Research article Topical Sections

C60 and Sc3N@C80(TMB-PPO) derivatives as constituents of singlet oxygen generating, thiol-ene polymer nanocomposites

  • Received: 31 May 2016 Accepted: 18 July 2016 Published: 21 July 2016
  • Numerous functionalization methods have been employed to increase the solubility, and therefore, the processability of fullerenes in composite structures, and of these radical addition reactions continue to be an important methodology. C60 and Sc3N@C80 derivatives were prepared via radical addition of the photodecomposition products from the commercial photoinitiator TMB-PPO, yielding C60(TMB-PPO)5 and Sc3N@C80(TMB-PPO)3 as preferred soluble derivatives obtained in high yields. Characterization of the mixture of isomers using standard techniques suggests an overall 1PPO:6TMB ratio of addends, reflecting the increased reactivity of the carbon radical. Although, a higher percentage of PPO is observed in the Sc3N@C80(TMB-PPO)3 population, perhaps due to reverse electronic requirements of the substrate. Visually dispersed thiol-ene nanocomposites with low extractables were prepared using two monomer compositions (PETMP:TTT and TMPMP:TMPDE) with increasing fullerene derivative loading to probe network structure-property relationships. Thermal stability of the derivatives and the resulting networks decreased with increased functionality and at high fullerene loadings, respectively. TMPMP:TMPDE composite networks show well-dispersed derivatives via TEM imaging, and increasing Tg’s with fullerene loading, as expected for the incorporation of a more rigid network component. PETMP:TTT composites show phase separation in TEM, which is supported by the observed Tg’s. Singlet oxygen generation of the derivatives decreases with increased functionality; however, this is compensated for by the tremendous increase in solubility in organic solvents and miscibility with monomers. Most importantly, singlet oxygen generation from the composites increased with fullerene derivative loading, with good photostability of the networks.

    Citation: Emily M. Barker, Ashli R. Toles, Kyle A. Guess, Janice Paige Buchanan. C60 and Sc3N@C80(TMB-PPO) derivatives as constituents of singlet oxygen generating, thiol-ene polymer nanocomposites[J]. AIMS Materials Science, 2016, 3(3): 965-988. doi: 10.3934/matersci.2016.3.965

    Related Papers:

  • Numerous functionalization methods have been employed to increase the solubility, and therefore, the processability of fullerenes in composite structures, and of these radical addition reactions continue to be an important methodology. C60 and Sc3N@C80 derivatives were prepared via radical addition of the photodecomposition products from the commercial photoinitiator TMB-PPO, yielding C60(TMB-PPO)5 and Sc3N@C80(TMB-PPO)3 as preferred soluble derivatives obtained in high yields. Characterization of the mixture of isomers using standard techniques suggests an overall 1PPO:6TMB ratio of addends, reflecting the increased reactivity of the carbon radical. Although, a higher percentage of PPO is observed in the Sc3N@C80(TMB-PPO)3 population, perhaps due to reverse electronic requirements of the substrate. Visually dispersed thiol-ene nanocomposites with low extractables were prepared using two monomer compositions (PETMP:TTT and TMPMP:TMPDE) with increasing fullerene derivative loading to probe network structure-property relationships. Thermal stability of the derivatives and the resulting networks decreased with increased functionality and at high fullerene loadings, respectively. TMPMP:TMPDE composite networks show well-dispersed derivatives via TEM imaging, and increasing Tg’s with fullerene loading, as expected for the incorporation of a more rigid network component. PETMP:TTT composites show phase separation in TEM, which is supported by the observed Tg’s. Singlet oxygen generation of the derivatives decreases with increased functionality; however, this is compensated for by the tremendous increase in solubility in organic solvents and miscibility with monomers. Most importantly, singlet oxygen generation from the composites increased with fullerene derivative loading, with good photostability of the networks.


