Top

Published in:

2017 | OriginalPaper | Chapter

3. Non-Chromatographic Separation of Endohedral Metallofullerenes by Utilizing Their Redox Properties

Authors : Nataliya Samoylova, Steven Stevenson

Published in: Endohedral Fullerenes: Electron Transfer and Spin

Publisher: Springer International Publishing

Activate our intelligent search to find suitable subject content or patents.

search-config

AI-assisted search

Off

Abstract

Development of non-chromatographic separation for endohedral metallofullerenes has been put forward by many research groups with the goal of more straightforward and less expensive alternatives to HPLC. This chapter describes the progress in non-chromatographic separation approaches utilizing redox properties of EMFs, including electrolysis-assisted separation, separation with the use of redox-active solvents and redox reagents, or the use of complexation of fullerenes with Lewis acids.

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

über 102.000 Bücher
über 537 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Finance + Banking
Management + Führung
Marketing + Vertrieb
Maschinenbau + Werkstoffe
Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

inform now

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

über 67.000 Bücher
über 390 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Maschinenbau + Werkstoffe

Jetzt Wissensvorsprung sichern!

inform now

previous chapter Electrochemistry and Frontier Molecular Orbitals of Endohedral Metallofullerenes

next chapter Ions of Endometallofullerenes in the Gas Phase

Stibor A, Schefzyk H, Fortagh J (2010) Sublimation of the endohedral fullerene Er₃N@C₈₀. Phys Chem Chem Phys 12(40):13076–13081CrossRef

Chai Y, Guo T, Jin CM et al (1991) Fullerenes with metals inside. J Phys Chem 95(20):7564–7568CrossRef

Raebiger JW, Bolskar RD (2008) Improved production and separation processes for gadolinium metallofullerenes. J Phys Chem C 112(17):6605–6612CrossRef

Diener MD, Smith CA, Veirs DK (1997) Anaerobic preparation and solvent-free separation of uranium endohedral metallofullerenes. Chem Mat 9(8):1773–1777CrossRef

Yeretzian C, Wiley JB, Holczer K et al (1993) Partial separation of fullerenes by gradient sublimation. J Phys Chem 97(39):10097–10101CrossRef

Ogawa T, Sugai T, Shinohara H (2000) Isolation and characterization of Er@C₆₀. J Am Chem Soc 122(14):3538–3539CrossRef

Lu X, Bao L, Akasaka T et al (2014) Recent progresses in the chemistry of endohedral metallofullerenes. Chem Commun 50:14701–14715CrossRef

Lu X, Akasaka T, Nagase S (2011) Chemistry of endohedral metallofullerenes: the role of metals. Chem Commun 47(21):5942–5957CrossRef

Song FY, Zhang S, Bonifazi D et al (2005) Self-assembly of [60]fullerene-thiol derivatives on mercury surfaces. Langmuir 21(20):9246–9250CrossRef

10.

Angeli CD, Cai T, Duchamp JC et al (2008) Purification of trimetallic nitride templated endohedral metallofullerenes by a chemical reaction of congeners with eutectic 9-methylanthracene. Chem Mat 20(15):4993–4997CrossRef

11.

Wu B, Wang T, Zhang Z et al (2013) An effective retro-cycloaddition of M₃N@C₈₀ (M = Sc, Lu, Ho) metallofulleropyrrolidines. Chem Commun 49(89):10489–10491CrossRef

12.

Stevenson S, Rose CB, Robson AA et al (2014) Effect of water and solvent selection on the SAFA purification times for metallic nitride fullerenes. Fullerenes, Nanotubes, Carbon Nanostruct 22(1–3):182–189CrossRef

13.

Stevenson S, Rottinger KA, Field JS (2014) Fractionation of rare-earth metallofullerenes via reversible uptake and release from reactive silica. Dalton Trans 43(20):7435–7441CrossRef

14.

Stevenson S, Harich K, Yu H et al (2006) Nonchromatographic “stir and filter approach” (SAFA) for isolating Sc₃N@C₈₀ metallofullerenes. J Am Chem Soc 128(27):8829–8835CrossRef

15.

Stevenson S, Mackey MA, Coumbe CE et al (2007) Rapid Removal of D _5h isomer using the “stir and filter approach” and isolation of large quantities of isomerically pure Sc₃N@C₈₀ metallic nitride fullerenes. J Am Chem Soc 129(19):6072–6073CrossRef

16.

