The Influence of Ir and Pt Addition on the Synthesis of Fullerenes at Atmospheric Pressure

The addition of metallic Ir and Pt to a fullerene-forming, atmospheric-pressure plasma reactor was found to influence the generation of carbonaceous products. It was observed that the added metals were efficiently dispersed into the plasma and that their presence increased the yield of fullerenes. The addition of Ir led to a noticeable shift in the fullerene distribution towards C₆₀, whereas the addition of Pt increased the proportion of C₆₀ oxides and decreased the proportion of higher fullerenes. Addition of Ir also caused a reduction of the soot particle size and the formation of a considerable quantity of carbon nanotubes.     

碳纳米管的制备及研究

介绍了在直流电弧放电法制备富勒烯过程中，从阴电极表面收集到大量的碳纳米管及巴基葱，产生率达到５０％，并用电子显微镜对其进行了观察和初步研究。     

Kinetic Studies of the Thermal Decomposition of C60H2 in Solution

Thermal decomposition of C₆₀H₂ in C₆D₄Cl₂ solution at 236°C for 2 hours was shown to produce hydrogen as a product, the hydrogen production was successfully followed by NMR. In order to further explore the rule of thermal decomposition of C₆₀H₂, the dynamics of decomposition reaction was studied and the results showed this decomposition reaction accorded with first order reaction dynamical equation. The experiment temperature was ranged separately in 459K, 455K, 451K, and 446K.     

Infra-red and Raman spectroscopic study on the thermal stability and high temperature transformation of hydroazafullerene C59HN

Hydroazafullerene C₅₉HN was studied by vibrational infra-red and Raman spectroscopy and its thermal stability was examined. Fingerprints modes were identified and unambiguously differentiate it from bisazafullerene. At 700 K full transformation to bisazafullerene occurred, while an intermediate metastable phase was identified at 540 K showing different spectra where the splitting of most of the lines is strongly reduced.     

Structural Analogies and Differences Between Graphite Oxide and C60 and C70 Polymeric Oxides (Fullerene Ozopolymers)

A brief survey of the chemical structural analogies and differences between graphite oxide and fullerene ozopolymers or polymeric fullerene oxides (PFO) is presented. Graphite oxide is the product of oxidation of graphite prepared with strong oxidizing agents while PFO is the products formed by prolonged ozonation of C₆₀ or C₇₀ in solution. Notwithstanding the different starting substrates and oxidation conditions, elemental analyses, FT-IR spectroscopy and ¹³C-NMR spectroscopy suggest a very similar chemical structure for graphite oxide and PFO. A further analogy is the possibility to perform reduction or oxidation reactions on both substrates considered. Graphite oxide and PFO have also in common the ability to act as ion exchangers and as metal ion binders. Even the thermal behavior is comparable. However, X-ray powder diffraction has confirmed that graphite oxide still has a layered structure derived from graphite but with the graphene sheets at much bigger distance from each other due to the intercalation of oxidized groups and solvent molecules, while PFO do not show at all any sign of layered structure either from the X-ray spectra and also by its behavior in solution which is strikingly different from that shown by graphite oxide.     

Synthesis and characterization of a new water-soluble endohedral metallofullerene for MRI contrast agents

Water-soluble amino acid derivatives of gadolinium (Gd) endohedral metallofullerenes (AAD-EMFs), Gd@C₈₂O_m(OH)_n(NHCH₂CH₂COOH)_l (m ≈ 6, n ≈ 16 and l ≈ 8) are synthesized by a direct reaction of the pure endohedral metallofullerene Gd@C₈₂ with an excess of alkaline solution of β-alanine. The structure of the AAD-EMFs is characterized by FTIR, XPS and laser-desorption time-of-flight (LD-TOF) mass spectrometries. Water proton relaxivity analysis indicates that the longitudinal relaxivity R₁ (the effect on 1/T₁, 9.1 mM⁻¹ s⁻¹) of AAD-EMFs is higher than that of the commercial MRI contrast agent, Magnevist (gadolinium-diethylenetriaminepentaacetic acid, Gd-DTPA, 5.6 mM⁻¹ s⁻¹). The MRI phantom studies are performed to confirm the high efficiency of this sample as MRI contrast agents.     

