Effects of Hexasulfobutylated C60 on the Thalamic Neurons in Neonatal Rat in vitro

Abstract

The effects of hexasulfobutylated C₆₀ (FC₄S) on membrane potentials and currents were studied by tight-seal, whole-cell recording in thin slices of the neonatal rat thalamus. Silent neuron with resting membrane potentials of around -62.4 ± 0.7 mV was found in whole-cell current clamp recordings. Hexasulfobutylated C₆₀ depolarized the neuron by a concentration dependent manner. It also (1) prolonged the decay time constant of action potential and (2) decreased the threshold of the directly elicited action potentials of the neuron. Hexasulfobutylated C₆₀ did not alter the input resistance of the excitable membrane. In whole-cell voltage clamp studies, depolarizing command pulses from a holding potential of about -70 mV evoked a fast inward current followed by an outward current in the thalamic neurons. Hexasulfobutylated C₆₀ (30 - 100 μM) increased the total inward sodium current of the neuron, while hexasulfobutylated C₆₀ did not alter the outward potassium currents in all voltage steps tested. It was concluded that hexasulfobutylated C₆₀ (1) decreased the threshold of the action potential and (2) prolonged the decay time constant of the directly elicited action potential of the neonatal rat thalamic neurons. The effect may be closely associated with the Na⁺ current in thalamic neurons.     

Effect of Substituents on the Redox Potentials of C60 Derivatives

The electrochemical properties of four C₆₀ derivatives (compounds 1∼4) were investigated with cyclic voltammetry (CV), and compared with that of C₆₀. The reduction potentials of compound 1∼3 shifted to more negative positions than C₆₀, and their oxidation peaks appeared at the lower potentials. Significantly, the reduction potentials of compound 4 shifted to more positive positions than C₆₀, which is advantageous to form charge-transfer complexes with more donors. So the reduction properties in different solvents and in situ NIR absorption spectra of compound 4 were studied in more details. In addition, the AM1 molecular orbital calculation was performed on C₆₀ and compound 1∼4 for the explanation of the potential shifts. The reduction potentials of these compounds exhibited good linear relationships with the calculation LUMO or LUMO+1 energy levels.     

MOLECULAR DYNAMICS SIMULATIONS OF PREFERRED ORIENTATIONS IN THE HIGH TEMPERATURE PHASE OF C60

Molecular dynamics simulations of the high temperature phase of C₆₀ have been performed for different intermolecular potentials proposed previously for the intermolecular interactions in solid C₆₀, i.e. the van der Waals (vdW) potential and two different bond charge models. In contrast to what has been previously inferred from a mean-field theory, bond charges do lead to a much better reproduction of the experimental results, including the preferred orientations of the C₆₀ molecule, than the vdW potential.     

Effect of Solvents and Supporting Electrolytes on the Electrochemical Properties of C70 and its Comparison with C60

Surrounding medium effect on the electrochemical properties of C₇₀ was studied in 9 single, 2 mixture solvents and 7 supporting electrolytes by cyclic. voltammetry in the temperature range between 260 and 288K. The obtained results were analyzed and compared with those of C₆₀. It was shown that, due to the different structure between C₇₀ and C₆₀, the degree of these medium effect on their reduction potential was different. The solvent effect on the reduction of C₇₀ was more significant than that of C₆₀; on the other hand, the solvophobic interaction between the larger cations of supporting electrolyte and C₇₀ anions was weaker than that between the same cations and C₆₀ anions. In addition, C₇₀ redox couple showed better reversibility when the supporting electrolyte contains larger cations. C₇₀ redox potentials were also measured as a function of temperature, and the entropy changes of C₇₀reduction were calculated.     

New Developments on the Photochlorination of C60 and C70 Fullerene and Preparation of Fullerene Derivatives: Polyfluorofullerenes and Polyfullerols.

Improved methods for photochlorination of C₆₀ and C₇₀ are described. The photoproducts fit respectively the average formulae C₆₀ Cl₄₀ and C₇₀ Cl₄₇. It is also shown that these photoproducts can be easily fluorinated by means of KF to give fluorofullerenes.

Polyhydroxyfullerene (fullerol) can be easily produced by the action of a methanolic solution of alkali over C₆₀ Cl₄₀.     

