two seven tungsten phosphorus oxygen cluster compounds of five vacant manganese, this compound has following anionic compound unit, and the chemical formula of anionic compound unit is: [Mn(HPW 7O 28) 2] 14-And described Mn, P, W, O have following structural formula:
Figure BDA00002636533500031
As preferably, the cation compound unit of this compound adopts one or more mixing in hydration sodium ion, hydrated potassium ion and the Hydrated Ammonium ion.
As preferred again, the cation compound unit of this compound adopts the hydration sodium ion.As preferred again, the hydration sodium ion adopts one or both in " H " type hydration sodium ion, " Z " type hydration sodium ion.
As most preferably, the chemical formula of this compound is [Na 14(H 2O) 38Mn(HPW 7O 28) 2] 6H 2O.
In order to realize second above-mentioned purpose, the present invention has adopted following technical scheme:
A kind of preparation method who prepares the two seven tungsten phosphorus oxygen cluster compounds of described five vacant manganese, the method comprises the steps:
1) takes by weighing manganese sulfate monohydrate MnSO 4H 2O adds an amount of dissolved in distilled water, adds excessive NaOH solution again, distilled water wash is also used in the precipitation of hydroxide centrifugation of gained, until do not contain negatively charged ion in the precipitation;
2) get Tungstophosphoric acid, sodium salt Na 2H 5P (W 2O 7) 6Be dissolved in the mixed solvent of organic solvent and distilled water, add oxyhydroxide and the methyl alcohol of new system behind stirring 20 ~ 40min;
3) transfer pH with sodium hydroxide solution, stir in the stainless steel cauldron of the inner liner polytetrafluoroethylene of packing into after 1.5 ~ 3 hours;
4) temperature programmed control, temperature rise rate: rose to 150 ~ 170 ℃ by room temperature in 4 ~ 6 hours, and kept beginning after 4 ~ 6 days cooling, rate of temperature fall: 10 ~ 14 hours by being down to room temperature;
5) solids removed by filtration insolubles, filtrate is spontaneous evaporation at ambient temperature, finds to have the crystal of suitable monocrystalline test to separate out after 2 months.
As preferably, the mol ratio of described Tungstophosphoric acid, sodium salt and manganous hydroxide is 2:1.
As preferably, described step 2) organic solvent is acetone or methyl alcohol in.
As preferably, the volume ratio of described organic solvent and distilled water is 1:2 ~ 2.5.
As preferably, sodium hydroxide solution is transferred pH=5.5 ~ 8.5 in the described step 3).
Of the present invention five vacant transition metal seven tungsten phosphorus oxygen bunch series compounds, in seven tungsten phosphorus oxygen bunch unit, seven WO 6Octahedron is failed a PO 4Tetrahedron is wrapped in the center, so that PO 4A tetrahedral side is exposed outside significantly.Two seven tungsten phosphorus oxygen of a Mn (II) atom bridging bunch have consisted of the sandwich two seven tungsten phosphorus oxygen bunch unit of manganese.
Of the present invention five vacant transition metal seven tungsten phosphorus oxygen bunch series compounds have following characteristic:
(1) five vacant transition metal seven tungsten phosphorus oxygen cocooning tools have and vacant compound H PA-23((NH 4) 17Na[NaSb 9W 21O 86]) ability of similar permeation cell, thereby realize antitumor, antiviral purpose by penetrating into virocyte nuclear;
(2) five vacant transition metal seven tungsten phosphorus oxygen cocooning tools have the redox property similar to PM-8, kill virocyte by redox reaction;
(3) five vacant transition metal seven tungsten phosphorus oxygen cocooning tools have with virus protein and form interlinkage in the chain by hydrogen bond, stop virus protease to copy, thereby realize antitumor, antiviral purpose;
(4) five vacant transition metal seven tungsten phosphorus oxygen bunch have potential application at aspects such as catalyzer and molecular based light, electricity, magneticsubstances.
Description of drawings
Fig. 1 is [Mn(HPW 7O 28) 2] 14-Structural unit.
Fig. 2 is Na 14(H 2O) 38Mn(HPW 7O 28) 2] 6H 2The O structural unit.
Fig. 3 is the structural unit of " H " type hydration sodium ion.
Fig. 4 is the structural unit of " Z " type hydration sodium ion.
Fig. 5 is H 90MnNa 14O 100P 2W 14The X-ray powder diffraction pattern.
Fig. 6 is H 90MnNa 14O 100P 2W 14Infrared spectrogram.
