Fullerenol C60 Research Articles

Investigation of polymer membranes modified by fullerenol for dehydration of organic mixtures

This study focuses on the development of novel dense and supported mixed-matrix membranes based on chitosan and poly(2,6-dimethyl-1,4-phenylenoxide) (PPO) with low-hydroxylated fullerenol C60(OH)12. These novel membranes containing nano-carbon particles were prepared to reach high membrane performances for further integration in a dehydration process like distillation coupled with pervaporation. SEM microscopy was used to visualize the internal morphology of the membrane. It was found that all membranes were well stable and highly water-selective in spite of the different nature of polymers.

Novel green PVA-fullerenol mixed matrix supported membranes for separating water-THF mixtures by pervaporation.

This study focuses first on the preparation of mixed matrix supported membranes of polyvinyl alcohol (PVA) and low-hydroxylated fullerenol C60(OH)12 used to create water selective membranes and then on their pervaporation properties for the separation of water-THF mixtures. These novel supported PVA membranes containing nano-carbon particles were prepared to reach high membrane performance for further integration in a dehydration process, such as distillation coupled to pervaporation. The separation of water-THF mixtures was performed with the supported membranes over a wide range of water concentrations in the feed mixture, i.e., from the azeotrope range up to 30wt%, to evaluate the performance and stability of the thin active layer. SEM was used to visualize the internal morphology of the membrane. The influence of temperature on the transport properties was also investigated. All the membranes were highly water selective and stable up to 30wt% water in the feed. The best compromise of transport properties was obtained for the C60(OH)12(5%)-PVA supported composite membrane: a permeate enrichment of 99.3±0.3wt% water and a flux of 0.25±0.02kg/(m2h) for the separation of a mixture containing 5.7wt% water and 94.3wt% tetrahydrofuran (THF) at 30°C. Considering its water stability, this supported membrane with a dense layer thinner than 2μm appears promising for use in hybrid industrial processes to upgrade solvents with a smaller environmental footprint than conventional methods.

Development and characterization of transparent waterborne polyurethane acrylate/fullerenols thin-film nanocomposite as thermal-insulating coating

Thermal-insulating coating can lower the energy consumption and cooling costs, which caters to the tendency of environmental protection and energy conservation. Transparent waterborne polyurethane acrylate thin-film nanocomposite was developed by incorporating the fullerenol C60(OH)12(ONa)2 into the system using ultrasonic dispersion. The thin-film nanocomposite was then synthesized by ultraviolet radiation curing and chemical crosslinking, and its morphology and chemical structures were characterized. Thermogravimetric analysis and differential thermal gravity were used to evaluate the thermal stability. The surface and mechanical properties were tested by the pendulum hardness and MEK resistance. The optical and thermal-insulating properties were assessed by the ultravioletvisible-near infrared spectrophotometer and indoor environmental simulation experiment. The thermal-insulating measurements showed that the glass coated thin-film nanocomposite possessed better thermal-insulation effect than empty glass.

Effects of fullerenol nanoparticles and amifostine on radiation-induced tissue damages: Histopathological analysis

Fullerenol C60(OH)24 nanoparticles (FNP) are promising radioprotectors in prevention of early and late ionizing radiation injury. The aim of this study was to compare the efficacy of FNP and amifostine (AMI) in protection of rats exposed to whole-body X-ray irradiation (7 or 8Gy). Both compounds (FNP, 100mg/kg ip; AMI, 300mg/kg ip) were given 30min before irradiation throughout the study. The general radioprotective efficacy of FNP and AMI were evaluated in rats irradiated with an absolutely lethal dose of X-rays (8Gy) and their survival were monitored during the period of 30days after irradiation. Both compounds were of comparable efficacy. Tissue-protective effects of tested compounds were assessed in rats irradiated with an sublethal dose of X-rays (7Gy). For this purpose, the animals were sacrificed on the 7th and 28th day after irradiation. Their lung, heart, liver, kidney, small intestine and spleen were taken for histopathological and semiquantitative analysis. Careful examination of established tissue and vascular alteration revealed better radioprotective effects of FNP compared to those of AMI on the small intestine, lung and spleen, while AMI had better radioprotective effects than FNP in protection of the heart, liver and kidney. Results of this study confirmed high radioprotective efficacy of FNP in irradiated rats that was comparable to that of AMI, a well-known radioprotector.

