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(12) United States Patent (10) Patent No.: US 7,208,132 B2 Bolskar Et Al

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(12) United States Patent (10) Patent No.: US 7,208,132 B2 Bolskar Et Al USOO7208132B2 (12) United States Patent (10) Patent No.: US 7,208,132 B2 Bolskar et al. (45) Date of Patent: Apr. 24, 2007 (54) PURIFICATION OF ENDOHEDRAL AND Boudon, C. et al. (1998), “Redox Characteristics of Covalent OTHERFULLERENES BY CHEMICAL Derivatives of the Higher Fullerenes Co, C7, and C.7s.” J. Am. METHODS Chen. Soc. 120:7860-7868. Cagle, D. W. et al. (1999), "In vivo studies of fullerene-based (75) Inventors: Robert D. Bolskar, Boulder, CO (US); materials using endohedral metallofullerene radiotracers.” Proc. J. Michael Alford, Lakewood, CO Natl. Acad. Sci. USA 96:5182-5187. Connelly, N. G.; Geiger, W. E. (1996), “Chemical Redox Agents for (US) Organometallic Chemistry.” Chem. Rev. 96:877-910. (73) Assignee: TDA Research, Inc., Wheat Ridge, CO Diederich, F. et al. (1991) “The Higher Fullerenes: Isolation and Characterization of C76, Cs, Coo Co., and CoO, and Oxide of (US) D-Co” Science 252:548-551. (*) Notice: Subject to any disclaimer, the term of this Diederich, F. and Whetten, R.L. (1992), “Beyond go: The Higher patent is extended or adjusted under 35 Fullerenes. Acc. Chem. Res. 25: 119-126. Diener, M. D. et al. (1997), “Anaerobic Preparation and Solvent U.S.C. 154(b) by 384 days. Free Separation of Uranium Endohedral Metallofullerenes.” Chem. Mater. 9:1773-1777. (21) Appl. No.: 10/263,374 Diener, M. D.; Alford, J. M. (1998), “Isolation and properties of Small-bandgap fullerenes' Nature 393:668-671. (22) Filed: Oct. 1, 2002 Hirsch, A. (1994)(a). The Chemistry of the Fullerenes, Georg (65) Prior Publication Data Thieme Verlag Stuttgart, New York. Hirsch, A. (1999), “Principles of Fullerene Reactivity,” in Topics in US 2003/0157016 A1 Aug. 21, 2003 Current Chemistry, vol. 199, Springer Verlag, Berlin, Heidelberg, pp. 1-65. Related U.S. Application Data Huang, Y. et al. (1991), “Externally Bound Metal Ion Complexes of Buckminster Fullerene, MC60"in the Gas Phase,” J. Am. Chem. (60) Provisional application No. 60/326,307, filed on Oct. Soc. 113:9418-9418. 1, 2001. Kikuchi, K. et al. (1993), “Isolation and characterization of the metallofullerene LaCs.” Chem. Phys. Lett. 216:67-71. (51) Int. Cl. Kitagawa, T. et al. (1999), “Electrophilic Addition of CIB 3L/ (2006.01) Polychloroalkanes to Co. Direct Observation of Alkylfullerenyl (52) U.S. Cl. ................... 423/461; 423/445 B;977/845 Cation Intermediates,” J. Am Chem. Soc. 121:4298-4299. (58) Field of Classification Search ............ 423/445 B, Krätschmer, W. et al. (1990), "Solid Co. a new form of carbon.” 423/461; 977/845 Notre 347:354-358. See application file for complete search history. Kubozono, Y. et al. (1996), “Extractions of Ca(aCo and Sr(a)Co with Aniline.” Chem. Lett. pp. 453-454. (56) References Cited Kubozono, Y. et al. (1995), "Preparation and Extraction of Ca U.S. PATENT DOCUMENTS (aCo.” Chem. Lett., pp. 457-458. Kubozono, Y. et al. (1996), “Extractions of Y(a Co. Baca Co. 6,303,016 B1 10/2001 Diener et al. ............... 205,687 LaCoCo, Ce(a) Co. ProCo, NdoCo, and Gd(a Co with Aniline.” 6,517,799 B2 2/2003 Alford et al. ... ... 423f445 J. Am. Chem. Soc., 118:6998-6999. 2003, OO65206 A1 4/2003 Bolsker et al. ............... 558/87 Lui, B. (Sep. 1998), "High efficient extraction of M(aC. (M-La, Ce) by a high pressure and high temperature method.” Tetrahedron OTHER PUBLICATIONS 54:11123-11128. Akasaka, T. et al. (Web published Sep. 7, 2000), "LacaCs Anion. (Continued) An Unusually Stable Metallofullerence,” J. Am. Chem. Soc., 122:931.6-93.17. Primary Examiner Stuart Hendrickson Akasaka, T. et al. (Mar. 2000), “Isolation and characterization of (74) Attorney, Agent, or Firm—Greenlee, Winner and two Pr(a)C isomers.” Chem. Phys. Lett. 319:153-156. Sullivan, P.C. Akasaka, T. et al. (Web published Mar. 24, 2001), "Structural Determination of the LaGC Isomer.” J. Phys. Chem. B., (57) ABSTRACT 105:2971-2974. Anderson, M. R. et al. (1997), “The Voltammetry of Sc. (a)Cs.”J. An. Chen. Soc. 119:437-438. The invention provides a method of separating a first and a Beer, F. et al. (1997), “High-Yield Reactive Extraction of Giant second set of fullerenes in a fullerene mixture. In the method Fullerenes from Soot, J. Mater: Chem., 7:1327-1330. of the invention, a stable fullerene cation is formed of one Bethune, D. S. et al. (1993), “Atoms in carbon cages: the structural of the first or the second set of fullerenes. The fullerene and properties of endohedral fullerenes.” Nature 366: 123-128. cation is then separated from the other set of fullerenes. Bolskar, R.D. et al. (Apr. 2003), “First Soluble M(aCo Derivatives Optionally, the fullerene cation may be returned to its neutral Provide Enhanced Access to Metallofullerenes and Permit in Vivo state. The method of the invention is particularly useful for Evaluation of GD(a CC(COOH) as a MRI Contrast Agent.” J. the purification and separation of endohedral fullerenes from Am. Chem. Soc. 125(8):5471-5478. empty fullerenes. However, the method may be applied to Bolskar, R. D. et al. (1996), “Synthesis and Isolation of a Fullerene the purification of a broad range of endohedral and empty Carbocation (C").” J. Am. Chem. Soc. 118: 13093-13094. fullerene materials. Bolskar, R. D. (1997), “The Synthesis and Characterization of Fullerene Anion and Cation Salts.” Ph.D. Dissertation, University of Southern California, Los Angeles, CA, 238 pp. 36 Claims, 15 Drawing Sheets US 7,208,132 B2 Page 2 OTHER PUBLICATIONS Suzuki, T. et al. (1996), “Electrochemical Properties of Fullernolanthanides’ Tetrahedron 52(14):4973-4982. Liu, S.; Sun, S. (Apr. 9, 2000), “Recent progress in the studies of endohedral metallofullerenes' J. Organomet. Chem. 599:79-86. Tagmatarchis, N. et al. 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