Embodiment
The two seven tungsten phosphorus oxygen cluster compound Na of 14 sodium hydrated ion bridging manganese (II) 14(H 2O) 38Mn(HPW 7O 28) 2] 6H 2O compound and preparation method thereof.
The two seven tungsten phosphorus oxygen cluster compound Na of 14 sodium hydrated ion bridging manganese (II) 14(H 2O) 38Mn(HPW 7O 28) 2] 6H 2The preparation method of O, the method comprises the steps:
(1) takes by weighing manganese sulfate monohydrate (MnSO 4H 2O) 0.845g(0.50mmol), add an amount of dissolved in distilled water, add again excessive 1mol/L NaOH solution, with the manganous hydroxide precipitation and centrifugal separation of gained and with distilled water wash 5 times, until sulphate-containing ion not in the precipitation;
(2) take by weighing Tungstophosphoric acid, sodium salt (Na 2H 5P(W 2O 7) 6) 1.480g(0.50mmol) be dissolved in 30mL1:2(v/v) in the mixed solvent of acetone and distilled water, stir the manganous hydroxide and the 10mL methyl alcohol that add new system after half an hour, transfer pH=8.5 with sodium hydroxide solution, stirred 2 hours;
(3) reaction suspension is packed in the stainless steel cauldron of 50mL inner liner polytetrafluoroethylene into temperature programmed control, temperature rise rate: rose to 160 ℃ by room temperature in 5 hours, and kept 160 ℃ to begin cooling, rate of temperature fall after 5 days: be down to room temperature by 160 ℃ in 12 hours.
Go out still after (4) one weeks, the solids removed by filtration insolubles, filtrate is spontaneous evaporation at ambient temperature, finds to have the yellow bulk crystals of suitable monocrystalline test to separate out after 2 months.
The two seven tungsten phosphorus oxygen cluster compounds of five vacant manganese of preparation are carried out X-ray single crystal diffraction, Infrared spectroscopy, confirm crystalline structure.X-ray powder diffraction pattern 5, infrared spectra Fig. 6.
Its crystallographic data is: H 90MnNa 14O 100P 2W 14, FW=4703.22, triclinic, space group P-1, a=11.877(2), b=12.125(2), c=17.960
Figure BDA00002636533500051
α=80.13(3) °, β=85.40(3) °, γ=60.80(3) °, V=2224.3(10)
Figure BDA00002636533500052
Z=1, D Calc=3.511Mg/m 3, λ=0.71073
Figure BDA00002636533500053
T=273K, R 1(wR 2)=0.0405(0.1008).
IR（KBr）cm -1:3430（OH,）,1090（P—Oa（W））,1010（P—Oa（Mn））,930（W—Od）,890（W—Ob—W）,800（W—Oc—W）。
Title ligand polymer structural unit is by two seven tungsten phosphorus oxygen of a manganese (II) bunch, 14 hydration sodium ions and 6 crystal water molecular compositions.In seven tungsten phosphorus oxygen bunch unit, seven WO 6Octahedron is failed a PO 4Tetrahedron is wrapped in the center, so that PO 4A tetrahedral side is exposed outside significantly.Two seven tungsten phosphorus oxygen of a Mn (II) atom bridging bunch have consisted of the sandwich two seven tungsten phosphorus oxygen bunch unit (Fig. 1) of manganese, the two seven tungsten phosphorus oxygen cluster compound (Na of 14 hydration sodium ion manganese 14(H 2O) 38Mn(HPW 7O 28) 2] 6H 2O) structural unit (Fig. 2).The hydration sodium ion is divided into two groups and forms respectively " H " type member (Fig. 3) and " Z " type one-dimensional chain (Fig. 4), and by one-dimensional chain the title is consisted of three-dimensional coordination polymer.Also have a small amount of crystal water and a large amount of O-H ... the O hydrogen bond is present in the crystalline structure.
Five above-mentioned vacant manganese seven tungsten phosphorus oxygen cocooning tools have following characteristic:
(1) five vacant manganese seven tungsten phosphorus oxygen cocooning tools have and vacant compound H PA-23((NH 4) 17Na[NaSb 9W 21O 86]) ability of similar permeation cell, thereby realize antitumor, antiviral purpose by penetrating into virocyte nuclear;
(2) five vacant manganese seven tungsten phosphorus oxygen cocooning tools have the redox property similar to PM-8, kill virocyte by redox reaction;
(3) five vacant manganese seven tungsten phosphorus oxygen cocooning tools have with virus protein and form interlinkage in the chain by hydrogen bond, stop virus protease to copy, thereby realize antitumor, antiviral purpose;
(4) five vacant manganese seven tungsten phosphorus oxygen bunch have potential application at aspects such as catalyzer and molecular based light, electricity, magneticsubstances.