Fullerenol spin probe containing isoindoline nitroxide and porphyrin groups

ABSTRACTA water-soluble fullerenol containing porphyrin and isoindoline nitroxide groups APTSPP-C60(OH)10-(TMIO)3 was synthesized by the incorporation of 5-(4-amino-phenyl)-10,15,20-tris(4-sulfonatophenyl)-porphyrin (APTSPP) as a tumor-targeting group and 5-formyl-1,1,3,3-tetramethylisoindolin-2-yloxyl (FTMIO) into fullerenol C60(OH)11. This nonmaterial was further characterized by FT-IR, UV, MS, TEM, fluorescence, etc. and its properties in vitro were also evaluated. Electrochemical experiments indicated that APTSPP-C60(OH)10-(TMIO)3 retained similar electrochemical properties and redox reaction mechanisms as 5-carboxy-1,1,3,3-tetramethylisoindolin-2-yloxyl (CTMIO). Electron paramagnetic resonance (EPR) spectra of APTSPP-C60(OH)10-(TMIO)3 exhibited the hyperfine splittings and characteristic spectra of CTMIO, with typical nitroxide g-values and nitrogen isotropic hyperfine coupling constants. In vitro cytotoxicity assay showed APTSPP-C60(OH)10-(TMIO)3 possessed low cytotoxicities to human renal tubular epithelial 293T cells and HepG-2 cells. Therefore APTSPP-C60(OH)10-(TMIO)3 may be considered as a potential candidate for novel biological spin probe using EPR spectroscopy.

Carbon Nanomaterials Alter Global Gene Expression Profiles.

Carbon nanomaterials (CNMs), which include carbon nanotubes (CNTs) and their derivatives, have diverse technological and biomedical applications. The potential toxicity of CNMs to cells and tissues has become an important emerging question in nanotechnology. To assess the toxicity of CNTs and fullerenol C60(OH)24, we in the present work used the budding yeast Saccharomyces cerevisiae, one of the simplest eukaryotic organisms that share fundamental aspects of eukaryotic cell biology. We found that treatment with CNMs, regardless of their physical shape, negatively affected the growth rates, end-point cell densities and doubling times of CNM-exposed yeast cells when compared to unexposed cells. To investigate potential mechanisms behind the CNMs-induced growth defects, we performed RNA-Seq dependent transcriptional analysis and constructed global gene expression profiles of fullerenol C60(OH)24- and CNT-treated cells. When compared to non-treated control cells, CNM-treated cells displayed differential expression of genes whose functions are implicated in membrane transporters and stress response, although differentially expressed genes were not consistent between CNT- and fullerenol C60(OH)24-treated groups, leading to our conclusion that CNMs could serve as environmental toxic factors to eukaryotic cells.

Improvement of pervaporation PVA membranes by the controlled incorporation of fullerenol nanoparticles

This work focuses on the incorporation of fullerenol nanoparticles to get PVA-fullerenol mixed matrix membranes for alcohol dehydration by pervaporation. Cross-linked hybrid membranes based on composites of polyvinyl alcohol (PVA) and low-hydroxylated fullerenol C60(OH)12 have been prepared by two different procedures. To improve the dispersion of the functionalized fullerene in the PVA network, the hydrodynamic properties of PVA, fullerenol and PVA/fullerenol composites in dilute solutions were studied by viscometry and dynamic light scattering. It was shown that the aggregate sizes increased with the increase of fullerenol content in the PVA/fullerenol composite solutions. The effect of low-hydroxylated fullerenol on the structure and morphology of PVA membranes was investigated by small-angle X-ray scattering and atomic force microscopy. It was observed that the incorporation of 5wt.% fullerenol and cross-linking with maleic acid led to a more uniform distribution of the amorphous PVA phase. As a result, membrane transport characteristics were improved for the dehydration of n-butanol–water mixtures by pervaporation. The PVA membranes containing 35wt.% maleic acid and 5wt.% fullerenol exhibited the best transport properties.

