CN103011120A - Five-vacancy transition metal di-hepta-tungsten phosphorus oxygen cluster series compound and preparation method thereof - Google Patents

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

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CN103011120A
CN103011120A CN2012105666575A CN201210566657A CN103011120A CN 103011120 A CN103011120 A CN 103011120A CN 2012105666575 A CN2012105666575 A CN 2012105666575A CN 201210566657 A CN201210566657 A CN 201210566657A CN 103011120 A CN103011120 A CN 103011120A
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transition metal
phosphorus oxygen
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tungsten phosphorus
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张必松
殷之武
李云霞
施存元
吴昌胜
裘建平
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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 transition metal di-hepta-tungsten phosphorus oxygen cluster series compound and a preparation method thereof. The five-vacancy transition metal di-hepta-tungsten phosphorus oxygen cluster series compound is provided with an anionic compound unit; a chemical formula of the anionic compound unit is [M(H(1-3)PW7O28)2]<n->; M is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn; and n is between 10 and 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 bunch series compounds of five vacant transition metal 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 bunch series compounds of five vacant transition metal 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] .BernoldHasenknopf, Polyoxometalates:Introductiontoaclassofinorganiccompound sandtheirbiomedicalapplications, FrontiersinBioscience, 2005,10:275-287. document [2] .JeffreyT.Rhule, CraigL.Hill, andDeborahA.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] (HuDH, ShaoC, GuanW, etal.StudiesontheinteractionsofTi-containingpolyoxometal ates(POMs) withSARS-CoV3CL ProBymolecularmodeling[J], JInorgBioohem, 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] (JianxinLi, RongxinTan, RuiLi, XiaohongWang, etal.Syntheses, propertiesandbiologicalactivityoforganogermaniumsubstitu tedheterpolytungstates[J], InorganicChemistryCommunications, 2007,10:216-219.), document [6] JianxinLi, FengyingZhai, XiaohongWang, etal.Synthesisandbiologicalactivityoftriorganogermaniums ubstitutedheteropolytungstates[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] (FengyingZhai, XiaohongWang, DongliuLi, etal.SynthesisandbiologicalevaluationofdecavanadateNa 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, etal.Anovelanti-tumoragent, polyoxomolybdateinducesapoptoticcelldeathinAsPC-1humanpa ncteaticcancercells[J], Biomedicine﹠amp; Pharmacotherapy, 2005,59:240-244.), document [9] (XiaohongWang, JingfuLiu, JianxinLi, etal.Synthesisandantitumoractivityofcyclopentadienyltita niumsubstitutedpolyoxotungstate[CoW 11O 39(CpTi)] 7-(Cp=η 5-C 5H 5) [J], JournalofInorganicBiochemistry, 2003,94:279-284.), document [10] (XiaohongWang, FengLi, ShuxiaLiuandM.T.Pope, Newliposome-encapsulated-polyoxometalates:synthesisandan titumoralactivity[J], JournalofInorganicBiochemistry, 2005,99:452-457), document [11] (FengyingZhai, DongliuLi, ChunliZhang, XiaohongWang, RuiLi, Synthesisandcharacterizationofpolyoxometalatesloadedstar tchnanocomplexanditsantitumoralactivity[J], EuropeanJournalofMedicinalChemistry, 2008,43:1911-1917), document [12] (Xiao-HongWang, Jing-FuLiu, Ya-GuangChen, QunLiu, Ju-TaoLiuandM.T.Pope, Synthesis, characterizationandbiologicalactiveityoforganotitaniumsu bstitutedheteropolytungstates, 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 bunch series compounds of five vacant transition metal, 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 bunch series compounds of a kind of above-mentioned five vacant transition metal.
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
The two seven tungsten phosphorus oxygen bunch series compounds of five vacant transition metal, this compound has following anionic compound unit, and the chemical formula of anionic compound unit is: [M(H (1-3)PW 7O 28) 2] N-Described M is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn; Described n=10 ~ 14; Described M, P, W, O have following structural formula:
Figure BDA00002636562700031
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 adopt " H " type, " Z " type, " S " type, " C " one or more graftings in the type hydration sodium ion.
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 bunch series compounds of described five vacant transition metal, the method comprises the steps:
1) gets transition metal salt soluble in water, described transition metal is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn, add an amount of dissolved in distilled water, add again excessive NaOH solution, 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: be down to room temperature by 150 ~ 170 ℃ in 10 ~ 14 hours;
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, 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 transition metal atoms bridging bunch have consisted of the sandwich two seven tungsten phosphorus oxygen bunch unit of transition metal.
