THE REACTION OF C60F20 WITH ANTHRACENE: FORMATION OF AN OXIDISED-ANTHRACENE 1 : 1 COMPLEX

ABSTRACT

The reaction of C₆₀F₂₀ (“Saturnene”) with anthracene yields a white 1?:?1 cycloadduct (1) in which two oxygen atoms have inserted into the anthracene framework due to fullerene-catalysed oxidation; the ¹⁹F NMR spectrum of the product shows evidence of through-cage homoconjugation.     

Penetration of Fullerene C60 Derivatives Through Biological Membranes

Penetration of fullerene C₆₀ in hydrated molecular-colloidal form (FMC) and various C₆₀ water-soluble derivatives (FDs) through membranes of human erythrocytes, platelets and symbiosomes (subcellular organelles of plant origin) were tested. The FDs bearing amino acids induced pronounced depolarization of symbiosome membranes energized with Mg-ATP. In erythrocytes and platelets incubated in K⁺-free medium in the presence of FCCP, FDs with malonic acid pendants promoted acidification of the intracellular medium thereby simulating an effect of the K⁺ ionophore valinomycin. Dissipation of ΔpH artificially induced on the plasma membrane of these cells was observed in the presence of C₆₀-γ-aminobutiric acid which, in addition, strongly stimulated Mg-ATP-dependent generation of membrane potential on symbiosome membranes. C₆₀-Arg was shown to dissipate K⁺-diffusion potential on erythrocyte membranes induced by valinomycin. Fullerene C₆₀ used in hydrated molecular-colloidal form (FMC) also entered symbiosomes and platelets as evidenced by the quenching of the fluorescence of the Ca²⁺ indicator chlorotetracycline localized in the interior of these cells. These findings provide evidence for ease of permeation of these fullerene-based compounds through biological membranes from different type cells.     

Functionalization of [60]Fullerene Using a Novel Chemical Vapor Modification Method

Abstract

Gas phase reactions of [60]fullerene with hydrogen atoms and/or methyl radicals have been performed by hot filament chemical vapor modification (CVM) to produce hydrogenated and/or methylated [60]fullerene. The CVM process parameters such as the time of reaction, pressure, and percentage of methane diluted in hydrogen have been varied so as to obtain the addended fullerene reaction products. Mass spectrometry and ¹H NMR techniques were used to characterize the reaction products obtained.     

Thermal desorption of fullerene C60 from polymer matrices

The data on thermally stimulated desorption (TSD) study of fullerene C₆₀ molecules from different polymer matrices are compared in view of the temperature positions and relative intensities of resolved thermal desorption stages. An increase of the low temperature C₆₀ desorption stages is observed for polydimethylsiloxane (PDMS) and polystyrene (PS) contrary to polyimide (PI). This is in agreement with the difference in glass transition temperatures (T_g) of these polymers. The TSD data allow us to conclude that above T_g of the polymer the solubility of fullerene C₆₀ in PDMS and PS is up to the order of magnitude higher compared with C₆₀ solubility in low molecular weight solvents.     

Synthesis of Calix[4, 5, 6] Resorcinarenes Using Fullerene C60 as Template

We present a new use of fullerene C₆₀ as a template for the synthesis of cyclic resorcinarenes, The cyclocondensation of 2-methyl-resorcinol with benzaldehyde and hexanal in THF, catalyzed by AlCl₃, in the presence of 1%, 5%, and 10% fullerene C₆₀, produces calix[4], [5], and [6] resorcinarenes, with the pentamer and hexamer as the major products. The resorcinarenes were characterized by ¹H, ¹³C NMR, FTIR, FAB⁺ mass spectrometry, and elemental analysis.     

Nanoencapsulation of [60]Fullerene with the Cavitand Cucurbit[7]uril

Novel supramolecular nanocapsules consisting of [60]fullerene and the macrocycle cucurbit[7]uril via self-assembly are reported. The nanocapsules, which were synthesized in a two-phase reaction at room temperature, were obtained in good yields. The stoichiometry of the product was found to be 1:2.     

Scalable, Solution Phase Synthesis of the Trans-1 Bisanthracene Adduct of [60]Fullerene

A new, scalable, one-pot solution phase synthesis of the D_2 h symmetric trans-1 bisanthracene adduct of [60]fullerene is described. The highly regioselective reaction utilizes commercially available 9,10-dihydroanthracene, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and [60]fullerene and exhibits an unusual temperature dependence.     