    加载中
    [1] Arbogast JW, Darmanyan AP, Foote CS, et al. (1991) Photophysical properties of sixty atom carbon molecule (C60). J Phys Chem 95: 11–12. doi: 10.1021/j100154a006
    [2] Ching WY, Huang MZ, Xu YN, et al. (1991) First-principles calculation of optical properties of the carbon sixty-atom molecule in the fcc. lattice. Phys Rev Lett 67: 2045–2048. doi: 10.1103/PhysRevLett.67.2045
    [3] Maser W, Roth S, Anders J, et al. (1992) P-Type doping of C60 fullerene films. Synth Met 51: 103–108. doi: 10.1016/0379-6779(92)90259-L
    [4] Sun Y-P, Lawson GE, Riggs JE, et al. (1998) Photophysical and Nonlinear Optical Properties of [60]Fullerene Derivatives. J Phys Chem A 102: 5520–5528.
    [5] Accorsi G, Armaroli N (2010) Taking Advantage of the Electronic Excited States of [60]-Fullerenes. J Phys Chem C 114: 1385–1403. doi: 10.1021/jp9092699
    [6] Allemand PM, Khemani KC, Koch A, et al. (1991) Organic molecular soft ferromagnetism in a fullerene C60. Science 253: 301–303.
    [7] Stephens PW, Cox D, Lauher JW, et al. (1992) Lattice structure of the fullerene ferromagnet TDAE-C60. Nature 355: 331–332.
    [8] Hebard AF, Rosseinsky MJ, Haddon RC, et al. (1991) Superconductivity at 18 K in potassium-doped fullerene (C60). Nature 350: 600–601.
    [9] Dubois D, Moninot G, Kutner W, et al. (1992) Electroreduction of Buckminsterfullerene, C60, in aprotic solvents. Solvent, supporting electrolyte, and temperature effects. J Phys Chem 96: 7137–7145.
    [10] Schon TB, Di Carmine PM, Seferos DS (2014) Polyfullerene Electrodes for High Power Supercapacitors. Adv Energy Mater 4: 1301509–1301515. doi: 10.1002/aenm.201301509
    [11] Pupysheva OV, Farajian AA, Yakobson BI (2008) Fullerene Nanocage Capacity for Hydrogen Storage. Nano Lett 8: 767–774. doi: 10.1021/nl071436g
    [12] Nadtochenko VA, Vasil'ev IV, Denisov NN, et al. (1993) Photophysical properties of fullerene C60: picosecond study of intersystem crossing. J Photochem Photobiol, A 70: 153–156. doi: 10.1016/1010-6030(93)85035-7
    [13] Foote CS (1994) Photophysical and photochemical properties of fullerenes. Electron Transfer I. Berlin, Heidelberg: Springer Berlin Heidelberg. pp. 347–363.
    [14] Sun R, Jin C, Zhang X, et al. (1994) Photophysical properties of C60. Wuli 23: 83–87.
    [15] Qu B, Chen SM, Dai LM (2000) Simulation analysis of ESR spectrum of polymer alkyl-C60 radicals formed by photoinitiated reactions of low-density polyethylene. Appl Magn Reson 19: 59–67. doi: 10.1007/BF03162261
    [16] Guldi DM, Asmus K-D (1997) Photophysical Properties of Mono- and Multiply-Functionalized Fullerene Derivatives. J Phys Chem A 101: 1472–1481. doi: 10.1021/jp9633557
    [17] McEwen CN, McKay RG, Larsen BS (1992) C60 as a radical sponge. J Am Chem Soc 114: 4412–4414. doi: 10.1021/ja00037a064
    [18] Tzirakis MD, Orfanopoulos M (2013) Radical Reactions of Fullerenes: From Synthetic Organic Chemistry to Materials Science and Biology. Chem Rev 113: 5262–5321.
    [19] Krusic PJ, Wasserman E, Keizer PN, et al. (1991) Radical reactions of C60. Science 254: 1183–1185.