Fullerenol C60(OH)24 increases ion permeability of lipid membranes in a pH-dependent manner

Fullerenols are water-soluble analogs of fullerene exhibiting both antioxidant and prooxidant activities in vitro and in vivo. Here we report, for the first time, that fullerenol C60(OH)24 can induce ion permeability of a planar lipid bilayer membrane via the formation of ion pores or conductive defects with a preference for cations over anions. The fullerenol-mediated electrical current displayed non-linear concentration dependence and was reversibly enhanced by alkalinization. Calcium and magnesium ions decreased the fullerenol-induced potassium ion permeability. Voltage dependence of the current was sensitive to membrane composition, with the conductance being well pronounced in fully saturated diphytanoylphosphatidylcholine. Fullerenol did not induce carboxyfluorescein leakage from liposomes, suggesting a small size of fullerenol-induced pores. In contrast to ion permeability, the binding of C60(OH)24 to liposomes increased at acidic pH, as measured by fluorescence quenching of pyrene-labeled lipid. In line with this, the photodynamic action of fullerenol on the peptide gramicidin A also increased at low pH. It is hypothesized that aggregates of fullerenol may stabilize transient conductive lipid defects or pores formed under a variety of stress conditions.

Study of porous sol-gel nanocomposites based on silicon dioxide and tin dioxide modified by fullerenol C60(OH)n (n = 22-24)

In this study silicon dioxide - tin dioxide nanomaterials modified by fullerenol were obtained through the sol-gel technology. The results of nitrogen thermal desorption, atomic force microscopy and X-ray diffraction measurements are discussed. It was shown that introducing fullerenol C60(OH)n (n = 22-24) at the stage of preparing a sol greatly affects the microstructure of composites and results in the formation of an additional system of pores with an average radius of 16 nm.

Concentrations dominated membrane permeability variation by fullerol nanoparticles on a single living HeLa cell.

The effects in HeLa cell membrane permeability caused by the fullerenols C60(OH)n with different concentrations were studied by scanning electrochemical microscopy (SECM). We demonstrate that C60(OH)n has very low cytotoxicity, although it can still have strong effects on the cell membrane permeability. In the presence of 1 × 10-3 mg mL-1 (1 ppm) C60(OH)n, the cell membrane permeability increases by 26% after 76 min, which is reversible. When C60(OH)n concentration is over 25 × 10-3 mg mL-1 (25 ppm), the change in membrane permeability (increased 19%) is irreversible.

Fullerenol C60(OH)16 prevents amyloid fibrillization of Aβ40-in vitro and in silico approach.

The generation of Aβ amyloid aggregates in the form of senile plaques in the brain is one of the pathological hallmarks of Alzheimer's disease (AD). There is no cure for AD and one of the recent treatment strategies is focused on the inhibition of amyloid fibrillization of Aβ peptide. Fullerene C60 has been proposed as a candidate for destroying Aβ aggregates but it is not soluble in water and its toxicity to cells remains largely ambiguous. To overcome these drawbacks, we synthesized and studied the effect of water-soluble fullerenol C60(OH)16 (fullerene C60 carrying 16 hydroxyl groups) on the amyloid fibrillization of Aβ40 peptide in vitro. Using a Thioflavin T fluorescent assay and atomic force microscopy it was found that C60(OH)16 effectively reduces the formation of amyloid fibrils. The IC50 value is in the low range (μg ml(-1)) suggesting that fullerenol interferes with Aβ40 aggregation at stoichiometric concentrations. The in silico calculations supported the experimental data. It was revealed that fullerenol tightly binds to monomer Aβ40 and polar, negatively charged amino acids play a key role. Electrostatic interactions dominantly contribute to the binding propensity via interaction of the oxygen atoms from the COO(-) groups of side chains of polar, negatively charged amino acids with the OH groups of fullerenol. This stabilizes contact with either the D23 or K28 of the salt bridge. Due to the lack of a well-defined binding pocket fullerenol is also inclined to locate near the central hydrophobic region of Aβ40 and can bind to the hydrophobic C-terminal of the peptide. Upon fullerenol binding the salt bridge becomes flexible, inhibiting Aβ aggregation. In order to assess the toxicity of fullerenol, we found that exposure of neuroblastoma SH-SY5Y cells to fullerenol caused no significant changes in viability after 24 h of treatment. These results suggest that fullerenol C60(OH)16 represents a promising candidate as a therapeutic for Alzheimer's disease.

Design of La–C60/TiO2 Nanocomposites: Study of the Effect of Lanthanum and Fullerenol Addition Order onto TiO2. Application for the Photocatalytic Degradation of Formic Acid

Abstract La–C60/TiO2 nanocomposites were successfully obtained by dry impregnation method. The effect of La and polyhydroxylated fullerenol C60(OH)n addition order onto TiO2 was carefully highlighted. Interesting photocatalytic activity was achieved for the material firstly added with lanthanum. The increase in photocatalytic activity is attributed mainly to the synergy between fullerenol and La. Fullerenol enhances the electron charge transfer; whereas La increases the TiO2 thermal stability by adjusting the TiO2 crystallites sizes to low values and also by creating some structural defects.