A DFT study on the physical adsorption of cyclophosphamide derivatives on the surface of fullerene C60 nanocage

The physical sorption of a series of cyclophosphamide drug derivatives with formula

where x = 2, X = F (2), Cl (3), Br (4); x = 3, X = F (5), Cl (6), Br (7) and x = 4, X = F (8), Cl (9), Br (10) on the surface of fullerene C₆₀ was studied using density functional theory (DFT) at B3LYP and B3PW91 levels. The most negative binding energies obtained using the B3LYP approach and corrected for geometrical BSSE and dispersion energies (gCP-D3-ΔE_binding) were measured for compounds 8 (among isolated drugs) and 13 (among complexes). The dipole moments of isolated drugs were obtained close to those of their complexes with C₆₀ (∼4.0–5.5 Debye) indicating their hydrophililic nature that is an appropriate property appealing for drug delivery in biological media. The adsorption of all drugs on the surface of fullerene was endergonic with all of the ΔG_adsorption > 0. The ΔH_adsorption values at B3PW91 level were only negative for complexes 14–16 indicating their exothermic adsorption nature. The HOMO–LUMO band gaps of complexes 11–19 were about 2.7 eV and are comparable with the gap in C₆₀ but are much smaller than the gaps in isolated drugs 2–10 (6.5–8.0 eV) reflecting the increase in electrical conductivities upon complexation. The QTAIM data supported the covalent character of the C–O, C–N and N–H bonds, the intermediate character of PO, P–O and P–N bonds while the electrostatic nature of PO…C(fullerene) interactions. According to the gCP-D3-ΔE_binding binding energies and ΔH_adsorption values at B3LYP level, it seems that the complexes 12 and 13 can be the most promising prodrug + carrier delivery systems.

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Fluorination of pressure-polymerized C60 phases

The reactivity of O-, T- and R-phases of the high pressure-high temperature (HPHT) polymerized C₆₀ towards gaseous fluorine in the temperature range of 50-250 °C was investigated. The reaction products were characterized by FTIR, powder X-ray diffraction, SEM, EDX, and VTP-EIMS to determine the bulk stoichiometries, bonding patterns, phase compositions, crystalline structures and thermal decomposition behavior of the fluorinated polymers. At 1 h isothermal treatment duration, fluorinated products with various bulk stoichiometries were obtained from different polymer phases with the R-phase showing the highest fluorine uptake. At 250 °C, all C₆₀ polymers showed partial decomposition to unfluorinated C₆₀ monomer under fluorine atmosphere. At 200 °C, the fluorination of R-phase yielded a pure fluoropolymer most likely having a {C₆₀F_x}_n (x = 36-44) composition. The same fluoropolymer was presumably obtained from O- and T-phases in lower yields. The linear chain structure was suggested for this new fluorocarbon polymer in agreement with the molecular mechanics modeling calculations.     

Self-assembly of C60 containing poly(methyl methacrylate) in ethyl acetate/decalin mixtures solvent

[60]Fullerene (C₆₀) was mono-substituted with well-defined poly(methyl methacrylate) (PMMA-b-C₆₀) using the atom transfer radical polymerization (ATRP) technique. The self-assembly behaviors of PMMA-b-C₆₀ in ethyl acetate (EA) and decalin mixtures were studied using laser light scattering (LLS) and transmission electron microscopy (TEM). Homogeneous solutions of PMMA-b-C₆₀ can be obtained in the solvent mixtures containing more than 40 wt% EA, where the molar ratio of decalin to EA is close to 1. For each solvent mixture, unimers coexist with micelles and large aggregates. The sizes of PMMA-b-C₆₀ micelles and aggregates are independent of polymer concentration, confirming that they are produced via the closed association mechanism. For the various solvent mixtures, the weight-averaged molecular weights, M_w of the PMMA-b-C₆₀ aggregates range from 4.1×10⁷ to 12.5×10⁷ g/mol. The hydrodynamic radii of the large aggregate, R_h, vary from 90 to 136 nm, while the z-averaged radii of gyration, R_g, range from 210 to 311 nm. The R_g/R_h value for each solvent mixture is ∼2.3, which is independent of decalin contents in the mixed solvents. The morphological study using the transmission electron microscope suggests that the large aggregates are composed of porous large compound micelles (LCM) in solution.