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.     

Synthesis of Radiolabeled Fullerenes C60 and C70

The synthesis of radiolabeled C₆₀/C₇₀ for potential biochemical tracer studies was carried out. Vaporization under plasma are conditions (~3000C) of graphite rods impregnated with the ¹⁴C labeled steroid progesterone generates the expected C₆₀/C₇₀ mixture. Isolation and characterization of the ¹⁴C-C₆₀ is reported. Interestingly, the C₇₀ had more radioactivity than the C₆₀.     

Structural transformations, reactions, and electronic properties of fullerenes, onions, and buckytubes

We describe the results of extensive quantum molecular dynamics calculations of the properties of fullerenes and microtubules. The topics to be discussed include: (i) stability of C₆₀ isomers and barriers to isomerization; (ii) reactivity of C₆₀ and C₅₈ with C₂ and C₃, and its implications on the formation and growth of fullerenes; and (iii) atomic and electronic structure and doping of semiconducting microtubules. We also discuss the structures, stabilities and atomic transformations of large multishell fullerenes and offer an explanation for the formation of spheroidal “onions” under high fluence electron irradiation conditions. The last results, which involved calculations for up to 15 000 atoms, were obtained using classical three-body potentials.     

Fullerane, the Hydrogenated C60 Fullerene: Properties and Astrochemical Considerations

Hydrogenated C₆₀ fullerene, C₆₀H₃₆ was prepared in different solvents using Zn/HCl as reducing agents. The structure of C₆₀H₃₆ was confirmed both by electronic and FT-IR spectroscopy and the purity of the reaction product was checked by HPLC analysis. It has been confirmed that C₆₀H₃₆ is not stable in air, especially in presence of light which enhances the oxidation. The oxidation of C₆₀H₃₆ was studied by FT-IR spectroscopy and by differential scanning calorimetry (DSC) in air; the formation of hydroxyl groups on the fullerene cage and ketonic groups (involving cage breakdown) have been detected. Furthermore, the action of O₃ on C₆₀H₃₆ was investigated and it has been found that O₃ exerts practically the same effect of air but causing an enhanced cage breakdown. The thermal stability of C₆₀H₃₆ was checked by a thermogravimetric analysis (TGA) coupled with a differential thermal analysis (DTA) under N₂ flow. The vaporization of C₆₀H₃₆ occurs at very high temperature: the DTA trace has shown an endothermic peak at 540°C (at a heating rate of 20°C/min). C₆₀H₃₆ shows an electronic absorption spectrum with a maximum at about 217 nm and it is able to match both in position and in half width the peak at 217.5 nm observed in the spectrum of the interstellar extinction of light which was attributed to hydrogenated, radiation processed and thermally annealed carbon dust. Similarly, the absorption spectrum of C₆₀H₃₆ is able to match several infrared emission bands (called UIBs) detected from certain astrophysical objects like the protoplanetary nebulae (PPNe). It is proposed that hydrogenated fullerenes can be used as model compounds in the laboratory simulation studies of interstellar carbon dust.     

Preparation, Separation and Characterisation of Fullerene - C60 and C70

This paper reports a simple apparatus for the synthesis of fullerenes and an efficient method for the separation of C₆₀ and C₇₀ in large amounts. The positive and negative ion mass spectra of C₆₀ and C₇₀ were measured using electron ionization and in-beam methods. Vibrational Raman spectra showed that the C₆₀ molecule adsorbed on the substrate surface may be distorted and its symmetry may be reduced under the action of the substrate surface.     

GROUP TRANSFER AND DIMERIZATION PROCESSES OF C60(CN)2 UNDER ATMOSPHERIC PRESSURE IONIZATION CONDITIONS

Neutral and anionic C₆₀(CN)₂ were investigated with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) mass spectrometry. It was observed that its anions underwent cyano- group and oxygen transfer, and dimerization processes in ESI conditions to form C₆₀(CN)₃H^-, C₆₀(CN)₂(OH₂)^-, [C₆₀(CN)₃H]^-₂, [C₆₀(CN)₂(OH₂)]^-₂ and [(C₆₀)₂(CN)₂(OH)]^-. Meanwhile, neutral C₆₀(CN)₂, for which no signal was observed in ESIMS, showed a base peak corresponding to C₆₀(CN)₂Cl^- in APCIMS spectra with CHCl₃ used as solvent, while only a molecular ion peak corresponding to C₆₀(CN)^-₂ was observed for the toluene solution of neutral C₆₀(CN)₂ in the same conditions. Possible mechanisms for group transfer and dimerization were proposed based on these observations.     

