CN1389395A - Direct process of reducing and separating metal-included fullerene compound from soot - Google Patents
Direct process of reducing and separating metal-included fullerene compound from soot Download PDFInfo
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- CN1389395A CN1389395A CN 02124174 CN02124174A CN1389395A CN 1389395 A CN1389395 A CN 1389395A CN 02124174 CN02124174 CN 02124174 CN 02124174 A CN02124174 A CN 02124174A CN 1389395 A CN1389395 A CN 1389395A
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- metal
- fullerenes
- soot
- solvent
- fullerene
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Abstract
The method for direct reduction and separation of fullerence metal clathrate from soot richly containing fullerene metal clathrate is characterized by that it utilizes the regulation of polarity of solvent to make the hollow fullerene and fullerene metal clathrate with high reduction potential separate from hollow fullerene and fullerene metal clathrate with low reduction potential. Said ivnented method has no need of HPLC separation, and can obtain lots of fullerene metal clathrate. The mixture separated out by means of said invented method can be used for directly synthesizing water soluble derivative, and said derivative can be used as excellent nuclear magnetic imaging contrast medium.
Description
Technical field: the present invention relates to a kind of method that reduction separates fullerenes metal from contain the fullerenes metal soot.
Background technology: up to now, to studies show that of fullerenes metal, fullerenes metal has novel structure and character, has broad application prospects in a lot of fields.For example, water miscible fullerenes metal derivative Gd@C
82(OH)
xBe a kind of good NMR (Nuclear Magnetic Resonance) imaging contrast medium, its relaxation rate is clinically 20 times of the relaxation rate of the contrast medium Gd-DTPA of usefulness now.(M.Mikawa，H.Kato，M.Okumura，M.Narazaki，Y.?Kanazawa，N.Miwa?and?H.Shinohara，Bioconjugate?Chem.，2001，12，510.)
Usually, fullerenes metal is by the arc process synthetic, and the synthetic product is the mixture of many kinds of fullerenes metals and empty fullerene, need just can obtain pure product (Shinohara H.Endohedral metallofullerenes.Rep.Prog.Phys.2000 with separating through extracting, 63,843-892).And the HPLC isolation technique is the means commonly used of separating fullerenes metal.Concrete grammar is, will contain the soot of fullerenes metal, utilizes solvent, as dithiocarbonic anhydride, pyridine etc. carried out for two steps even multistep is extracted, and were dissolved in toluene behind the extracting solution evaporate to dryness again, be moving phase with toluene at last, utilize chromatographic column specially to carry out two steps or multistep HPLC separation.
The shortcoming of this separation method is that sepn process is longer, and the extraction yield of solvent extraction fullerenes metal is lower, and the HPLC separation is a very heavy work, need to utilize the long time, consume a large amount of solvents, therefore be difficult to obtain a large amount of fullerenes metals.For the application of fullerenes metal, this is an obstacle that is difficult to overcome.
Summary of the invention:
Purpose of the present invention is exactly the defective at prior art, a kind of method that directly reduction separates fullerenes metal from soot is proposed, needn't separate through HPLC, just can obtain a large amount of fullerenes metals, simple, consuming time less, reagent consumption is few, extraction efficiency is high.
The method that directly reduction separates fullerenes metal from soot of the present invention, its step comprises:
1, utilizing arc process, is source metal with the alloy, the synthetic soot that contains fullerenes metal; (LianYF, Shi ZJ, Zhou XH, He XR, Gu ZN.Chemistry of materials 2001,13 (1), 39-42)
2, with the soot of collecting, under oxygen free condition, with reductive agent with mol ratio 1: 1-1: 5 mixed;
Used reductive agent is selected from: metal, organic and inorganic reducing agents such as alumino nickel, magnesium powder, zinc powder, glass putty, sodium hydride, Sulfothiorine, lithium aluminium hydride, dicyclopentadienylcobalt.When using metal such as alumino nickel, Sulfothiorine or inorganic reducing agent, need to add sodium hydroxide and water with mol ratios such as reductive agent;
3, under oxygen free condition, add the solvent of the opposed polarity of deoxygenation, stirred 12-36 hour;
Solvent for use is selected from: tetrahydrofuran (THF), toluene, acetonitrile, dimethyl formamide, methyl-sulphoxide or benzene nitrile isopolarity and non-polar solvent and mixed solvent thereof;
4, remove water layer and residue;
5, organic layer has been removed the solid particulate that suspends behind membrane filtration, obtains the negative solution of fullerenes metal.In the organic solvent of opposed polarity, can obtain the negative ion of the fullerenes metal of different components.
Principle of the present invention is: (1) different fullerenes metal has different reduction potentials with soccerballene.(2) polarity of solvent has very big influence to the reduction potential of soccerballene and fullerenes metal.In different solvents, C
60Reduction potential can change 0.4v (Noviandri I., Bolskar R.D., Lay P.A., Reed, C.A., J.Phys.Chem.B, 1997,101,6350).When polarity of solvent reduced, the reduction potential of soccerballene moved to negative direction.This just means, under the identical condition of reductive agent, and C
60In weak polar solvent, reduce than difficulty in the intensive polar solvent.Although and Gd@C
82Reduction potential have same C
60Identical variation tendency, but because the reduction potential of itself compares C
60Low, thereby in weak polar solvent, still can be reduced.