Effects of fullerenol C60(OH)24 on physiological and compensatory erythropoiesis

In this work, the effect of fullerenol on erythropoiesis was investigated in healthy rats and in rats that had suffered blood loss in the amount of 2% of body weight. Fullerenol C60(OH)24 was diluted in 2 mL of 0.9% sodium chloride solution and injected intraperitoneally in a dose of 0.1 or 0.2 mg/kg body weight. The counts of reticulocytes, erythrocytes, and serum erythropoietin levels were determined in 48 and 96 h, as were the numbers of erythroid cells and erythroblastic islands (EIs) of different maturity fractions in the bone marrow and the fraction of the red pulp in the spleen. In intact rats, the reconstruction of erythropoiesis was augmented 1.5-fold in response to 0.1 mg/kg fullerenol C60(OH)24 and 3.3-fold in response to 0.2 mg/kg fullerenol. Both doses increased the number of oxyphylic erythroblasts in the bone marrow twofold, and 0.2 mg/kg fullerenol increased the red pulp fraction in the spleen by 9%; at the same time, fullerenol did not affect the counts of reticulocytes and erythrocytes, or the serum erythropoietin level in the case of normal erythropoiesis. Following hemorrhage, exposure to a 0.2 mg/kg dose of fullerenol C60(OH)24 increased serum erythropoietin levels, delayed the maturation of erythroid cells in EIs, partially blocked the release of reticulocytes from the bone marrow, and promoted an increase in the relative spleen weight and the red pulp fraction in the spleen.

Polyvinyl alcohol membranes modified by low-hydroxylated fullerenol C60(OH)12

Hybrid membranes based on composites of polyvinyl alcohol (PVA) and low-hydroxylated fullerenol C60(OH)12 have been assembled. In this study, two different procedures for PVA membrane cross-linking were applied including a thermal treatment, with elevated temperatures (140°C 100min) and chemical treatment with the addition of 35% maleic acid to the polymer matrix and thermal treatment (110°C 120min). The structure of the membranes was examined by wide-angle X-ray scattering (WAXS) and scanning electron microscopy (SEM). Thermal properties and stability were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). It was found that fullerenol, being an effective cross-linker for PVA, prevented the crystallization of the polymer during annealing, resulting in the increase of membrane permeability for chemically cross-linked membranes. Transport properties of hybrid membranes containing up to 5wt% fullerenol were studied by the pervaporation of (1) chemical-equilibrium quaternary mixtures of n-propyl acetate, acetic acid, n-propanol and water in order to identify the properties of the membranes used in the hybrid process of esterification+pervaporation, and (2) ternary azeotropic n-propyl acetate–n-propanol–water mixtures. All the membranes were selective with respect to water and the optimal transport properties were obtained for the PVA-5% fullerenol membranes containing maleic acid.

Review of Synthesis and Antioxidant Potential of Fullerenol Nanoparticles

This review describes the chemical synthesis of polar polyhydroxylated fullerene C60 derivatives, fullerenols C60(OH)n, 2 ≤ n ≤ 44, C60HzOx(OH)y, and polyanion fullerenols C60(OH)15(ONa)9, ranging from the very first synthetic methods up to some contemporary approaches to synthesis and separation. It also provides some basic information about physical characteristics of fullerenols. With the increasing number of hydroxyl groups, water solubility of fullerenols increases as well. Fullerenols both in water and biological media build nanoparticles of different dimensions and stability. In different chemical and biological model systems a large number of various polyhydroxylated fullerene derivatives were tested and they showed both their antioxidative and prooxidative characteristics. Several mechanisms have been proposed for the antioxidant activity of fullerenol. In addition, this paper also provides insight into patents referring to the antioxidant properties of fullerenol.