    [20] Krusic PJ, Wasserman E, Parkinson BA, et al. (1991) Electron spin resonance study of the radical reactivity of C60. J Am Chem Soc 113: 6274–6275. doi: 10.1021/ja00016a056
    [21] Wu S-H, Sun W-Q, Zhang D-W, et al. (1998) Reaction of [60]fullerene with trialkylphosphine oxide. Tetrahedron Lett 39: 9233–9236. doi: 10.1016/S0040-4039(98)02131-5
    [22] Cheng F, Yang X, Fan C, et al. (2001) Organophosphorus chemistry of fullerene: synthesis and biological effects of organophosphorus compounds of C60. Tetrahedron 57: 7331–7335. doi: 10.1016/S0040-4020(01)00670-6
    [23] Cheng F, Yang X, Zhu H, et al. (2000) Synthesis and optical properties of tetraethyl methano[60]fullerenediphosphonate. Tetrahedron Lett 41: 3947–3950. doi: 10.1016/S0040-4039(00)00491-3
    [24] Liu Z-B, Tian J-G, Zang W-P, et al. (2003) Large optical nonlinearities of new organophosphorus fullerene derivatives. Appl Opt 42: 7072–7076. doi: 10.1364/AO.42.007072
    [25] Ford WT, Nishioka T, Qiu F, et al. (1999) Structure Determination and Electrochemistry of Products from the Radical Reaction of C60 with Azo(bisisobutyronitrile). J Org Chem 64: 6257–6262. doi: 10.1021/jo990346w
    [26] Ford WT, Nishioka T, Qiu F, et al. (2000) Dimethyl Azo(bisisobutyrate) and C60 Produce 1,4- and 1,16-Di(2-carbomethoxy-2-propyl)-1,x-dihydro[60]fullerenes. J Org Chem 65: 5780–5784. doi: 10.1021/jo000686d
    [27] Shustova NB, Peryshkov DV, Kuvychko IV, et al. (2011) Poly(perfluoroalkylation) of Metallic Nitride Fullerenes Reveals Addition-Pattern Guidelines: Synthesis and Characterization of a Family of Sc3N@C80(CF3)n (n = 2-16) and Their Radical Anions. J Am Chem Soc 133: 2672–2690. doi: 10.1021/ja109462j
    [28] Shu C, Slebodnick C, Xu L, et al. (2008) Highly Regioselective Derivatization of Trimetallic Nitride Templated Endohedral Metallofullerenes via a Facile Photochemical Reaction. J Am Chem Soc 130: 17755–17760. doi: 10.1021/ja804909t
    [29] Shu C, Cai T, Xu L, et al. (2007) Manganese(III)-Catalyzed Free Radical Reactions on Trimetallic Nitride Endohedral Metallofullerenes. J Am Chem Soc 129: 15710–15717. doi: 10.1021/ja0768439
    [30] Shustova NB, Popov AA, Mackey MA, et al. (2007) Radical Trifluoromethylation of Sc3N@C80. J Am Chem Soc 129: 11676–11677. doi: 10.1021/ja074332g
    [31] Cardona CM, Kitaygorodskiy A, Echegoyen L (2005) Trimetallic nitride endohedral metallofullerenes: Reactivity dictated by the encapsulated metal cluster. J Am Chem Soc 127: 10448–10453. doi: 10.1021/ja052153y
    [32] Yu G, Gao J, Hummelen JC, et al. (1995) Polymer photovoltaic cells: enhanced efficiencies via a network of internal donor-acceptor heterojunctions. Science 270: 1789–1791.
    [33] Troshin PA, Hoppe H, Renz J, et al. (2009) Material Solubility-Photovoltaic Performance Relationship in the Design of Novel Fullerene Derivatives for Bulk Heterojunction Solar Cells. Adv Funct Mater 19: 779–788. doi: 10.1002/adfm.200801189
    [34] Jiao F, Liu Y, Qu Y, et al. (2010) Studies on anti-tumor and antimetastatic activities of fullerenol in a mouse breast cancer model. Carbon 48: 2231–2243. doi: 10.1016/j.carbon.2010.02.032