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 structural unit of O.
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 [Na 14(H 2O) 38Mn(HPW 7O 28) 2] 6H 2The X-ray powder diffraction pattern of O.
Fig. 6 is [Na 14(H 2O) 38Mn(HPW 7O 28) 2] 6H 2The infrared spectrogram of O.
Fig. 7 is [Fe(H 2PW 7O 28) 2] 12-Structural unit.
Fig. 8 is [Na 12(H 2O) 34Fe(H 2PW 7O 28) 2] 10H 2The structural unit of O.
Fig. 9 is the structural unit of " S " type hydration sodium ion.
Figure 10 is the structural unit of " C " type hydration sodium ion.
Figure 11 is [Na 12(H 2O) 34Fe(H 2PW 7O 28) 2] 10H 2The X-ray powder diffraction pattern of O.
Figure 12 is [Na 12(H 2O) 34Fe(H 2PW 7O 28) 2] 10H 2The infrared spectrogram of O.
Embodiment
Embodiment 1
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/LNaOH 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 embodiment 1 preparation are carried out X-ray single crystal diffraction, Infrared spectroscopy, confirm crystalline structure.Its bunch unit such as Fig. 2, counter cation are hydrated cation such as Fig. 3,4, X-ray powder diffraction pattern 5, infrared spectra Fig. 6.
Its crystallographic data is: H 90MnNa 14O 100P 2W 14, FW=4703.22, triclinic, spacegroupP-1, a=11.877(2), b=12.125(2),
Figure BDA00002636562700051
α=80.13(3) °, β=85.40(3) °, γ=60.80(3) °, Z=1, D Calc=3.511Mg/m 3,
Figure BDA00002636562700053
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）。
Five above-mentioned vacant manganese seven tungsten phosphorus oxygen cluster compounds have following characteristic:
(1) five vacant manganese seven tungsten phosphorus oxygen cluster compounds 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 cluster compounds have the redox property similar to PM-8, kill virocyte by redox reaction;
(3) five vacant manganese seven tungsten phosphorus oxygen cluster compounds 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 cluster compounds have potential application at aspects such as catalyzer and molecular based light, electricity, magneticsubstances
Embodiment 2
Two seven phosphorus oxygen cluster compounds of ten disodium hydrated ion bridgings, five vacant iron and preparation method thereof.
The preparation of the two seven phosphorus oxygen cluster compounds of provided by the invention five vacant iron, the method comprises the steps:
(1) gets ferrous sulfate crystal (FeSO 4.7H 2O), add an amount of dissolved in distilled water, add again excessive 1mol/LNaOH solution, with ferrous hydroxide (ironic 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) be dissolved in 1:2(v/v) in the mixed solvent of acetone and distilled water, stir the ironic hydroxide and the 10mL methyl alcohol that slowly add new system after half an hour;
(3) transfer pH with sodium hydroxide solution, stir in the stainless steel cauldron of the 50mL inner liner polytetrafluoroethylene of packing into after 2 hours;
(4) 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;
(5) solids removed by filtration insolubles, filtrate is spontaneous evaporation at ambient temperature, finds to have the light yellow bulk crystals of suitable monocrystalline test to separate out after 2 months.
With the two seven tungsten phosphorus oxygen cluster compound [Na of embodiment 20 disodium hydrated ion bridging iron (II) 12(H 2O) 34Fe(H 2PW 7O 28) 2] 10H 2The structural identification of O.
Its crystallographic data is: H 92FeNa 12O 100P 2W 14, FW=4660.17, triclinic, spacegroupP-1, a=10.572(2), b=11.009(2),
Figure BDA00002636562700061
α=85.01(3) °, β=77.72(3) °, γ=67.48(3) °,
Figure BDA00002636562700062
Z=1, D Calc=3.503Mg/m 3,
Figure BDA00002636562700063
T=273K, R 1(wR 2)=0.0532(0.1589).Title ligand polymer structural unit is by two seven tungsten phosphorus oxygen of an iron (II) bunch, 12 hydration sodium ions and 6 crystal water molecular compositions.In seven tungsten phosphorus oxygen bunch unit, comprise seven WO 6Octahedron and a PO 4Tetrahedron, Fe(II) two seven tungsten phosphorus oxygen of atom bridging bunch have consisted of the two seven tungsten phosphorus oxygen bunch unit (Fig. 7, Fig. 8) of the iron clamp heart.Counter cation is hydrated cation such as Fig. 9,10, X-ray powder diffraction pattern 11, infrared spectra Figure 12.
Five above-mentioned vacant iron seven tungsten phosphorus oxygen cluster compounds have following characteristic:
(1) five vacant iron seven tungsten phosphorus oxygen cluster compounds 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 iron seven tungsten phosphorus oxygen cluster compounds have the redox property similar to PM-8 [2], kill virocyte by redox reaction;
(3) five vacant iron seven tungsten phosphorus oxygen cluster compounds have with virus protein and form interlinkage in the chain by hydrogen bond, stop virus protease to copy, thereby realize lacking tumour, antiviral purpose;
(4) five vacant iron seven tungsten phosphorus oxygen cluster compounds have potential application at aspects such as catalyzer and molecular based light, electricity, magneticsubstances.

