CA2151225A1 - Process for preparing fullerene inclusion compounds - Google Patents
Process for preparing fullerene inclusion compoundsInfo
- Publication number
- CA2151225A1 CA2151225A1 CA002151225A CA2151225A CA2151225A1 CA 2151225 A1 CA2151225 A1 CA 2151225A1 CA 002151225 A CA002151225 A CA 002151225A CA 2151225 A CA2151225 A CA 2151225A CA 2151225 A1 CA2151225 A1 CA 2151225A1
- Authority
- CA
- Canada
- Prior art keywords
- fullerene
- cyclodextrin
- host lattice
- inclusion compound
- calix
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/70—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a condensed ring system consisting of at least two, mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic ring, e.g. cyclophanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
- C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/92—Systems containing at least three condensed rings with a condensed ring system consisting of at least two mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic system, e.g. cyclophanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Carbon And Carbon Compounds (AREA)
- Crushing And Grinding (AREA)
- Medicinal Preparation (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a process for preparing an inclusion compound of C60 fullerene and a host lattice selected from .gamma.-cyclodextrin and calix-[8]-arene, which comprises forming the inclusion compound by mechano-chemical activation of a solid mixture comprising C60 fullerene and the host lattice.
Description
215122~
HOECHST ARTIENGESELBSCHAFT HOE 94/F 158 Dr.DR/PP
Description Process for preparing fullerene inclusion compounds Numerous studies on fullerenes have been carried out, owing to their hydrophobic character, in organic solvents, although the fullerenes are only sparingly soluble in most of these solvents (N. Sivaraman et al., J. Org. Chem. 1992, 57, 6077-6079).
Recently, C60 fullerene has also been successfully dissolved in water, by heating solid C60 fullerene and an aqueous ~-cyclodextrin solution to the boiling point and converting the fullerene into a ~-cyclodextrin-C60-fullerene inclusion compound by re$1uxing for 50 hours or more (M. S~n~Ahl et al., Synthetic Metals, 55-57, 1993, 3252-3257; T. Andersson et al., J. Chem.
Soc., Chem. Commun. 1992, 604).
Water-soluble calixarene-C60-fullerene inclusion com-pounds, prepared by a 32 hour reaction of C60 powder and an aqueous calixarene solution under reflux, are described by R.U. Williams et al. (Recl. Trav. Chim.
Pays-Ba~ 111, 531-532 (1992)).
A disadvantage of the processes described is the time-consuming preparation under reflux conditions, which can lead to damage to the C60 molecule.
It is therefore an object of the invention to develop a simple and more rapid process for preparing water-soluble fullerene inclusion compounds.
The invention provides a process for preparing an inclu-sion compound of C60 fullerene and a host lattice selected from ~-cyclodextrin and calix-[8]-arene, which comprise6 forming the inclusion compouncl by mechano-chemical activation of a solid mixture comprising C60 fullerene and the host lattice.
In the process of the invention, solid C60 fullerene i~
mechanochemically treated with solid ~-cyclodextrin or solid calix-[8]-arene, i.e. intimately mixed for example by mechanical gr;n~;ng in a mortar or use of a ball mill.
The molar ratio of fullerene used to ~-cyclodextrin or calix-[8~-arene is generally from 1:1 to 1:15, preferably from 1:8 to 1:12, particularly preferably 1:10. The process of the invention is generally carried out at a temperature of from -20 to 100C, preferably from 20 to 50C, particularly preferably 25C, over a period of from 0.5 to 20 hours.
The C60 fullerene can be used in pure form (~ 99% by weight), as a mixture (70-99% by weight) or else as constituent of fullerene-cont~;n;ng carbon black (C60 content: 1-15% by weight). The process of the invention is therefore also suitable for separating C60 fullerene from fullerene-cont~;n;ng carbon black in a simple manner.
Preference is given to using pure C60 fullerene.