    [35] Xu J-Y, Su Y-Y, Cheng J-S, et al. (2010) Protective effects of fullerenol on carbon tetrachloride-induced acute hepatotoxicity and nephrotoxicity in rats. Carbon 48: 1388–1396. doi: 10.1016/j.carbon.2009.12.029
    [36] Mikawa M, Kato H, Okumura M, et al. (2001) Paramagnetic Water-Soluble Metallofullerenes Having the Highest Relaxivity for MRI Contrast Agents. Bioconjugate Chem 12: 510–514. doi: 10.1021/bc000136m
    [37] Chen C, Xing G, Wang J, et al. (2005) Multihydroxylated [Gd@C82(OH)22]n Nanoparticles: Antineoplastic Activity of High Efficiency and Low Toxicity. Nano Lett 5: 2050–2057. doi: 10.1021/nl051624b
    [38] Aoshima H, Kokubo K, Shirakawa S, et al. (2009) Antimicrobial activity of fullerenes and their hydroxylated derivatives. Biocontrol Sci 14: 69–72. doi: 10.4265/bio.14.69
    [39] Guldi DM, Asmus K-D (1999) Activity of water-soluble fullerenes towards ·OH-radicals and molecular oxygen. Radiat Phys Chem 56: 449–456. doi: 10.1016/S0969-806X(99)00325-4
    [40] Lai HS, Chen WJ, Chiang LY (2000) Free radical scavenging activity of fullerenol on the ischemia-reperfusion intestine in dogs. World J Surg 24: 450–454. doi: 10.1007/s002689910071
    [41] Sun D, Zhu Y, Liu Z, et al. (1997) Active oxygen radical scavenging ability of water-soluble fullerenols. Chin Sci Bull 42: 748–752. doi: 10.1007/BF03186969
    [42] Dugan LL, Gabrielsen JK, Yu SP, et al. (1996) Buckminsterfullerenol free radical scavengers reduce excitotoxic and apoptotic death of cultured cortical neurons. Neurobiol Dis 3: 129–135. doi: 10.1006/nbdi.1996.0013
    [43] Chiang LY, Lu F-J, Lin J-T (1995) Free radical scavenging activity of water-soluble fullerenols. J Chem Soc, Chem Commun: 1283–1284.
    [44] Xiao L, Takada H, Maeda K, et al. (2005) Antioxidant effects of water-soluble fullerene derivatives against ultraviolet ray or peroxylipid through their action of scavenging the reactive oxygen species in human skin keratinocytes. Biomed Pharmacother 59: 351–358. doi: 10.1016/j.biopha.2005.02.004
    [45] Oberdorster E (2004) Manufactured nanomaterials (fullerenes, C60) induce oxidative stress in the brain of juvenile largemouth bass. Environ Health Perspect 112: 1058–1062. doi: 10.1289/ehp.7021
    [46] Hamano T, Okuda K, Mashino T, et al. (1997) Singlet oxygen production from fullerene derivatives: effect of sequential functionalization of the fullerene core. Chem Commun 21–22.
    [47] Guldi DM, Prato M (2000) Excited-State Properties of C60 Fullerene Derivatives. Acc Chem Res 33: 695–703. doi: 10.1021/ar990144m
    [48] Jensen AW, Daniels C (2003) Fullerene-Coated Beads as Reusable Catalysts. J Org Chem 68: 207–210. doi: 10.1021/jo025926z
    [49] Jensen AW, Maru BS, Zhang X, et al. (2005) Preparation of fullerene-shell dendrimer-core nanoconjugates. Nano Lett 5: 1171–1173. doi: 10.1021/nl0502975
    [50] Foote CS (1994) Photophysical and photochemical properties of fullerenes. Top Curr Chem 169: 347–363. doi: 10.1007/3-540-57565-0_80