Claims (8)

1. the two seven tungsten phosphorus oxygen bunch series compounds of five vacant transition metal is characterized in that this compound has following anionic compound unit, and the chemical formula of anionic compound unit is: [M (H (1-3)PW 7O 28) 2] N-Described M is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn; Described n=10 ~ 14; And described M, P, W, O have following structural formula:
Figure FDA00002636562600011
2. the two seven tungsten phosphorus oxygen bunch series compounds of according to claim 1 five vacant transition metal 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 bunch series compounds of according to claim 2 five vacant transition metal is characterized in that: the cation compound unit employing hydration sodium ion of this compound.
4. the two seven tungsten phosphorus oxygen bunch series compounds of according to claim 3 five vacant transition metal is characterized in that: one or more graftings in hydration sodium ion employing " H " type, " Z " type, " S " type, " C " type hydration sodium ion.
5. a preparation method who prepares the two seven tungsten phosphorus oxygen bunch series compounds of claimed in claim 1 five vacant transition metal is characterized in that the method comprises the steps:
1) gets transition metal salt soluble in water, described transition metal is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn, add an amount of dissolved in distilled water, add again excessive NaOH solution, 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: be down to room temperature by 150 ~ 170 ℃ in 10 ~ 14 hours;
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.
6. the preparation method of the two seven tungsten phosphorus oxygen bunch series compounds of according to claim 4 five vacant transition metal is characterized in that: step 2) in organic solvent be acetone or methyl alcohol.
7. according to claim 4 or the preparation method of the two seven tungsten phosphorus oxygen bunch series compounds of 5 described five vacant transition metal, it is characterized in that: the volume ratio of organic solvent and distilled water is 1:2 ~ 2.5.
8. the preparation method of the two seven tungsten phosphorus oxygen bunch series compounds of according to claim 4 five vacant transition metal is characterized in that: step 3) middle sodium hydroxide solution accent pH=5.5 ~ 8.5.
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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
CN106622372A (en) * 2016-12-17 2017-05-10 聊城大学 Barium-silicon tungsten oxygen cluster catalyst, preparation method and application thereof
CN107417741A (en) * 2017-08-09 2017-12-01 龙岩学院 Diethylenetriamine vanadium (III) tungsten (VI) vanadium (IV) oxygen cluster compound and its synthetic method
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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Cited By (9)

* 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
CN106622372A (en) * 2016-12-17 2017-05-10 聊城大学 Barium-silicon tungsten oxygen cluster catalyst, preparation method and application thereof
CN106622372B (en) * 2016-12-17 2018-12-11 聊城大学 A kind of barium silica tungsten oxygen cluster catalyst, preparation method and its usage
CN107417741A (en) * 2017-08-09 2017-12-01 龙岩学院 Diethylenetriamine vanadium (III) tungsten (VI) vanadium (IV) oxygen cluster compound and its synthetic method
CN107417741B (en) * 2017-08-09 2019-10-22 龙岩学院 Diethylenetriamine vanadium (III)-tungsten (VI)-vanadium (IV)-oxygen cluster compound and its synthetic method
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
CN114084909B (en) * 2021-11-12 2023-01-17 河南大学 Manganese-oxygen cluster constructed based on isopolytungstate and synthetic method thereof

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