CN1312031C - Method for synthesizing gadolinium metal fullerol using ultrasonic wave - Google Patents
Method for synthesizing gadolinium metal fullerol using ultrasonic wave Download PDFInfo
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- CN1312031C CN1312031C CNB2004100095099A CN200410009509A CN1312031C CN 1312031 C CN1312031 C CN 1312031C CN B2004100095099 A CNB2004100095099 A CN B2004100095099A CN 200410009509 A CN200410009509 A CN 200410009509A CN 1312031 C CN1312031 C CN 1312031C
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- gadolinium metal
- toluene
- fullerol
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Abstract
The present invention belongs to the field of synthesizing double-hydroxy metal-fullerol compound, which particularly relates to a method of synthesizing Gd@C82 (OH)2 using ultrasonic waves. A dioxygen water solution and a toluene or ortho-dichlorobenzene solution of gadolinium metal fullerol are filled in a reaction vessel at the temperature of 0 DEG C-20 DEG C, wherein the volume ratio of the dioxygen water solution to the toluene or the ortho-dichlorobenzene solution of the gadolinium metal fullerol is 5 to 20: 1; the dioxygen water solution and the toluene or ortho-dichlorobenzene solution generate oscillating reaction by using ultrasonic waves; a mixed solution in the reaction vessel is statically placed, liquid separation is than carried out after delaminating, and then the solution of the gadolinium metal fullerol is obtained. The method has the advantages of simple and easy operation, mild experimental condition, easy control and single reaction product; in addition, because a phase-transfer reagent is not added in the reaction process, other impurities can not be led in the solution of the gadolinium metal fullerol, and therefore, the method greatly simplifies a separation and purification step and reduces separation and purification cost.
Description
Technical field
The invention belongs to synthetic two hydroxy metal fullerene compound field, particularly with the synthetic Gd@C of ultrasonic wave
82(OH)
2Method.
Background technology
Metal fullerene has just caused common people's attention with its particular structure and special nature from producing, and becomes the focus that the association area scientist pays close attention to.Especially in recent years it is synthetic that water-soluble poly-hydroxy metal richness is reined in pure success, and this compounds becomes the active material of Materials science and biomedical sector gradually.
C
60(OH) n (n ≈ 30～40) can be used as virus of AIDS inhibitor, radical scavenger and carcinostatic agent (Chem.Phys.Lett.2000,324,255-259); And the richness that belongs to covered with gold leaf is reined in alcohol in water miscible, and its Special Significance is more arranged.For example, poly-hydroxy Gd@C
82Derivative Gd@C
82(OH) n (n ≈ 40) can be used as the Magnetic resonance imaging contrast medium and is applied to medical science aspect (Bioconjugate.Chem.2001,12,510～514).But the synthetic method of the two is similar, promptly at ambient temperature, adding tetrabutylammonium chloride in the strong base solution as phase-transfer catalyst, the toluene solution with the gadolinium metal fullerene mixes then, make water and organic phase is miscible reacts by vigorous stirring, generate Gd@C
82(OH) n (n ≈ 40) separates obtaining the mixture that gadolinium metal richness is reined in alcohol again.Also there is document (Chem.Mater.1999,11,1003～1006) to mention nitric acid and the Pr@C that uses 65wt%
82Carbon tetrachloride solution reflux 12 hours, prepared in reaction praseodymium metal richness is reined in pure Pr@C
82Om (OH) n (m ≈ 10) (n ≈ 40).Reining in alcohol by aforesaid method synthetic metal richness has better water solubility, but hydroxy number is uncertain in addition for the carbon cage, does not promptly have the composition of determining; Stability also has much room for improvement.In addition, because composition is complicated, the separation purification ratio of reaction product is difficulty.
At present, domestic have only only a few R﹠D institution to carry out the synthetic of metal fullerene and derivative thereof and research, though also obtained challenging result, and abroad compares, and also exists very big gap.Adopt the synthetic metal richness of the simple method that is suitable for to rein in the develop rapidly that alcohol will promote association areas such as Materials science and biomedicine greatly.
Summary of the invention
It is simple that one of purpose of the present invention provides a kind of separation purified reaction product, and can make the metal richness of preparing rein in the high method of reining in alcohol with the synthetic metal richness of ultrasonic wave of alcohol stability.
Two of purpose of the present invention is the Gd@C that adopt after high performance liquid chromatography separates
82Toluene or o-dichlorobenzene solution, with commonly used concentration be the H of 10wt%～30wt%
2O
2The aqueous solution generates gadolinium metal richness and reins in alcohol-Gd@C as raw material under the certain reaction condition
82(OH)
2And determine its structure by the simple analysis method.
Method of reining in alcohol of the present invention with the synthetic gadolinium metal richness of ultrasonic wave:
In temperature is under 0 ℃～20 ℃ conditions, with the hydrogen peroxide (H of 10wt%～30wt%
2O
2) solution and gadolinium metal fullerene (Gd@C
82) toluene or o-dichlorobenzene solution place reaction vessel, wherein hydrogen peroxide and gadolinium metal fullerene (Gd@C
82) toluene or the volume ratio of o-dichlorobenzene solution be 5～20: 1; With ultra-sonic oscillation reaction 6～9 hours; Ultrasonic power remains on 50～200 watts in reaction process, and the mixing solutions in the reaction vessel is left standstill for some time, treat its layering after, carry out separatory and handle and to obtain the solution that gadolinium metal richness is reined in alcohol.
The gadolinium metal richness that the present invention prepares is reined in pure available MALDI-TOF and is analyzed its mole molecular mass.
The present invention be with hydrogen peroxide as the reactant that oh group is provided, finally generate Gd@C
82(OH)
2Be main purpose.Consider gadolinium metal fullerene Gd@C
82Synthetic and separate difficulty on purifying, and hydrogen peroxide decomposing property very easily, in order to improve gadolinium metal fullerene Gd@C as much as possible
82Transformation efficiency, Gd@C
82Toluene or the H of o-dichlorobenzene solution and 10wt%～30wt%
2O
2The volume ratio of solution is 1: 5～20, after reaction is finished, takes out reaction vessel, treats to pass through separatory in the container after the solution layering, can obtain gadolinium metal richness and rein in alcoholic solution.
The present invention requires temperature is controlled, temperature can be accelerated the random thermal motion of molecule, and then improve the dynamics and the frequency of intermolecular mutual collision, therefore, the rising temperature of reaction helps improving speed of reaction, shortens the reaction times, suitable from considering in this respect, be reflected to compare under the higher temperature; On the other hand, even H at normal temperatures
2O
2Also very unstable, generation oxygen G﹠W takes place to decompose, if temperature is too high, most of H
2O
2Just decompose before reacting with the gadolinium metal fullerene, make reaction-ure conversion-age reduce, this will negate and should carry out under lower temperature.Take all factors into consideration the factor of two aspects, should be controlled at temperature in 0 ℃～20 ℃ scopes, so that this is reflected at reactant (Gd@C
82) carry out with speed faster under the prerequisite of fully reaction.
The present invention is that employing method of ultra-sonic oscillation in water-bath is mixed immiscible organic phase with mutually inorganic.Normally add tensio-active agent or make two immiscible blended by stirring.Add tensio-active agent and can introduce other impurity, increase the difficulty of later stage separation and purification; Vigorous stirring can make two solution fully contact, and also can not introduce other impurity, quickens H but solution temperature is raise
2O
2Decompose, under this condition, the H of the overwhelming majority
2O
2Decompose rapidly, do not react with the gadolinium metal fullerene.Adopt ultrasonic concussion neither can introduce other useless impurity, can control oscillation intensity again organic phase is mixed mutually with inorganic, and the temperature of control reaction is unlikely too high or too low.
Aforesaid method can synthesize Gd@C fast
82(OH)
2, the mixing solutions in the reaction vessel is left standstill for some time, treat its layering after, carry out separatory and handle and just can obtain Gd@C
82(OH)
2Solution.
Of the present invention method is simple, the gentle and control easily of experiment condition; Reaction product is single, owing to do not add phase transfer reagent in the reaction process, therefore reins in the impurity that also can not introduce other in the alcoholic solution in gadolinium metal richness in addition, and this has just simplified the step of separation and purification greatly, has reduced the cost of separation and purification.
Description of drawings
Fig. 1. the mass spectrum of the embodiment of the invention 1.
Embodiment
Embodiment 1.
1. synthetic: as in reaction vessel, to add brown Gd@C
82O-dichlorobenzene solution feeds nitrogen oxygen is got rid of, and adds the H that concentration is 30wt% then
2O
2Solution, wherein hydrogen peroxide and Gd@C
82The volume ratio of o-dichlorobenzene solution is 15: 1; The sealing back is immersed container in the ultrasonic oscillation device, controls bath temperature at 10 ℃, 100 watts of ultrasonic powers, and successive reaction is stopped reaction after 9 hours.
2. characterize: by the post reaction mixture standing demix, the upper and lower solution that takes a morsel respectively after the solution layering carries out flight time mass spectrum (TOF) analysis respectively.The intensity of the molecular ion peak that exists in the mass spectrum before and after the comparative analysis reaction can roughly draw the degree of reaction.See accompanying drawing 1.
By observing the mass spectrum of embodiment 1, on mass spectrum, there are 1173～1180 molecular ion peaks, meaning has Gd@C in the product
82(OH)
2, be positioned at 1155～1162 and 1139～1146 molecular ion peak and then correspond respectively to by product Gd@C
82(O) and do not have a Gd@C of complete reaction
82Change reaction conditions, the ratio of the corresponding molion peak intensity of reactant, by product and principal product also will change thereupon.
Embodiment 2.
1. synthetic: as in reaction vessel, to add brown Gd@C
82O-dichlorobenzene solution feeds nitrogen oxygen is got rid of, and adds the H of concentration 30wt% then
2O
2Solution, wherein hydrogen peroxide and Gd@C
82The volume ratio of o-dichlorobenzene solution is 6: 1; The sealing back is immersed container in the ultrasonic oscillation device, controls bath temperature at 20 ℃, 100 watts of ultrasonic powers, and successive reaction is stopped reaction after 7 hours.
2. characterize: by the post reaction mixture standing demix, the upper and lower solution that takes a morsel respectively after the solution layering carries out flight time mass spectrum (TOF) analysis respectively.
Embodiment 3.
1. synthetic: as in reaction vessel, to add brown Gd@C
82O-dichlorobenzene solution feeds nitrogen oxygen is got rid of, and adds the H that concentration is 30wt% then
2O
2Solution, wherein hydrogen peroxide and Gd@C
82The volume ratio of o-dichlorobenzene solution is 18: 1; Sealing back is immersed container in the ultrasonic oscillation device, with and whose mixture control bath temperature at 0 ℃, 200 watts of ultrasonic powers, successive reaction is stopped reaction after 8 hours.
2. characterize: by the post reaction mixture standing demix, the upper and lower solution that takes a morsel respectively after the solution layering carries out flight time mass spectrum (TOF) analysis respectively.
Embodiment 4.
1. synthetic: as in reaction vessel, to add brown Gd@C
82Toluene solution feeds nitrogen oxygen is got rid of, and adds the H that concentration is 30wt% then
2O
2Solution, wherein hydrogen peroxide and Gd@C
82The volume ratio of o-dichlorobenzene solution is 12: 1; The sealing back is immersed container in the ultrasonic oscillation device, controls bath temperature at 20 ℃, 100 watts of ultrasonic powers, and successive reaction is stopped reaction after 8 hours.
2. characterize: by the post reaction mixture standing demix, the upper and lower solution that takes a morsel respectively after the solution layering carries out flight time mass spectrum (TOF) analysis respectively.
Claims (6)
1. ultrasonic synthesizing Gd metal fullerenol Gd
82(OH)
2Method, it is characterized in that:
In temperature is under 0 ℃～20 ℃ conditions, with hydrogen peroxide solution and gadolinium metal fullerene Gd@C
82Toluene or o-dichlorobenzene solution place reaction vessel, wherein hydrogen peroxide and gadolinium metal fullerene Gd@C
82Toluene or the volume ratio of o-dichlorobenzene solution be 5～20: 1; React with ultra-sonic oscillation; Mixing solutions in the reaction vessel is left standstill, treat its layering after, carry out separatory and handle and to obtain gadolinium metal richness and rein in pure Gd@C
82(OH)
2Solution.
2. method according to claim 1 is characterized in that: described hydrogen peroxide concentration is 10wt%～30wt%.