The inclusion compound can be characterized by W
spectroscopy in aqueous solution. For the purposes of characterization, the solid mixture can, after the mechanochemical treatment, be converted into a suspension by addition of from 10 to 30 ml of deionized water. This suspen~ion is generally again treated mechanochemically, for example by use of a ball mill (from 30 to 80 minutes) or of ultrasound (from 5 to 10 minutes). During this procedure, the inclusion compound formed by the process of the invention goes into solution.
The solution cont~; n; ng the inclusion compound can then be separated off by customary physical methods (centri-fugation, decantation and the like) and characterized.
The incluslon compounds of C60 fullerene and a host lattlce selected from y-cyclodextrin and calix-[8]-arene can be used, for example, as photocatalysts.
The y-cyclodextrin and calix-[8]-arene host lattices used are commercially available, for exarnple, from Chinoln (Budapest) and Sigma Chemical Co. (St. Louis, USA) respectively. C60 fullerene is likewise commercially available (from Hoechst AG) or is prepared from fullerene-containing carbon black by the method known from Kratschmer and Huffman (Kratschmer W., Lamb L.D., Fostiropoulos K., Huffman D.R.: Nature 347 (1990) 354).
The accompanying drawings show absorption spectra ln the wavelength range 200-600 nm.
Figure la is the spectrum of C60 in cyclohexane;
Figure lb is the spectrum shown by an aqueous solution of a mechanochemically produced C60/y~CD complex; and Figure lc is the spectrum shown by an aqueous solution of a C60/ -CD complex produced mechanochemically from fullerene-containing carbon black.
Example 1 A homogeneous mixture of 10 mg of C60 (Hoechst AG) having a purity of over 99.4% and 100 mg of y-cyclodextrin [y-CD]
(Chinoin, Budapest, Hungary) was milled in a ball mill (Pulverisette model 701, from Fritsch, Germany) for 20 hours.
~1~12~5 3a The mixture was subsequently mllled with 30 ml of delonlzed water for a further hour. The suspension was subsequently centrifuged, the violet supernatant liquld ls made up to 50 ml wlth water, and the absorptlon spectrum ls determined ln a UV/vls spectrometer (Perkln-Elmer Lambda 9) (see Flg. lb) Example 2 A homogeneous mixture of 30 mg of fullerene-contalning carbon black (prepared by the method of Kratschmer and Huffman) having a fullerene content of about 7% and 300 mg of ~-CD
(Chlnoln, Budapest, Hungary) was mllled ln a ball mlll (Pulverlsette model 701, from Fritsch, Germany) for 10 hours.
The mixture was subsequently milled with 30 ml of delonlzed water for a further hour. The suspension was centrifuged, the vlolet supernatant llquld was made up to 50 ml with water and the absorptlon spectrum was determined ln a UV/vls spectrometer (Perkln-Elmer Lambda g) (see Fig. lc).
HOECHST ARTIENGESELBSCHAFT HOE 94/F 158 Dr.DR/PP
Description Process for preparing fullerene inclusion compounds Numerous studies on fullerenes have been carried out, owing to their hydrophobic character, in organic solvents, although the fullerenes are only sparingly soluble in most of these solvents (N. Sivaraman et al., J. Org. Chem. 1992, 57, 6077-6079).
Recently, C60 fullerene has also been successfully dissolved in water, by heating solid C60 fullerene and an aqueous ~-cyclodextrin solution to the boiling point and converting the fullerene into a ~-cyclodextrin-C60-fullerene inclusion compound by re$1uxing for 50 hours or more (M. S~n~Ahl et al., Synthetic Metals, 55-57, 1993, 3252-3257; T. Andersson et al., J. Chem.
Soc., Chem. Commun. 1992, 604).
Water-soluble calixarene-C60-fullerene inclusion com-pounds, prepared by a 32 hour reaction of C60 powder and an aqueous calixarene solution under reflux, are described by R.U. Williams et al. (Recl. Trav. Chim.