Electronic structure and electrical transport characteristics of C60, 2C60 and 4C60 fullerene molecules

The extended H?ckel method and the Green s function method were used to calculate the electronic structure and electrical transport of Au electrode-C₆₀, 2C₆₀ or 4C₆₀ fullerene-Au electrode systems. Furthermore, their electronic structure and electrical transport characteristics were compared and analyzed. The results show that (i) owing to the contact with the Au electrodes, the C₆₀, 2C₆₀ and 4C₆₀ molecules change in their electronic structures significantly, and their energy gaps between LUMO and HOMO are narrow; (ii) the bonding between C₆₀, 2C₆₀ or 4C₆₀ fullerene and Au electrodes is partially covalent and partially electrovalent; and (iii) the conductance of the three fullerenes conforms to the order of C₆₀>2C₆₀>4C₆₀.     

聚乙烯亚胺修饰富勒烯的制备及其对聚丙烯热氧稳定性的影响

利用聚乙烯亚胺(PEI)分子中活泼的?NH?与富勒烯(C₆₀)结构中C=C键之间的加成反应,制备了PEI修饰C₆₀杂化物(C₆₀?PEI),并采用FTIR、TEM等测试方法对C₆₀?PEI的分子结构和形态进行表征。采用熔融共混法制备了C₆₀?PEI/聚丙烯(PP)复合材料,并对其热性能和阻燃性能进行研究。热失重分析结果表明,C₆₀?PEI可以更有效地发挥C₆₀的自由基捕捉作用,对PP热稳定性的提高效果较C₆₀更明显;氧化诱导测试(OIT)结果表明,C₆₀?PEI/PP复合材料比C₆₀/PP复合材料具有更优异的抗氧性能;微型量热测试也表明,燃烧过程中C₆₀?PEI/PP复合材料比C₆₀/PP复合材料具有更低的热释放量。      

Bromination of [60]Fullerene. I. High-Yield Synthesis of C60Brx (x=6, 8, 24)

The systematic study of the bromination of C₆₀ was performed under various experimental conditions. Application of some chloroarenes as reaction media resulted in the high-yield (70-96%) selective synthesis of C₆₀Br₆ and C₆₀Br₈. Direct bromination of fullerene yielded either C₆₀Br₈, C₆₀Br₁₄, or C₆₀Br₂₄ depending on the reaction time. Possible pathways of bromination of C₆₀Br₈ were analyzed using semiempirical (AM1) calculations, two most probable molecular structures are conjectured for the first isolated C₆₀Br₁₄.     

Addition Reactions of Benzyne, Dienes, Dichlorocarbene, and Oxygen to C60

Benzyne was found to add to C₆₀ in good yield to give C₆₀(C₆H₄)_n (n=1-4). Typical Diels-Alder dienes were also found to add to C₆₀ under thermally mild conditions. Adducts of C₆₀ with 2,3-dimethylbutadiene, cyclopentadiene, hexa-chlorocyclopentadiene, 1,3-diphenylisobenzofuran, and anthracene were obtained. Further reactions of these products such as elimination and autooxidation reactions were investigated. Addition reaction of dichlorocarbene to C₆₀ gave C₆₁Cl₂. Oxidation of C₆₀ with m-chloroperbenzoic acid gave C₆₀O_n(n=1, 2). All of the products were isolated by means of HPLC and characterized by mass spectroscopy.     

Quantitative Determination of C60 and C70 in Soot Extracts by High Performance Liquid Chromatography and Mass Spectrometric Characterization

A quantitative HPLC method was applied to determine the amounts of C₆₀ and C₇₀ present in extracts of soot produced in the electric arc reactor and in flames. The combustion method was found to yield a higher C₇₀/C₆₀ ratio (0.67) compared with the evaporation experiment where the C₇₀/C₆₀ ratio amounts to 0.27.     