Diener MD, Alford JM (1998) Isolation and properties of small-bandgap fullerenes. Nature 393(6686):668–671CrossRef

17.

Tsuchiya T, Wakahara T, Shirakura S et al (2004) Reduction of endohedral metallofullerenes: a convenient method for isolation. Chem Mat 16(22):4343–4346CrossRef

18.

Tsuchiya T, Wakahara T, Lian YF et al (2006) Selective extraction and purification of endohedral metallofullerene from carbon soot. J Phys Chem B 110(45):22517–22520CrossRef

19.

Fuchs D, Rietschel H, Michel RH et al (1996) Extraction and chromatographic elution behavior of endohedral metallofullerenes: inferences regarding effective dipole moments. J Phys Chem 100(2):725–729CrossRef

20.

Laukhina EE, Bubnov VP, Estrin YI et al (1998) Novel proficient method for isolation of endometallofullerenes from fullerene-containing soots by two-step o-xylene-N. N-dimethylformamide extraction. J Mater Chem 8(4):893–895

21.

Ding JQ, Yang SH (1996) Efficient N, N-dimethylformamide extraction of endohedral metallofullerenes for HPLC purification. Chem Mat 8(12):2824–2827CrossRef

22.

Yamamoto K, Funasaka H, Takahashi T et al (1994) Isolation of an ESR-active metallofullerene of La@C₈₂. J Phys Chem 98(8):2008–2011CrossRef

23.

Kubozono Y, Ohta T, Hayashibara T et al (1995) Preparation and extraction of Ca@C₆₀. Chem Lett 6:457–458CrossRef

24.

Xiao J, Savina MR, Martin GB et al (1994) Efficient HPLC purification of endohedral metallofullerenes on a porphyrin-silica stationary phase. J Am Chem Soc 116(20):9341–9342CrossRef

25.

Anderson MR, Dorn HC, Stevenson SA (2000) Making connections between metallofullerenes and fullerenes: electrochemical investigations. Carbon 38(11–12):1663–1670CrossRef

26.

Liu BB, Zou GT, Yang HB et al (1997) Synthesis, extraction and electronic structure of Ce@C_2n. J Phys Chem Solids 58(11):1873–1876CrossRef

27.

Sun DY, Liu ZY, Guo XH et al (1997) High-yield extraction of endohedral rare-earth fullerenes. J Phys Chem B 101(20):3927–3930CrossRef

28.

Kubozono Y, Maeda H, Takabayashi Y et al (1996) Extractions of Y@C₆₀, Ba@C₆₀, La@C₆₀, Ce@C₆₀, Pr@C₆₀, Nd@C₆₀ and Gd@C₆₀ with aniline. J Am Chem Soc 118(29):6998–6999CrossRef

29.

Lian YF, Shi ZJ, Zhou XH et al (2004) Different extraction behaviors between divalent and trivalent endohedral metallofullerenes. Chem Mat 16(9):1704–1714CrossRef

30.

Solodovnikov SP, Tumanskii BL, Bashilov VV et al (2001) Spectral study of reactions of La@C-82 and Y@C-82 with amino-containing solvents. Russ Chem Bull 50(11):2242–2244CrossRef

31.

Kareev IE, Bubnov VP, Laukhina EE et al (2004) Experimental evidence in support of the formation of anionic endohedral metallofullerenes during their extraction with N. N-dimethylformamide. Fuller Nanotub Carbon Nanostruct 12(1–2):65–69

32.

Bolskar RD, Alford JM (2003) Chemical oxidation of endohedral metallofullerenes: identification and separation of distinct classes. Chem Commun 11:1292–1293CrossRef

33.

Aoyagi S, Nishibori E, Sawa H et al (2010) A layered ionic crystal of polar Li@C₆₀ superatoms. Nat Chem 2(8):678–683CrossRef

34.

Okada H, Komuro T, Sakai T et al (2012) Preparation of endohedral fullerene containing lithium (Li@C₆₀) and isolation as pure hexafluorophosphate salt ([Li⁺@C₆₀][PF₆ ⁻]). RSC Adv 2(28):10624–10631CrossRef

35.

