- Preparation and Characterization of Six Bis(N-methylpyrrolidine)-C60 Isomers: Magnetic Deshielding in Isomeric Bisadducts of C60
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A series isomers of bis(N-methylpyrrolidine)-C60 2 (prato bisdducts) was prepared by the 1,3-dipolar cycloaddition of N-methylazomethine ylide to C60.Six isomers were separated and characterized by ESI-MS, UV/vis, and 1H and 13C NMR spectroscopy.TThe structures of these bisadducts were assigned based on (1) comparison of their molecular symmetries with their 1H and 13C NMR spectra, (2) comparison of their UV/vis spectra with those of corresponding Bingel-Hirsch bisadducts, and (3) the order of deshielding of the methylene and N-methyl 1H NMR resonances.Prato bisaddition is less chemoselective than Bingel-Hirsch bisaddition to C60.
- Lu, Qing,Schuster, David I.,Wilson, Stephen R.
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- A New Dyad Based on C60 and a Conjugated Dimethylaniline-Substituted Dithienylethylene Donor
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A facile synthesis of the title compound is described, and its optical and electrochemical properties are discussed.
- Liu, Sheng-Gao,Shu, Lianhe,Rivera, Jose,Liu, Haiying,Raimundo, Jean-Manuel,Roncali, Jean,Gorgues, Alain,Echegoyen, Luis
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- Microwave-Assisted 1,3-Dipolar Cycloaddition of Azomethine Ylides to [60]Fullerene: Thermodynamic Control of Bis-Addition with Ionic Liquids Additives
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The cycloaddition of azomethine ylides to [60]fullerene (C60) has been studied in ortho-dichlorobenzene (o-DCB) by evaluating the impact of an ionic liquid (IL) additive. The solvent effect has been addressed by evaluating the activation parameters of the cycloaddition and the boosting effect of the microwave (MW) induced dielectric heating. The IL additive plays a twofold role of stabilizing the dipolar ylide intermediate and favoring the retro-cycloaddition at high temperature regime. Under the conditions explored, a combined kinetic and thermodynamic preference favors the selective formation of trans bis-fulleropyrrolidine regioisomers, in agreement with the DFT computational analysis.
- Bonchio, Marcella,Carraro, Mauro,Martinis, Estefanía M.,Montellano, Alejandro,Prato, Maurizio,Sartorel, Andrea
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- Investigation of the Photoelectrochemistry of C60 and Its Pyrrolidine Derivatives by Monolayer-Modified SnO2 Electrodes
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A monolayer of a C60 mixture with arachidic acid (1:1) and C60-pyrrolidine derivatives were successfully obtained at the air/water interface and deposited onto solid substrates with tra
- Luo, Chuping,Huang, Chunhui,Gan, Liangbing,Zhou, Dejian,Xia, Wensheng,et al.
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- BOPHY-Fullerene C60 Dyad as a Photosensitizer for Antimicrobial Photodynamic Therapy
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A novel BOPHY–fullerene C60 dyad (BP-C60) was designed as a heavy-atom-free photosensitizer (PS) with potential uses in photodynamic treatment and reactive oxygen species (ROS)-mediated applications. BP-C60 consists of a BOPHY fluorophore covalently attached to a C60 moiety through a pyrrolidine ring. The BOPHY core works as a visible-light-harvesting antenna, while the fullerene C60 subunit elicits the photodynamic action. This fluorophore–fullerene cycloadduct, obtained by a straightforward synthetic route, was fully characterized and compared with its individual counterparts. The restricted rotation around the single bond connecting the BOPHY and pyrrolidine moieties led to the formation of two atropisomers. Spectroscopic, electrochemical, and computational studies disclose an efficient photoinduced energy/electron transfer process from BOPHY to fullerene C60. Photodynamic studies indicate that BP-C60 produces ROS by both photomechanisms (type I and type II). Moreover, the dyad exhibits higher ROS production efficiency than its individual constitutional components. Preliminary screening of photodynamic inactivation on bacteria models (Staphylococcus aureus and Escherichia coli) demonstrated the ability of this dyad to be used as a heavy-atom-free PS. To the best of our knowledge, this is the first time that not only a BOPHY–fullerene C60 dyad is reported, but also that a BOPHY derivative is applied to photoinactivate microorganisms. This study lays the foundations for the development of new BOPHY-based PSs with plausible applications in the medical field.