Evaluation of Effects of C60 Fullerene and Its Derivatives on Selected Microorganisms

The contribution deals with preparation of C50 fullerene derivatives （oxo derivative, bromo derivative, hydrolyzed bromoderivative, bromo-chloro derivative）, their identification and pilot testing of their biological effects on unicellular organisms. The contribution describes effects of C60 fullerene derivatives, both on prokaryotic organisms （bacteria, cyanobacteria） and eukaryotic organisms （algae） and assesses their potential use as biocides.     

Synthesis of Calix[4, 5, 6] Resorcinarenes Using Fullerene C60 as Template

Abstract

We present a new use of fullerene C₆₀ as a template for the synthesis of cyclic resorcinarenes, The cyclocondensation of 2‐methyl‐resorcinol with benzaldehyde and hexanal in THF, catalyzed by AlCl₃, in the presence of 1%, 5%, and 10% fullerene C₆₀, produces calix[4], [5], and [6] resorcinarenes, with the pentamer and hexamer as the major products. The resorcinarenes were characterized by ¹H, ¹³C NMR, FTIR, FAB⁺ mass spectrometry, and elemental analysis.     

C60H18, C60H36 and C70H36 Fullerene Hydrides: Study by Methods of IR,NMR, XPS,EELS and Magnetochemistry

Abstract

Fullerene hydrides of C₆₀H₁₈, C₆₀H₃₆ and C₇₀H₃₆ are studied by using IR, ¹H and ¹³C NMR, X-ray photoelectron and electron energy loss spectroscopies, and magnetochemistry. The comparison of IR and solid state ¹H and ¹³C NMR data for C₆₀H₃₆ with the theoretical ones allows the suggestion that fullerene hydride has a T symmetric structure and contains 4 isolated benzenoid rings located at tetrahedral positions on the surface of a closed skeleton of the molecule. The EELS revealed that the transition from fullerene to the hydride is accompanied by the decrease of the density of valence electrons. Magnetization measurements showed C₆₀H₃₆ to be a ferromagnet. The hydrogenated fullerenes were prepared by transfer hydrogenation procedures involving 9,10-dihydroanthracene. The compositions of the hydrides are determined by field desorption mass-spectral analysis.     

吐温-60对钢在H2SO4中的缓蚀性能

用失重法研究了非离子表面活性剂吐温-60对冷轧钢在0.5-7.0 mol/L H2SO4溶液中的缓蚀作用。结果表明：吐温-60对冷轧钢在1.0 mol/L H2SO4溶液中具有良好的缓蚀作用,且在钢表面的吸附符合校正的Langmuir吸附模型。缓蚀率随缓蚀剂浓度的增加而增大,但随温度和硫酸浓度的增加而减小。求出了相应的吸附热力学（吸附自由能ΔG^0, 吸附焓ΔH^0, 吸附熵ΔS^0）和动力学参数（腐蚀速率常数k, 腐蚀动力学常数B）,并根据这些参数讨论了缓蚀作用机理。     

High-pressure behavior of the crystal structure of the fullerene molecular complex with ferrocene C60·{Fe(C5H5)2}2

Abstract

The crystal structure of the molecular complex C₆₀·{Fe(C₅H₅)₂}₂ was studied by single crystal X-ray diffraction (XRD) analysis at pressures up to 5?GPa using the diamond anvil cell (DAC) technique. The XRD data and subsequent structural analysis clearly show that there is no pressure-induced polymerization in fullerene layers in pressure range studied. The reciprocal unit cell volume V₀/V is a smooth and monotonous function of pressure and fits well to the Murnaghan equation of state (V₀/V) ^B'=?{1?+?P·(B'/B₀)}, where V₀ is the volume at ambient pressure, B₀=8.7?GPa and B'=10.5 are the bulk modulus and its derivative, respectively. Pressure dependence of the shortest distance between the C₅H₅ ring of the ferrocene molecule and the center of the nearest fullerene molecule is linear, while the slope changes at 2.2?GPa indicating on the intermolecular interactions crossover. Other relevant parameter, the Fe-C bond lengths of ferrocene, sensitive to iron charge state, gradually increases. This peculiarity can a sign of pressure-induced partial charge transfer between the donor ferrocene and acceptor fullerene molecules.     