Among the present invention, by regulating polarity of solvent, empty fullerene that can be gradually that reduction potential is high separates with fullerenes metal with the low empty fullerene of fullerenes metal and reduction potential.For example, M@C
82And M
2@C
80(wherein, M represents rare earth element) has the reduction potential of corrigendum than other soccerballene and fullerenes metal, can be extracted by the reduction of selectivity, directly and other separating substances come.
Characteristics of the present invention and excellent effect thereof:
1, a kind of separation method of new fullerenes metal has been proposed.Promptly utilize the control polarity of solvent, the direct method of separating fullerenes metal of from soot, optionally reducing.
2, the extraction efficiency height of the solvent extraction that this method ratio is commonly used, and method is simple and efficient.
3, present method selectivity height, empty fullerene that can be gradually that reduction potential is high separates with fullerenes metal with the low empty fullerene of fullerenes metal and reduction potential.For example, can be with M@C
82And M
2@C
80Directly from soot, separate in a large number.
4, utilize the isolated Gd@C of present method
82And Gd
2@C
80The direct synthesizing water-solubility derivative of mixture, this derivative can become outstanding NMR (Nuclear Magnetic Resonance) imaging contrast medium, has broad application prospects at medical field.
Description of drawings:
Fig. 1 reduces the mass spectrum that contains the resulting solution of Gd fullerenes metal soot in the solvent of tetrahydrofuran (THF)
1----C
60，2----C
70，3----Gd@C
60，4----Gd@C
82
Fig. 2 reduces the mass spectrum of solution of soot gained in tetrahydrofuran (THF)/toluene mixed solvent
5----Gd
2@C
80
Specific embodiments:
For clearer explanation the present invention, enumerate following examples, but these there is not any restriction to scope of the present invention.The change of any non-intrinsically safe on basis of the present invention still belongs to scope of the present invention.
The soot and the 200-400mgAl-Ni alloy that 50-100mg are contained the Gd fullerenes metal, 400-800mg NaOH mixes, under oxygen free condition, add the 5-10ml oxygen-free water, add respectively afterwards the tetrahydrofuran (THF) of 10-20ml deoxygenation or the tetrahydrofuran (THF) that is mixed in proportion and toluene (2: 1-1: mixing solutions 2), stir more than 12 hours the mixture centrifugation respectively, lower floor is a water layer, and the upper strata is an organic phase.Remove water layer and unreacted residue, organic phase is through the membrane filtration of 0.45 μ m.
As can be seen from Figure 1, in this polar solvent, nearly all fullerenes metal and soccerballene can be reduced extraction, and extraction yield is that sooty is more than 7%.And in mixing solutions, the C of content maximum in many fullerenes metals and the soot
60And C
70Can not be reduced.As can be seen from Figure 2, has only Gd@C
82And Gd
2@C
80Reduction by selectivity extracts.
Claims (3)
1, a kind of method that directly reduction separates fullerenes metal from soot, its step comprises
1) utilizing arc process, is source metal with the alloy, the synthetic soot that contains fullerenes metal;
2) with the soot of collecting, under oxygen free condition, with reductive agent with mol ratio 1: 1-1: 5 mixed;
3) under oxygen free condition, add the solvent of the opposed polarity of deoxygenation, stirred 12-36 hour;
4) remove water layer and residue;
5) organic layer has been removed the solid particulate that suspends behind membrane filtration, obtains the negative solution of fullerenes metal.
2, the method that directly reduction separates fullerenes metal from soot as claimed in claim 1 is characterized in that used reductive agent is selected from metal, organic and inorganic reducing agents such as alumino nickel, magnesium powder, zinc powder, glass putty, sodium hydride, Sulfothiorine, lithium aluminium hydride, dicyclopentadienylcobalt; When using metal such as alumino nickel, Sulfothiorine or inorganic reducing agent, need to add sodium hydroxide and water with mol ratios such as reductive agent.
3, the method that directly reduction separates fullerenes metal from soot as claimed in claim 1 is characterized in that solvent for use is selected from tetrahydrofuran (THF), toluene, acetonitrile, dimethyl formamide, methyl-sulphoxide or benzene nitrile isopolarity and non-polar solvent and mixed solvent thereof.
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|---|---|---|---|
| CNB021241740A CN1170765C (en) | 2002-07-15 | 2002-07-15 | Direct process of reducing and separating metal-included fullerene compound from soot |
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|---|---|---|---|
| CNB021241740A CN1170765C (en) | 2002-07-15 | 2002-07-15 | Direct process of reducing and separating metal-included fullerene compound from soot |
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|---|---|
| CN1389395A true CN1389395A (en) | 2003-01-08 |
| CN1170765C CN1170765C (en) | 2004-10-13 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285798B (en) * | 2007-04-13 | 2012-04-04 | 武汉烟草(集团)有限公司 | Test method for cigarette added tea polyphenol stability |
| CN102115074B (en) * | 2009-12-30 | 2013-09-04 | 中国科学院高能物理研究所 | Extraction method of internally-embedded metal fullerene |
-
2002
- 2002-07-15 CN CNB021241740A patent/CN1170765C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285798B (en) * | 2007-04-13 | 2012-04-04 | 武汉烟草(集团)有限公司 | Test method for cigarette added tea polyphenol stability |
| CN102115074B (en) * | 2009-12-30 | 2013-09-04 | 中国科学院高能物理研究所 | Extraction method of internally-embedded metal fullerene |
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| Publication number | Publication date |
|---|---|
| CN1170765C (en) | 2004-10-13 |
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