The Effect of Highly Hydroxylated Fullerenol C60(OH)36on Human Erythrocyte Membrane Organization

The mechanism of the interaction of highly hydroxylated fullerenol C60(OH)36with erythrocyte membranes was studied by electron spin resonance spectroscopy (ESR) of stearic acid derivatives labeled with a nitroxyl radical at C-12 or C-16 and with a nitroxyl derivative of maleimide covalently attached to sulfhydryl groups of membrane proteins. A significant increase in membrane fluidity in the hydrophobic region of the lipid bilayer was observed for 12-doxylstearic acid at fullerenol concentrations of 100 mg/L or 150 mg/L, while for 16-doxylstearic acid significant increase in fluidity was only observed at 150 mg/L. Fullerenol at 100 mg/L or 150 mg/L caused conformational changes in membrane proteins, expressed as an increase in thehw/hsparameter, when fullerenol was added before the maleimide spin label (MSL) to the membrane suspension. The increase of thehw/hsparameter may be caused by changes in lipid-protein or protein-protein interactions which increase the mobility of the MSL label and as a result increase the membrane fluidity. Incubation of the membranes with the MSL before the addition of fullerenol blocked the available membrane protein –SH groups and minimized the interaction of fullerenol with them. This confirms that fullerenol interacts with erythrocyte membrane proteins via available protein –SH groups.

Synergistic effect of phosphite with fullerene C60 and fullerenol C60(OH)24 as antioxidants in polypropylene

Polypropylene samples with fullerene C60, fullerenol C60(OH)24, 1010, C60/168, C60-OH/168 and 1010/168 as antioxidants were prepared by extrusions. MFR, YI, TGA and OIT of all the samples were tested. According to the results of MFR, during the melt extrusion, fullerene showed excellent stability effect on PP. The antioxidative ability of fullerene was comparable to the traditional antioxidant 1010. The antioxidative ability of fullerenol was not significant in the first extrusion and it accelerated the degradation of PP in the second and the third extrusions. TGA and OIT tests showed that the stability effects of fullerene and fullerenol were slightly lower than antioxidant 1010. In the first time, antioxidant 168 was reported to show great synergistic effects with fullerene and fullerenol as antioxidants, which sussested a simple way to enhance the antioxidative abilities of fullerene and fullerenol.

The influence of distribution of hydroxyl groups on vibrational spectra of fullerenol C60(OH)24 isomers: DFT study

The infrared and Raman spectra of C60(OH)24 molecule with uniform and non-uniform distribution of hydroxyl groups have been investigated using first principle DFT calculations at the B3LYP/6-31G(d,p) level of theory. The important features of the obtained geometries have been measured and compared to experimental results. The reference calculations of C60 molecule geometry and vibrational spectra have been made and compared to available experimental data. The striking differences of infrared spectra between C60(OH)24 molecule with uniform and non-uniform distribution of hydroxyl groups have been shown and discussed. The OH modes have been identified as the most sensitive to C60(OH)24 isomer configuration. The C–C stretching modes in the Raman spectra of the C60(OH)24 molecule have been found as a potential sensor of OH groups distribution over fullerene C60 surface.

Effects of fullerenol nanoparticles on acetamiprid induced cytoxicity and genotoxicity in cultured human lung fibroblasts

The aim of this study was to investigate the effects of water soluble fullerene (fullerenol) nanoparticles on the in vitro genotoxicity induced by the insecticide acetamiprid. Healthy human lung cells (IMR-90) were treated with fullerenol C60(OH)n (n: 18–22) alone and in combination with acetamiprid for 24h. The micronucleus test, comet assay and γ-H2AX foci formation assays were used as genotoxicity endpoints. Cytotoxicity was evaluated using the clonogenic assay. The maximum tested concentration of fullerenol (1.600μg/ml) induced 77% survival where as the lowest concentration (25μg/ml) was not cytotoxic where as acetamiprid was cytotoxic. Fullerenol did not induce genotoxicity at tested concentrations (50–1600μg/L). On the other hand, acetamiprid (>50μM) significantly induced formation of micronuclei, and double and single stranded DNA breaks in IMR-90 cells. For simultaneous exposure studies, two non-cytotoxic concentrations (50 and 200μg/ml) of fullerenol and three cytotoxic concentrations of acetamiprid (100, 200 and 400μM) were selected. As a result, we observed that co-exposure with fullerenol significantly reduced the cytotoxicity and genotoxicity of acetamiprid in IMR-90 cells. Our results indicated the protective effect of water soluble fullerene particles on herbicide induced genotoxicity.

Effects of fullerenol C₆₀(OH)₂₄ on erythropoiesis in vitro.

The effects of fullerenol C60(OH)24 in doses of 0.1-100 μg/ml on erythropoiesis were studied in the culture of erythroblastic islets of the bone marrow. Fullerenol in concentrations of 10 and 100 μg/ml had negative effects on the development of erythroid tissue: it inhibits proliferation of erythroid cells, delays erythroblast maturation, decelerates recruitment of erythroid CFU to differentiation, and suppresses repeated involvement of macrophages in erythroblastic islets.