- Gonzalez Lopez, Edwin J.,Sarotti, Ariel M.,Martínez, Sol R.,Macor, Lorena P.,Durantini, Javier E.,Renfige, Melisa,Gervaldo, Miguel A.,Otero, Luis A.,Durantini, Andrés M.,Durantini, Edgardo N.,Heredia, Daniel A.
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- A covalent organic cage compound acting as a supramolecular shadow mask for the regioselective functionalization of C60
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A trigonal-bipyramidal covalent organic cage compound serves as an efficient host to form stable 1?:?1-complexes with C60 and C70. Fullerene encapsulation has been comprehensively studied by NMR and UV/Vis spectroscopy, mass spectrometry as well as single-crystal X-ray diffraction. Exohedral functionalization of encapsulated C60via threefold Prato reaction revealed high selectivity for the symmetry-matched all-trans-3 addition pattern. This journal is
- Beuerle, Florian,Fimmel, Stefanie,Krause, Ana-Maria,Leonhardt, Viktoria
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p. 8409 - 8415
(2020/09/07)
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- Highly hydroxide conductive ionomers with fullerene functionalities
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A novel ionomer was designed that will not poison the catalyst in alkaline fuel cells, by incorporating for the first time N-methyl pyrrolidine-C60 cation in polymeric anion exchange ionomers. The resultant fullerene-based anion exchange ionomer shows an extremely high hydroxide conductivity (182 mS cm-1) at a low cation concentration (0.62 mmol g-1).
- Yang, Zhengjin,Liu, Yazhi,Guo, Rui,Hou, Jianqiu,Wu, Liang,Xu, Tongwen
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supporting information
p. 2788 - 2791
(2016/02/18)
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- Fullerene derivatives strongly inhibit HIV-1 replication by affecting virus maturation without impairing protease activity
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Three compounds (1, 2, and 3) previously reported to inhibit HIV-1 replication and/or in vitro activity of reverse transcriptase were studied, but only fullerene derivatives 1 and 2 showed strong antiviral activity on the replication of HIV-1 in human CD4
- Martinez, Zachary S.,Castro, Edison,Seong, Chang-Soo,Cerón, Maira R.,Echegoyen, Luis,Llano, Manuel
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supporting information
p. 5731 - 5741
(2016/11/04)
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- Study on the thermal reactions of [60]fullerene with amino acids and amino acid esters
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Thermal reactions of [60]fullerene with a series of amino acids and amino acid esters under aerobic and dark conditions have been investigated. Fulleropyrrolidines can be obtained from these reactions although an aldehyde is not added purposely. Possible reaction mechanisms involving uncommon C-N bond cleavages have been proposed to generate aldehydes, which then react with amino acids and amino acid esters to provide azomethine ylides, followed by 1,3-dipolar cycloaddition to [60]fullerene affording fulleropyrrolidines. Control experiments support our proposed mechanisms, and elucidate the innate nature of C-N bond cleavages of amino acids and amino acid esters.
- Zhu, San-E,Cheng, Xin,Li, Yu-Jin,Mai, Cheng-Kang,Huang, Yong-Shun,Wang, Guan-Wu,Peng, Ru-Fang,Jin, Bo,Chu, Shi-Jin
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p. 8720 - 8729
(2013/01/15)
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- Synthesis of fulleropyrrolidines through the reaction of [60]fullerene with quaternary ammonium salts and amino acids
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The reactions of [60]fullerene with amino acids and quaternary ammonium salts in toluene afforded two fulleropyrrolidine derivatives. One fulleropyrrolidine derivative contained a RCH moiety originating from quaternary ammonium salts through C-N bond cleavages and other fulleropyrrolidine derivatives contained a PhCH moiety originating from toluene through C-H bond cleavage. By using chlorobenzene instead of toluene as solvent, only one fulleropyrrolidine derivative containing a RCH moiety was obtained in the reactions.
- Jin, Bo,Peng, Ru-Fang,Shen, Juan,Chu, Shi-Jin
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supporting information; experimental part
p. 5640 - 5643
(2011/02/22)
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- Regioselective intramolecular nucleophilic addition of alcohols to C 60: One-step formation of a cis-1 bicyclic-fused fullerene
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(Chemical Equation Presented) The first example of intramolecular nucleophilic addition of an alcohol to a fullerene double bond is described. In particular, the straightforward one-step reaction of commercially available sarcosine, hydroxyacetaldehyde, a
- Izquierdo, Marta,Osuna, Silvia,Filippone, Salvatore,Martin-Domenech, Angel,Sola, Miquel,Martin, Nazario
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supporting information; experimental part
p. 6253 - 6259
(2009/12/06)
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- H-bond-assisted regioselective (cis-1) intramolecular nucleophilic addition of the hydroxyl group to [60]fullerene
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The one-step reaction of 2,6-dihydroxyphenylmethyl ketone and sarcosine with [60]fullerene in refluxing chlorobenzene affords, in a totally regioselective process, the cis-1 bicyclic-fused organofullerene through a new intramolecular nucleophilic addition
- Izquierdo, Marta,Osuna, Silvia,Filippone, Salvatore,Martin-Domenech, Angel,Sola, Miquel,Martin, Nazario
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supporting information; experimental part
p. 1480 - 1487
(2009/07/11)
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- [60]fullerene-pyrrolidine-N-oxides
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Eight members of a new family of fullerene derivatives, [60]fulleropyrrolidine-N-oxides, have been synthesized and characterized. Facile oxidation, by a peracid, of the parent [60]fulleropyrrolidine gave clean conversions into the product molecules, in wh
- Brough, Peter,Klumpp, Cedric,Bianco, Alberto,Campidelli, Stephane,Prato, Maurizio
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p. 2014 - 2020
(2007/10/03)
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- Anti-HIV properties of cationic fullerene derivatives
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A series of regioisomeric bis-fulleropyrrolidines bearing two ammonium groups have been synthesized and their activities against HIV-1 and HIV-2 have been evaluated. Two trans isomers have been endowed with interesting antiviral properties, confirming the importance of the relative positions of the substituent on the C60 cage. In addition, reduced amphiphilicity of molecules to other compounds previously reported decreases their cytotoxicity in CEM cell cultures. None of the compounds showed any inhibitory activity against a variety of DNA and RNA viruses other than HIV.
- Marchesan, Silvia,Da Ros, Tatiana,Spalluto, Giampiero,Balzarini, Jan,Prato, Maurizio
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p. 3615 - 3618
(2007/10/03)
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- Isolation and characterization of nine tris-adducts of N- methylfulleropyrrolidine derivatives
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We report the isolation and characterization of bis- and tris-adducts of fulleropyrrolidine derivatives. First, all eight N-methyl regioisomers with two addends on the C60 sphere have been isolated; second, C60 was used as starting m
- Marchesan, Silvia,Da Ros, Tatiana,Prato, Maurizio
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p. 4706 - 4713
(2007/10/03)
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- Solvent-free reactions of fullerenes and N-alkylglycines with and without aldehydes under high-speed vibration milling
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The solvent-free reactions of fullerenes and N-alkylglycines with and without aldehydes (RCHO) 2a-e under high-speed vibration milling (HSVM) conditions have been investigated. Fulleropyrrolidines 4a-e (C60(CH2N(CH3)CHR), R=H (4a), C6H5 (4b), p-NO2-C6H4 (4c), p-CH3O-C6H4 (4d), p-(CH3)2N-C6H4 (4e)) were obtained in moderate yields from reactions of C60 with aldehydes 2a-e and N-methylglycine (Prato reaction). In all these solvent-free reactions, 4a was found to be formed besides 4b-e, indicating that fullerenes can react with N-substituted glycines in the absence of aldehyde to give fulleropyrrolidines. For this novel reaction, a possible reaction mechanism involving an electron transfer process has been proposed. Intrigued by this observation, the dependence of the yield on the reagent ratio for the reaction of C60 with paraformaldehyde and/or N-methylglycine was examined to search the optimal conditions. The reaction of C70 with paraformaldehyde and/or N-methylglycine under HSVM conditions was also studied and was found to give the positional isomers of [70]fulleropyrrolidines.
- Wang, Guan-Wu,Zhang, Ting-Hu,Hao, Er-Hong,Jiao, Li-Juan,Murata, Yasujiro,Komatsu, Koichi
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- The chemical retro-Bingel reaction: Selective removal of bis(alkoxycarbonyl)methano addends from C60 and C70 with amalgamated magnesium
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Bis(alkoxycarbonyl)methano addends are removed from C60 and C70 derivatives by reaction with amalgamated magnesium in dry THF; this facile and selective retro-Bingel reaction, which leaves pyrrolidine rings fused to C60 intact, opens up the possibility of using bis(alkoxycarbonyl)methano addends as protecting and reversible directing groups in the regioselective multiple functionalization of fullerenes.
- Moonen, Nicolle N. P.,Thilgen, Carlo,Echegoyen, Luis,Diederich, Francois
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p. 335 - 336
(2007/10/03)
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- Selective electrolytic removal of bis(alkoxycarbonyl)methano addends from C60 bis-adducts and electrochemical stability of C70 derivatives
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The novel mixed his-adducts of C60, (±)-4-(±)-8 and 9, with a bis(ethoxycarbonyl)methano addend (Bingel addend) and a second addend ([1,2]benzeno, but[2]eno, methaniminomethano, or diarylmethano) bridging 6,6-closed bonds of the carbon sphere were synthesized in two-step reactions. Each bis-adduct was exhaustively electrolyzed at the potential of the second fullerene-centered reduction step, resulting in the selective removal of the Bingel addend (retro-Bingel reaction) to produce the corresponding mono-adducts, which were isolated in yields of over 60%. These results open up the possibility of using the Bingel addend as a temporary protecting and directing group in the construction of multiple adducts of C60 with unusual addition patterns. The Bingel-type mono-adduct of C70 10 and the constitutionally isomeric bis-adducts 11, (±)-12, and (±)-13 were also included in this investigation. A large difference in the electrochemical behavior between C70, bis-adducts and the corresponding C60 derivatives was observed. Thus, the intramolecular "walk-on-the-sphere" isomerization which occurs readily with Bingel-type bis-adducts of C60 under the conditions of two-electron controlled potential electrolysis (CPE) is only a minor reaction pathway in the series of C70 derivatives. The latter preferentially undergo retro-Bingel reaction.
- Kessinger, Roland,Fender, Nicolette S.,Echegoyen, Lourdes E.,Thilgen, Carlo,Echegoyen, Luis,Diederich, Francois
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p. 2184 - 2192
(2007/10/03)
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- Self-assembling supramolecular nanostructures from a C60 derivative: Nanorods and vesicles
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Simple modification of solution conditions provides facile access to supramolecular fullerene nanostructures. The fullerene derivative shown self- assembles to give nanorods or vesicles. The nanorods have diameters of 10-250 nm, depending on the counterion, and lengths greater than 70 μm. If ultrasonication is used, no nanorods form, but vesicles result having diameters of 10-70 nm and wall thicknesses of 3-6 nm.
- Cassell, Alan M.,Asplund, C. Lee,Tour, James M.
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p. 2403 - 2405
(2007/10/03)
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- Linear free-energy relationship for electron-transfer processes of pyrrolidinofullerenes with tetrakis(dimethylamino)ethylene in ground and excited states
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Systematic studies of electron-transfer processes in the ground states and excited triplet states of pyrrolidinofullerenes {C60(C3H6N)R [R = H (1), p-C6H4NO2 (2), p-C6H4CHO (3), p-C6H5 (4), p-C6H4Me (5), p- C6H4NMe2 (6)]} with tetrakis(dimethylamino)ethylene (TDAE) have been carried out by steady-state and transient absorption measurements in the visible-NIR region. Analyses of the equilibria of the electron-transfer processes in the ground states indicate that free ion radicals are produced in polar solvents. Photoinduced electron-transfer processes via (T)(C60(C3H6N)R)* were observed by applying a perturbation to the equilibria of the electron-transfer reactions in the ground states by laser flash photolysis. Based on the relationship of the thermodynamic data and kinetic data, the electron-transfer rate constants in the ground states (k(et)/(G)) can be evaluated. The k(et)/(G) values are affected by the substituents to a smaller extent compared with the equilibrium constants (K) in polar solvents; α = 0.6 in Δ log k(et)/(G) = α Δ log K. This α value indicates that the activation energies of forward electron transfer in the ground states vary moderately with the thermodynamic stabilities of (C60(C3H6N)R).-. Electron-transfer rate constants via (T)(C60(C3H6N)R)* which are close to the diffusion-controlled limit, do not show a large substituent effect (α = 0), because of their highly exothermic processes. Such a linear free-energy relationship can be extended to other systems such as (T)(C60(C3H6N)R)*/N,N-dimethylaniline, from which valuable information for electron-transfer processes can be obtained.
- Luo, Chuping,Fujitsuka, Mamoru,Huang, Chun-Hui,Ito, Osamu
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p. 2923 - 2928
(2007/10/03)
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- Photoinduced reactions of tertiary amines with [60]fullerene; addition of an α-C-H bond of amines to [60]fullerene
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The photochemical reaction of [60]fullerene with RNMe2 (R = Ph and Me) gives an adduct (1, R = Ph; 2, R = Me) formed by the addition of an α-C-H bond of the amine to a 6/6 ring junction of [60]fullerene; 2 on further irradiation in the presence
- Liou, Kou-Fu,Cheng, Chien-Hong
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p. 1423 - 1424
(2007/10/03)
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