Pays-Ba~ 111, 531-532 (1992)).
A disadvantage of the processes described is the time-consuming preparation under reflux conditions, which can lead to damage to the C60 molecule.
It is therefore an object of the invention to develop a simple and more rapid process for preparing water-soluble fullerene inclusion compounds.
The invention provides a process for preparing an inclu-sion compound of C60 fullerene and a host lattice selected from ~-cyclodextrin and calix-[8]-arene, which comprise6 forming the inclusion compouncl by mechano-chemical activation of a solid mixture comprising C60 fullerene and the host lattice.
In the process of the invention, solid C60 fullerene i~
mechanochemically treated with solid ~-cyclodextrin or solid calix-[8]-arene, i.e. intimately mixed for example by mechanical gr;n~;ng in a mortar or use of a ball mill.
The molar ratio of fullerene used to ~-cyclodextrin or calix-[8~-arene is generally from 1:1 to 1:15, preferably from 1:8 to 1:12, particularly preferably 1:10. The process of the invention is generally carried out at a temperature of from -20 to 100C, preferably from 20 to 50C, particularly preferably 25C, over a period of from 0.5 to 20 hours.
The C60 fullerene can be used in pure form (~ 99% by weight), as a mixture (70-99% by weight) or else as constituent of fullerene-cont~;n;ng carbon black (C60 content: 1-15% by weight). The process of the invention is therefore also suitable for separating C60 fullerene from fullerene-cont~;n;ng carbon black in a simple manner.
Preference is given to using pure C60 fullerene.
The inclusion compound can be characterized by W
spectroscopy in aqueous solution. For the purposes of characterization, the solid mixture can, after the mechanochemical treatment, be converted into a suspension by addition of from 10 to 30 ml of deionized water. This suspen~ion is generally again treated mechanochemically, for example by use of a ball mill (from 30 to 80 minutes) or of ultrasound (from 5 to 10 minutes). During this procedure, the inclusion compound formed by the process of the invention goes into solution.
The solution cont~; n; ng the inclusion compound can then be separated off by customary physical methods (centri-fugation, decantation and the like) and characterized.
The incluslon compounds of C60 fullerene and a host lattlce selected from y-cyclodextrin and calix-[8]-arene can be used, for example, as photocatalysts.
The y-cyclodextrin and calix-[8]-arene host lattices used are commercially available, for exarnple, from Chinoln (Budapest) and Sigma Chemical Co. (St. Louis, USA) respectively. C60 fullerene is likewise commercially available (from Hoechst AG) or is prepared from fullerene-containing carbon black by the method known from Kratschmer and Huffman (Kratschmer W., Lamb L.D., Fostiropoulos K., Huffman D.R.: Nature 347 (1990) 354).
The accompanying drawings show absorption spectra ln the wavelength range 200-600 nm.
Figure la is the spectrum of C60 in cyclohexane;
Figure lb is the spectrum shown by an aqueous solution of a mechanochemically produced C60/y~CD complex; and Figure lc is the spectrum shown by an aqueous solution of a C60/ -CD complex produced mechanochemically from fullerene-containing carbon black.
Example 1 A homogeneous mixture of 10 mg of C60 (Hoechst AG) having a purity of over 99.4% and 100 mg of y-cyclodextrin [y-CD]
(Chinoin, Budapest, Hungary) was milled in a ball mill (Pulverisette model 701, from Fritsch, Germany) for 20 hours.
~1~12~5 3a The mixture was subsequently mllled with 30 ml of delonlzed water for a further hour. The suspension was subsequently centrifuged, the violet supernatant liquld ls made up to 50 ml wlth water, and the absorptlon spectrum ls determined ln a UV/vls spectrometer (Perkln-Elmer Lambda 9) (see Flg. lb) Example 2 A homogeneous mixture of 30 mg of fullerene-contalning carbon black (prepared by the method of Kratschmer and Huffman) having a fullerene content of about 7% and 300 mg of ~-CD
(Chlnoln, Budapest, Hungary) was mllled ln a ball mlll (Pulverlsette model 701, from Fritsch, Germany) for 10 hours.