热分解动力学在含能材料中的应用

文章主要介绍了热分解动力学在含能材料中的重要性,列举了热分解动力学的主要分析方法及几种常用的反应机理,并对其进行简要分析。热分析技术具有快捷简便、准确度高以及适用范围广的特点,在含能材料的热分解动力学中发挥重要作用。热分解动力学广泛应用于含能材料的动力学参数的求解、反应机理的推断以及动力学补偿效应的确定,为其有效使用寿命的预测以及安全性能的评定等提供科学依据。同时,热分析技术的自身完善以及与其他技术的联机使用将促进热分解动力学的不断发展。     

粉状乳化炸药热分解动力学研究

利用热重法（TG）研究了粉状乳化炸药的热分解过程和非等温反应动力学,采用Ozawa法和非线性等转化率积分法获得了其热分解动力学参数和机理函数。结果表明,粉状乳化炸药初始分解温度稍高于乳化炸药基质,分解活化能为97kJ／mool,是热稳定性良好的工业炸药。粉状乳化炸药的热分解机理属随机成核和随后成长,热分解动力学方程为dα/dt=1×10^10×（1-α）exp（-1．2×10^4／T）。     

C60 and Giant Fullerenes in Soot Condensed in Vapors with Variable C/H2 Ratio

A transmission electron microscope (TEM) study of individual soot grains forming fluffy carbon particles produced using the arc-discharge technique revealed close-packed arrangements of single-wall ring structures with average diameters of 0.7, 1.1, 3.0, 5.5, and 8.2 nm. These structures were hypothesized to be C₆₀ and giant, C₅₄₀, C₉₆₀, and C₁₅₀₀, fullerenes that could form by coalescence during condensation and soot agglomeration, although in situ solid-state growth cannot be excluded. Mass spectroscopy and high performance liquid chromatography (HPLC) chromatography of the samples confirmed the presence of C₆₀ fullerene in all samples giving confidence to the giant fullerene growth scenario. Our results suggest that fullerenes could be common in soot grains produced by this technique as well as being an important carbon phase in C-rich accretion disks around young stellar objects and among the dust in the interstellar medium.     

热重法研究漆酚镍螯合高聚物热分解动力学

用非等温热重法研究了漆酚镍螯合高聚物的热分解反应动力学,结果表明漆酚镍螯合高聚物热分解过程是一级反应,用Ozaw-(I)法和Reich法求得的热分解反应平均活化能分别是173.21KJ mol~(-1) 和181.12KJ mol~(-1)。     

Kinetic Properties of Orientational Phase Transition in Polymerized States of Fullerites C60

Abstract

In the present work, we have shown that at early stages of dimerization, which occur during synthesis of C₆₀ fullerite T _syn = 10–40°C and P _syn = 1.5–8 GPa, kinetics of the sc→fcc phase transition, may be well described by Avrami law with Avrami's exponent n _Avr = 3 (i.e., in this case we are dealing with martensite‐like transformation). Fullerite's samples produced at higher temperatures (40°C < T _syn < 120°C) exhibit different kinetics with lower Avrami‐exponent. This behavior we attribute to the transformation switching to diffusion‐controlled kinetics.     

Equilibrium Phase Diagram of Polymerized C60 and Kinetics of Decomposition of the Polymerized Phases

Abstract

Equilibrium phase diagram (T=0–1000 K; p=0–8 GPa) of pressure‐temperature polymerized C₆₀ has been constructed. It included rhombohedral; orthorhombic and tetragonal polymerized phases of C₆₀ along with fcc monomeric phases of C₆₀. The isothermal kinetics of depolymerization (T=373–513 K) of the O‐, R‐, T‐ and D‐phases was studied by means of the IR‐spectroscopy. The isothermal rate of decomposition goes up along the series: (T‐)<(O‐)<(R‐)<(D‐).     

On the Effect of the Rotational State of C60 Molecules on Electronic Transport in the C60 Fullerite

Abstract

A phenomenological scenario is suggested in an attempt to explain controversies in the published data concerning the effect of orientational order on electronic transport in solid C₆₀. The main factor of crucial importance is the dependence of the charge hop probability on the mutual orientation of the molecules. Magnitude and the sign of the conductivity response to the changes in the rotational state of C₆₀ across the orientational phase transition are the results of the interplay between the changes in dynamic and static disorder that accompany the transition and may vary in the samples with different structure perfection.