3. method according to claim 1 is characterized in that: described ultra-sonic oscillation are to adopt to carry out ultra-sonic oscillation in water-bath.
4. according to claim 1 or 3 described methods, it is characterized in that: the described ultra-sonic oscillation reaction times is 6～9 hours.
5. according to claim 1 or 3 described methods, it is characterized in that: described ultrasonic power is 50～200 watts.
6. method according to claim 4 is characterized in that: described ultrasonic power is 50～200 watts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100095099A CN1312031C (en) | 2004-09-03 | 2004-09-03 | Method for synthesizing gadolinium metal fullerol using ultrasonic wave |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100095099A CN1312031C (en) | 2004-09-03 | 2004-09-03 | Method for synthesizing gadolinium metal fullerol using ultrasonic wave |
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|---|---|
| CN1743264A CN1743264A (en) | 2006-03-08 |
| CN1312031C true CN1312031C (en) | 2007-04-25 |
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|---|---|---|---|
| CNB2004100095099A Expired - Fee Related CN1312031C (en) | 2004-09-03 | 2004-09-03 | Method for synthesizing gadolinium metal fullerol using ultrasonic wave |
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| CN108203088A (en) * | 2016-12-16 | 2018-06-26 | 北京福纳康生物技术有限公司 | A kind of high water solubility fullerol and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5376353A (en) * | 1991-10-28 | 1994-12-27 | Vasilevskis; Janis | Method for the production of H2 O2 using Fullerenes |
| JPH0748302A (en) * | 1993-07-30 | 1995-02-21 | Tokyo Gas Co Ltd | Method for synthesizing fullerol |
| JPH07233093A (en) * | 1994-02-24 | 1995-09-05 | Otsuka Pharmaceut Co Ltd | Contrasting agent for forming magnetic resonance image |
| CN1316411A (en) * | 2001-03-14 | 2001-10-10 | 陈滇宝 | Process for preparing Cy(OH)n |
| US20030006684A1 (en) * | 2001-03-27 | 2003-01-09 | Shinichi Kawate | Catalyst used to form carbon fiber, method of making the same and electron emitting device, electron source, image forming apparatus, secondary battery and body for storing hydrogen |
| CN1449993A (en) * | 2003-04-22 | 2003-10-22 | 上海大学 | Process for preparing fullerols |
-
2004
- 2004-09-03 CN CNB2004100095099A patent/CN1312031C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5376353A (en) * | 1991-10-28 | 1994-12-27 | Vasilevskis; Janis | Method for the production of H2 O2 using Fullerenes |
| JPH0748302A (en) * | 1993-07-30 | 1995-02-21 | Tokyo Gas Co Ltd | Method for synthesizing fullerol |
| JPH07233093A (en) * | 1994-02-24 | 1995-09-05 | Otsuka Pharmaceut Co Ltd | Contrasting agent for forming magnetic resonance image |
| CN1316411A (en) * | 2001-03-14 | 2001-10-10 | 陈滇宝 | Process for preparing Cy(OH)n |
| US20030006684A1 (en) * | 2001-03-27 | 2003-01-09 | Shinichi Kawate | Catalyst used to form carbon fiber, method of making the same and electron emitting device, electron source, image forming apparatus, secondary battery and body for storing hydrogen |
| CN1449993A (en) * | 2003-04-22 | 2003-10-22 | 上海大学 | Process for preparing fullerols |
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| Publication number | Publication date |
|---|---|
| CN1743264A (en) | 2006-03-08 |
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| C06 | Publication | ||
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| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Shandong Blue Sail Plastic & Rubber Co., Ltd. Assignor: Institute of Chemistry, Chinese Academy of Sciences Contract fulfillment period: 2007.4.28 to 2022.4.28 contract change Contract record no.: 2009370000218 Denomination of invention: Method for synthesizing gadolinium metal Fuller alcohol Gd@C#-[82] (OH) #-[2] by ultrasonic wave Granted publication date: 20070425 License type: Exclusive license Record date: 2009.8.19 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.4.28 TO 2022.4.28; CHANGE OF CONTRACT Name of requester: SHANDONG LANFAN PLASTIC CO., LTD. Effective date: 20090819 |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070425 Termination date: 20120903 |