Elliott B, Yu L, Echegoyen L (2005) A Simple Isomeric Separation of D _5h and I _h Sc₃N@C₈₀ by Selective Chemical Oxidation. J Am Chem Soc 127(31):10885–10888CrossRef

36.

Cerón MR, Li F-F, Echegoyen L (2013) An efficient method to separate Sc₃N@C₈₀ I _h and D _5h isomers and Sc₃N@C₇₈ by selective oxidation with acetylferrocenium [Fe(COCH₃C₅H₄)Cp]⁺. Chem-Eur J 19(23):7410–7415CrossRef

37.

Olah GA, Bucsi I, Lambert C et al (1991) Considered polycarbon supercage chemistry. 3. Polyarenefullerenes, C₆₀(H–Ar)N, obtained by acid-catalyzed fullerenation of aromatics. J Am Chem Soc 113(24):9387–9388CrossRef

38.

Olah GA, Bucsi I, Aniszfeld R et al (1992) Chemical-reactivity and functionalization of C₆₀ and C₇₀ fullerenes. Carbon 30(8):1203–1211CrossRef

39.

Olah GA, Bucsi I, Ha DS et al (1997) Friedel-crafts reactions of buckminsterfullerene. Fullerene Sci Technol 5(2):389–405CrossRef

40.

Bucsi I, Aniszfeld R, Shamma T et al (1994) Convenient separation of high-purity C₆₀ from crude fullerene extract by selective complexation with AlCl₃. Proc Natl Acad Sci U S A 91(19):9019–9021CrossRef

41.

Stevenson S, Mackey MA, Pickens JE et al (2009) Selective complexation and reactivity of metallic nitride and oxometallic fullerenes with lewis acids and use as an effective purification method. Inorg Chem 48(24):11685–11690CrossRef

42.

Akiyama K, Hamano T, Nakanishi Y et al (2012) Non-HPLC rapid separation of metallofullerenes and empty cages with TiCl₄ lewis acid. J Am Chem Soc 134(23):9762–9767CrossRef

43.

Wang Z, Nakanishi Y, Noda S et al (2012) The origin and mechanism of non-HPLC purification of metallofullerenes with TiCl₄. J Phys Chem C 116(48):25563–25567CrossRef

44.

Wang Z, Nakanishi Y, Noda S et al (2013) Missing small-bandgap metallofullerenes: their isolation and electronic properties. Angew Chem-Int Edit Engl 52(45):11770–11774CrossRef

45.

Stevenson S, Rottinger KA (2013) CuCl₂ for the isolation of a broad array of endohedral fullerenes containing metallic, metallic carbide, metallic nitride, and metallic oxide clusters, and separation of their structural isomers. Inorg Chem 52(16):9606–9612CrossRef

46.

Cai T, Xu L, Shu C et al (2008) Selective formation of a symmetric Sc₃N@C₇₈ bisadduct: adduct docking controlled by an internal trimetallic nitride cluster. J Am Chem Soc 130(7):2136–2137CrossRef

47.

Yang SF, Rapta P, Dunsch L (2007) The spin state of a charged non-IPR fullerene: the stable radical cation of Sc₃N@C₆₈. Chem Commun 2:189–191CrossRef

48.

Cai T, Xu LS, Anderson MR et al (2006) Structure and enhanced reactivity rates of the D _5h Sc₃N@C₈₀ and Lu₃N@C₈₀ metallofullerene isomers: the importance of the pyracylene motif. J Am Chem Soc 128(26):8581–8589CrossRef

49.

Krause M, Dunsch L (2004) Isolation and characterisation of two Sc₃N@C₈₀ isomers. Chem Phys Chem 5(9):1445–1449CrossRef

50.

Anderson MR, Dorn HC, Stevenson S et al (1997) The voltammetry of Sc₃@C₈₂. J Am Chem Soc 119(2):437–438CrossRef

51.

Wakahara T, Sakuraba A, Iiduka Y et al (2004) Chemical reactivity and redox property of Sc₃@C₈₂. Chem Phys Lett 398:553–556CrossRef

52.

Ghiassi KB, Olmstead M, Balch AL (2014) Gadolinium-containing endohedral fullerenes: structures and function as magnetic resonance imaging (MRI) agents. Dalton Trans 43:7346–7358CrossRef

53.