    [51] McCluskey DM, Smith TN, Madasu PK, et al. (2009) Evidence for Singlet-Oxygen Generation and Biocidal Activity in Photoresponsive Metallic Nitride Fullerene-Polymer Adhesive Films. ACS Appl Mater Interfaces 1: 882–887. doi: 10.1021/am900008v
    [52] Alberti MN, Orfanopoulos M (2010) Recent mechanistic insights in the singlet oxygen ene reaction. Synlett 999–1026.
    [53] Foote CS, Wexler S, Ando W (1965) Singlet oxygen. III. Product selectivity. Tetrahedron Lett 4111–4118.
    [54] Dallas P, Rogers G, Reid B, et al. (2016) Charge separated states and singlet oxygen generation of mono and bis adducts of C60 and C70. Chem Phys 465–466: 28–39.
    [55] Yano S, Naemura M, Toshimitsu A, et al. (2015) Efficient singlet oxygen generation from sugar pendant C60 derivatives for photodynamic therapy [Erratum to document cited in CA163:618143]. Chem Commun 51: 17631–17632.
    [56] Prat F, Stackow R, Bernstein R, et al. (1999) Triplet-State Properties and Singlet Oxygen Generation in a Homologous Series of Functionalized Fullerene Derivatives. J Phys Chem A 103: 7230–7235. doi: 10.1021/jp991237o
    [57] Tegos GP, Demidova TN, Arcila-Lopez D, et al. (2005) Cationic Fullerenes Are Effective and Selective Antimicrobial Photosensitizers. Chem Biol 12: 1127–1135. doi: 10.1016/j.chembiol.2005.08.014
    [58] Schinazi RF, Sijbesma R, Srdanov G, et al. (1993) Synthesis and virucidal activity of a water-soluble, configurationally stable, derivatized C60 fullerene. Antimicrob Agents Chemother 37: 1707–1710. doi: 10.1128/AAC.37.8.1707
    [59] Dai L (1999) Advanced syntheses and microfabrications of conjugated polymers, C60-containing polymers and carbon nanotubes for optoelectronic applications. Polym Adv Technol 10: 357–420.
    [60] Phillips JP, Deng X, Todd ML, et al. (2008) Singlet oxygen generation and adhesive loss in stimuli-responsive, fullerene-polymer blends, containing polystyrene-block-polybutadiene- block-polystyrene and polystyrene-block-polyisoprene-block-polystyrene rubber-based adhesives. J Appl Polym Sci 109: 2895–2904. doi: 10.1002/app.28337
    [61] Lundin JG, Giles SL, Cozzens RF, et al. (2014) Self-cleaning photocatalytic polyurethane coatings containing modified C60 fullerene additives. Coatings 4: 614–629. doi: 10.3390/coatings4030614
    [62] Phillips JP, Deng X, Stephen RR, et al. (2007) Nano- and bulk-tack adhesive properties of stimuli-responsive, fullerene-polymer blends, containing polystyrene-block-polybutadiene- block-polystyrene and polystyrene-block-polyisoprene-block-polystyrene rubber-based adhesives. Polymer 48: 6773–6781. doi: 10.1016/j.polymer.2007.08.050
    [63] Samulski ET, DeSimone JM, Hunt MO, Jr., et al. (1992) Flagellenes: nanophase-separated, polymer-substituted fullerenes. Chem Mater 4: 1153–1157. doi: 10.1021/cm00024a011
    [64] Chiang LY, Wang LY, Kuo C-S (1995) Polyhydroxylated C60 Cross-Linked Polyurethanes. Macromolecules 28: 7574–7576. doi: 10.1021/ma00126a042
    [65] Ahmed HM, Hassan MK, Mauritz KA, et al. (2014) Dielectric properties of C60 and Sc3N@C80 fullerenol containing polyurethane nanocomposites. J Appl Polym Sci 131: 40577–40588.