Arylation of [60]Fullerene with Br2/FeCl3/PhH: Formation of C58 Derivatives via CO Loss

Heating a mixture of [60]fullerene, bromine, ferric chloride and benzene under reflux for 24 h products a range of phenylated [60]fullerene derivatives. The main product is C₆₀Ph₅H but other components identified by mass spectrometry (and in some cases separated by HPLC) are: C_6oPh_n(n = 4, 6, 8, 10, 12), C₆₀Ph_nO₂(n = 4, 6, 8, 10, 12), C₆₀Ph_nOH (n = 7, 9, 11), C₆₀Ph_nH₂ (n = 4, 10), C₆₀Ph₄H₄, C₆₀Ph₅H₃, C₆₀Ph_n0₂H (n = 5, 9), C₆₀Ph₄C₆H₄O₂, C₆₀Ph₉OH₃, and C₆₀Ph₁₁ O₃H₂. In the corresponding reaction with toluene, the crude reaction mixture contained C₆₀(MeC₆H₄)₄ as a main product; C₆₀(ClC₆H₄)₅H was obtained from the reaction with chlorobenzene. Formation of these derivatives is believed to involve radical bromination of the fullerene, followed by electrophilic substitution of the hatogenofullerene into the aromatic, accompanied in some case by hydrolysis, elimination and epoxide formation; oxidation may also introduce ketone/dioxetane functionality. The EI mass spectra of C₆₀Ph₄O₂ and C₆₀Ph₈O₂show degradation to C₅₈Ph_n (n = 0-8), having structures believed to be related to the pseudofollerenes C₆₈Ph_n (n = 0-8) reported recently. These results suggest that some derivatisations of fullerenes confer stability, due to the relief of strain.     

Charge Transfer in Fullerene-Conducting Polymer Compositex: Electronic and Excitonic Properties

C₆₀ doping into conducting polymer with highly extended π-electron system in the main chain induces remarkable quenching of photoluminescence in conducting polymer and drastic enhancement of photoconductivity. These results can be explained in terms of photo-induced charge transfer between conducting polymer and C₆₀. That is, photoexcited excitons or exciton-polarons on conducting polymer are effectively dissociated at C₆₀ molecules transferring electrons to C₆₀. Photoexcitation of C₆₀ results in the transfer of hole from C₆₀ to conducting polymer. These novel C₆₀ doping effects have been observed not only in conducting polymers with non-degenerated ground state structures but also those with degenerated ground state structure such as di-substituted acetylene polymers with solitonic electronic systems.

Highly effective photo-induced charge transfer has been also observed in conducting polymer/C₆₀ heterojunctions, which are interpreted as donor (D)-acceptor (A) photocell. Based on this finding we have demonstrated an organic photovoltaic cell with D-A double heterojunction, Al/C₆₀/OEP/conducting polymer/TTO, in which OEP is octaethylporphine as an light absorbing antenna molecule. Novel characteristics have also been observed in various other junction devices utilizing C₆₀ doped conducting polymer.

Granular and multiphase superconductivity has been found in C₆₀-conducting polymer-alkali metal composites.

Effect of other type of fullerenes such as C₇₀, modified C₆₀ and C₆₀ polymers, and also effect of C₆₀ doping in polysilanes and their derivatives have also been studied.     

Imaging Fullerene C60 with Atomic Resolution Using a Scanning Tunnelling Microscope

C₆₀ was purified and imaged utilizing scanning tunnelling microscopy (STM) in a constant current mode. By fixing the Fullerenes on the substrate (“frozen state” - no movement or rotation), direct imaging of C₆₀ with atomic resolution was possible, showing one pentagon and one hexagon carbon ring of C₆₀.     

Synthesis and Spectral Characterization of Difunctional Fullerenes

The oxidation of C₆₀ with m-chloroperbenzoic acid gave C₆₀O₂ with a high positional selectivity, as the ¹³C NMR analysis suggested. Diadducts C₆₀CCI₂O, C₆₀CCl₂(anthracene), C₆₀CCl₂[(CH₂CH₂)₂N₂], and C₆₀CCI₂[Pt-(PPh₃)₂] were synthesized, isolated, and characterized by negative ion FAB mass spectroscopy.