Zhang JF, Fatouros PP, Shu CY et al (2010) High relaxivity trimetallic nitride (Gd₃N) metallofullerene MRI contrast agents with optimized functionality. Bioconjugate Chem 21(4):610–615CrossRef

54.

Zhang J, Ye Y, Chen Y et al (2014) Gd₃N@C₈₄(OH)_x: a new egg-shaped metallofullerene magnetic resonance imaging contrast agent. J Am Chem Soc 136(6):2630–2636CrossRef

55.

Shu CY, Gan LH, Wang CR et al (2006) Synthesis and characterization of a new water-soluble endohedral metallofullerene for MRI contrast agents. Carbon 44(3):496–500CrossRef

56.

Toth E, Bolskar RD, Borel A et al (2005) Water-soluble gadofullerenes: toward high-relaxivity, pH-responsive MRI contrast agents. J Am Chem Soc 127(2):799–805CrossRef

57.

Sitharaman B, Bolskar RD, Rusakova I et al (2004) Gd@C₆₀[C(COOH)₂]₁₀ and Gd@C₆₀(OH)_x: nanoscale aggregation studies of two metallofullerene MRI contrast agents in aqueous solution. Nano Lett 4(12):2373–2378CrossRef

58.

Kato H, Kanazawa Y, Okumura M et al (2003) Lanthanoid endohedral metallofullerenols for MRI contrast agents. J Am Chem Soc 125(14):4391–4397CrossRef

59.

Bolskar RD, Benedetto AF, Husebo LO et al (2003) First soluble M@C₆₀ derivatives provide enhanced access to metallofullerenes and permit in vivo evaluation of Gd@C₆₀[C(COOH)₂]₁₀ as a MRI contrast agent. J Am Chem Soc 125(18):5471–5478CrossRef

60.

Fatouros PP, Shultz MD (2013) Metallofullerenes: a new class of MRI agents and more? Nanomedicine 8(11):1853–1864CrossRef

61.

Okumura M, Mikawa M, Yokawa T et al (2002) Evaluation of water-soluble metallofullerenes as MRI contrast agents. Academic Radiology 9:S495–S497CrossRef

62.

Mikawa M, Kato H, Okumura M et al (2001) Paramagnetic water-soluble metallofullerenes having the highest relaxivity for MRI contrast agents. Bioconjugate Chem 12(4):510–514CrossRef

63.

Stevenson S, Rottinger KA, Fahim M et al (2014) Tuning the selectivity of Gd₃N cluster endohedral metallofullerene reactions with lewis acids. Inorg Chem 53(24):12939–12946CrossRef

64.

Chaur MN, Melin F, Elliott B et al (2007) Gd₃N@C_2n (n = 40, 42, and 44): remarkably low HOMO-LUMO gap and unusual electrochemical reversibility of Gd₃N@C₈₈. J Am Chem Soc 129(47):14826–14829CrossRef

65.

Chaur MN, Athans AJ, Echegoyen L (2008) Metallic nitride endohedral fullerenes: synthesis and electrochemical properties. Tetrahedron 64(50):11387–11393CrossRef

66.

Stevenson S, Thompson HR, Arvola KD et al. (2015) Isolation of CeLu₂N@I _h-C₈₀ through a non-chromatographic, two-step chemical process and crystallographic characterization of the pyramidalized CeLu₂N within the icosahedral cage. Chemistry (Weinheim an der Bergstrasse, Germany) 21 (29):10362–10368

67.

Stevenson S, Arvola KD, Fahim M et al (2016) Isolation and crystallographic characterization of Gd₃N@D ₂(35)-C₈₈ through non-chromatographic methods. Inorg Chem 55(1):62–67CrossRef

Title: Non-Chromatographic Separation of Endohedral Metallofullerenes by Utilizing Their Redox Properties
Authors: Nataliya Samoylova
Steven Stevenson
Publisher: Springer International Publishing
Book: Endohedral Fullerenes: Electron Transfer and Spin
Print ISBN: 978-3-319-47047-4

Electronic ISBN: 978-3-319-47049-8

Copyright Year: 2017
DOI: https://doi.org/10.1007/978-3-319-47049-8_3

Springer Professional

Abstract

Please log in to get access to your license.

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Springer Professional "Technik"

Premium Partners