    [66] Kokubo K, Takahashi R, Kato M, et al. (2014) Thermal and thermo-oxidative stability of thermoplastic polymer nanocomposites with arylated [60]fullerene derivatives. Polym Compos: 1–9.
    [67] Shin J, Nazarenko S, Phillips JP, et al. (2009) Physical and chemical modifications of thiol-ene networks to control activation energy of enthalpy relaxation. Polymer 50: 6281–6286. doi: 10.1016/j.polymer.2009.10.053
    [68] Hoyle CE, Bowman CN (2010) Thiol-ene click chemistry. Angew Chem Int Ed 49: 1540–1573. doi: 10.1002/anie.200903924
    [69] Hoyle CE, Lee TY, Roper T (2004) Thiol–enes: Chemistry of the past with promise for the future. J Polym Sci A Polym Chem 42: 5301–5338. doi: 10.1002/pola.20366
    [70] Cramer NB, Scott JP, Bowman CN (2002) Photopolymerizations of Thiol-Ene Polymers without Photoinitiators. Macromolecules 35: 5361–5365. doi: 10.1021/ma0200672
    [71] Li Q, Zhou H, Hoyle CE (2009) The effect of thiol and ene structures on thiol–ene networks: Photopolymerization, physical, mechanical and optical properties. Polymer 50: 2237–2245. doi: 10.1016/j.polymer.2009.03.026
    [72] Northrop BH, Coffey RN (2012) Thiol-Ene Click Chemistry: Computational and Kinetic Analysis of the Influence of Alkene Functionality. J Am Chem Soc 134: 13804–13817. doi: 10.1021/ja305441d
    [73] Singh R, Goswami T (2011) Understanding of thermo-gravimetric analysis to calculate number of addends in multifunctional hemi-ortho ester derivatives of fullerenol. Thermochimica Acta 513: 60–67. doi: 10.1016/j.tca.2010.11.012
    [74] Barker EM, Buchanan JP (2016) Thiol-ene polymer microbeads prepared under high-shear and their successful utility as a heterogeneous photocatalyst via C60-capping. Polymer 92: 66–73. doi: 10.1016/j.polymer.2016.03.091
    [75] Jockusch S, Turro NJ (1998) Phosphinoyl Radicals: Structure and Reactivity. A Laser Flash Photolysis and Time-Resolved ESR Investigation. J Am Chem Soc 120: 11773–11777.
    [76] Ruoff RS, Tse DS, Malhotra R, et al. (1993) Solubility of fullerene (C60) in a variety of solvents. J Phys Chem 97: 3379–3383. doi: 10.1021/j100115a049
    [77] Ginzburg BM, Shibaev LA, Melenevskaja EY, et al. (2004) Thermal and Tribological Properties of Fullerene-Containing Composite Systems. Part 1. Thermal Stability of Fullerene-Polymer Systems. J Macromol Sci Phys 43: 1193–1230.
    [78] Leifer SD, Goodwin DG, Anderson MS, et al. (1995) Thermal decomposition of a fullerene mix. Phys Rev B Condens Matter 51: 9973–9981. doi: 10.1103/PhysRevB.51.9973
    [79] Mackey MA (2011) Exploration in metallic nitride fullerenes and oxometallic fullerenes: A new class of metallofullerenes [Ph.D. Dissertation]. Hattiesburg, MS: The University of Southern Mississippi.
  • Reader Comments
  • © 2016 the Author(s), licensee AIMS Press. This is an open access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0)
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

Metrics

Article views(6127) PDF downloads(1098) Cited by(0)

Article outline

Figures and Tables

Figures(10)  /  Tables(4)

/

DownLoad:  Full-Size Img  PowerPoint
Return
Return

Catalog