Claims (10)

1. the two seven tungsten phosphorus oxygen cluster compounds of five vacant manganese is characterized in that this compound has following anionic compound unit, and the chemical formula of anionic compound unit is: [Mn(HPW 7O 28) 2] 14-And described Mn, P, W, O have following structural formula:
Figure FDA00002636533400011
。
2. the two seven tungsten phosphorus oxygen cluster compounds of according to claim 1 five vacant manganese is characterized in that: one or more mixing in cation compound unit employing hydration sodium ion, hydrated potassium ion and the Hydrated Ammonium ion of this compound.
3. the two seven tungsten phosphorus oxygen cluster compounds of according to claim 2 five vacant manganese is characterized in that: the cation compound unit employing hydration sodium ion of this compound.
4. the two seven tungsten phosphorus oxygen cluster compounds of according to claim 3 five vacant manganese is characterized in that: one or more in hydration sodium ion employing " H " type hydration sodium ion, " Z " type hydration sodium ion.
5. two seven tungsten phosphorus oxygen cluster compounds of according to claim 1 five vacant manganese, it is characterized in that: the chemical formula of this compound is [Na 14(H 2O) 38Mn(HPW 7O 28) 2] 6H 2O.
6. a preparation method who prepares the two seven tungsten phosphorus oxygen cluster compounds of claimed in claim 5 five vacant manganese is characterized in that the method comprises the steps:
1) takes by weighing manganese sulfate monohydrate MnSO 4H 2O adds an amount of dissolved in distilled water, adds excessive NaOH solution again, distilled water wash is also used in the precipitation of hydroxide centrifugation of gained, until do not contain negatively charged ion in the precipitation;
2) get Tungstophosphoric acid, sodium salt Na 2H 5P (W 2O 7) 6Be dissolved in the mixed solvent of organic solvent and distilled water, add oxyhydroxide and the methyl alcohol of new system behind stirring 20 ~ 40min;
3) transfer pH with sodium hydroxide solution, stir in the stainless steel cauldron of the inner liner polytetrafluoroethylene of packing into after 1.5 ~ 3 hours;
4) temperature programmed control, temperature rise rate: rose to 150 ~ 170 ℃ by room temperature in 4 ~ 6 hours, and kept beginning after 4 ~ 6 days cooling, rate of temperature fall: 10 ~ 14 hours by being down to room temperature;
5) solids removed by filtration insolubles, filtrate is spontaneous evaporation at ambient temperature, finds to have the crystal of suitable monocrystalline test to separate out after 2 months.
7. the preparation method of the two seven tungsten phosphorus oxygen cluster compounds of according to claim 6 five vacant manganese, it is characterized in that: the mol ratio of Tungstophosphoric acid, sodium salt and manganous hydroxide is 2:1.
8. the preparation method of the two seven tungsten phosphorus oxygen cluster compounds of according to claim 6 five vacant manganese is characterized in that: step 2) in organic solvent be acetone or methyl alcohol.
9. according to claim 6 or the preparation method of the two seven tungsten phosphorus oxygen cluster compounds of 8 described five vacant manganese, it is characterized in that: the volume ratio of organic solvent and distilled water is 1:2 ~ 2.5.
10. the preparation method of the two seven tungsten phosphorus oxygen cluster compounds of according to claim 6 five vacant manganese is characterized in that: step 3) middle sodium hydroxide solution accent pH=5.5 ~ 8.5.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104771411A (en) * 2015-03-20 2015-07-15 金华职业技术学院 Novel pharmaceutical application of five-vacancy ferric dihepta-tungsten phosphorus oxygen cluster compound
CN110817971A (en) * 2019-08-29 2020-02-21 吉林化工学院 Polyoxometallate and preparation method and application thereof
CN114084909A (en) * 2021-11-12 2022-02-25 河南大学 Manganese-oxygen cluster constructed based on isopolytungstate and synthetic method thereof

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CN1765751A (en) * 2004-10-28 2006-05-03 中国科学院福建物质结构研究所 A kind of polyoxometallic acid salt compound

Non-Patent Citations (1)

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Title
DONGDI ZHANG, ET AL.: "Four Members of the Sandwich-Type Polytungstophosphate Family Based on Pentalacunary [HPW7O28]8- Building Blocks", 《EUROPEAN JOURNAL OF INORGANIC CHEMISTRY》, vol. 2013, no. 1011, 6 December 2012 (2012-12-06) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104771411A (en) * 2015-03-20 2015-07-15 金华职业技术学院 Novel pharmaceutical application of five-vacancy ferric dihepta-tungsten phosphorus oxygen cluster compound
CN104771411B (en) * 2015-03-20 2018-05-01 金华职业技术学院 The new medical use of the five vacant double seven tungsten phosphorus oxygen cluster compounds of iron
CN110817971A (en) * 2019-08-29 2020-02-21 吉林化工学院 Polyoxometallate and preparation method and application thereof
CN114084909A (en) * 2021-11-12 2022-02-25 河南大学 Manganese-oxygen cluster constructed based on isopolytungstate and synthetic method thereof

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