The mixture was subsequently milled with 30 ml of delonlzed water for a further hour. The suspension was centrifuged, the vlolet supernatant llquld was made up to 50 ml with water and the absorptlon spectrum was determined ln a UV/vls spectrometer (Perkln-Elmer Lambda g) (see Fig. lc).
Claims (4)
1. A process for preparing an inclusion compound of C60 fullerene and a host lattice selected from .gamma.-cyclo-dextrin and calix-[8]-arene, which comprises forming the inclusion compound by mechanochemical activation of a solid mixture comprising C60 fullerene and the host lattice.
2. The process as claimed in claim 1, wherein the molar ratio of C60 fullerene and host lattice is from 1:1 to 1:15.
3. The process as claimed in claim 1 or 2, wherein the host lattice used is .gamma.-cyclodextrin.
4. Use of an inclusion compound of C60 fullerene and a host lattice selected from .gamma.-cyclodextrin and calix-[8]-arene as photocatalyst.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4419981A DE4419981A1 (en) | 1994-06-08 | 1994-06-08 | Process for the preparation of fullerene inclusion compounds |
| DEP4419981.3 | 1994-06-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2151225A1 true CA2151225A1 (en) | 1995-12-09 |
Family
ID=6520065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002151225A Abandoned CA2151225A1 (en) | 1994-06-08 | 1995-06-07 | Process for preparing fullerene inclusion compounds |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0686644A3 (en) |
| JP (1) | JPH083201A (en) |
| CA (1) | CA2151225A1 (en) |
| DE (1) | DE4419981A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004067678A1 (en) * | 2003-01-27 | 2004-08-12 | Mitsubishi Corporation | Antioxidative composition and composition for external use |
| JP4827384B2 (en) * | 2004-03-24 | 2011-11-30 | 株式会社アイ・ティー・オー | Purifying agent for inhibiting the formation of lipid peroxides in the body |
| WO2006109774A1 (en) * | 2005-04-12 | 2006-10-19 | Vitamin C60 Bioresearch Corporation | Cosmetic, process for production of complex of fullerene and ϝ-cyclodextrin, solution of complex of fullerene and ϝ-cyclodextrin and process for production of the same |
| JP4142675B2 (en) | 2005-08-10 | 2008-09-03 | 株式会社ＡＢｓｉｚｅ | Method for producing fullerene dispersion |
| JP4695944B2 (en) * | 2005-08-31 | 2011-06-08 | 一般財団法人 化学物質評価研究機構 | Method for producing fullerene aqueous dispersion |
| JP5004482B2 (en) * | 2006-03-10 | 2012-08-22 | 独立行政法人科学技術振興機構 | Water-soluble fullerene / polysaccharide complex |
| CN100443120C (en) * | 2006-07-07 | 2008-12-17 | 中国科学院长春应用化学研究所 | Process for preparing water soluble cyclodextrin-C60 super molecule inclusion compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4139597A1 (en) * | 1991-11-30 | 1993-06-03 | Hoechst Ag | METHOD FOR PRODUCING FULLEREN AND HETEROFULLEREN |
-
1994
- 1994-06-08 DE DE4419981A patent/DE4419981A1/en not_active Withdrawn
-
1995
- 1995-05-26 EP EP95108051A patent/EP0686644A3/en not_active Withdrawn
- 1995-06-06 JP JP7139164A patent/JPH083201A/en active Pending
- 1995-06-07 CA CA002151225A patent/CA2151225A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0686644A3 (en) | 1996-03-06 |
| EP0686644A2 (en) | 1995-12-13 |
| DE4419981A1 (en) | 1995-12-14 |
| JPH083201A (en) | 1996-01-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |