Protective Effect of Water-Soluble C60 Fullerene Nanoparticles on the Ischemia-Reperfusion Injury of the Muscle Soleus in Rats

The biomechanical parameters of muscle soleus contraction in rats and their blood biochemical indicators after the intramuscular administration of water-soluble C₆₀ fullerene at doses of 0.5, 1, and 2 mg/kg 1 h before the onset of muscle ischemia were investigated. In particular, changes in the contraction force of the ischemic muscle soleus, the integrated power of the muscle, the time to achieve the maximum force response, the dynamics of fatigue processes, and the parameters of the transition from dentate to smooth tetanus, levels of creatinine, creatine kinase, lactate and lactate dehydrogenase, and parameters of prooxidant–antioxidant balance (thiobarbituric acid reactive substances, hydrogen peroxide, and reduced glutathione and catalase) were analyzed. The positive therapeutic changes in the studied biomechanical and biochemical markers were revealed, which indicate the possibility of using water-soluble C₆₀ fullerenes as effective prophylactic nanoagents to reduce the severity of pathological conditions of the muscular system caused by ischemic damage to skeletal muscles.     

C60 Fullerene Reduces 3-Nitropropionic Acid-Induced Oxidative Stress Disorders and Mitochondrial Dysfunction in Rats by Modulation of p53, Bcl-2 and Nrf2 Targeted Proteins

C₆₀ fullerene as a potent free radical scavenger and antioxidant could be a beneficial means for neurodegenerative disease prevention or cure. The aim of the study was to define the effects of C₆₀ administration on mitochondrial dysfunction and oxidative stress disorders in a 3-nitropropionic acid (3-NPA)-induced rat model of Huntington’s disease. Animals received 3-NPA (30 mg/kg i.p.) once a day for 3 consecutive days. C₆₀ was applied at a dose of 0.5 mg/kg of body weight, i.p. daily over 5 days before (C₆₀ pre-treatment) and after 3-NPA exposure (C₆₀ post-treatment). Oxidative stress biomarkers, the activity of respiratory chain enzymes, the level of antioxidant defense, and pro- and antiapoptotic markers were analyzed in the brain and skeletal muscle mitochondria. The nuclear and cytosol Nrf2 protein expression, protein level of MnSOD, γ-glutamate-cysteine ligase (γ-GCLC), and glutathione-S-transferase (GSTP) as Nrf2 targets were evaluated. Our results indicated that C₆₀ can prevent 3-NPA-induced mitochondrial dysfunction through the restoring of mitochondrial complexes’ enzyme activity, ROS scavenging, modulating of pro/antioxidant balance and GSH/GSSG ratio, as well as inhibition of mitochondria-dependent apoptosis through the limitation of p53 mitochondrial translocation and increase in Bcl-2 protein expression. C₆₀ improved mitochondrial protection by strengthening the endogenous glutathione system via glutathione biosynthesis by up-regulating Nrf2 nuclear accumulation as well as GCLC and GSTP protein level.     

Grafting of poly(ethylene oxide) onto C60 fullerene using macroazo initiators

In order to improve the solubility of C₆₀ fullerene in conventional solvents, grafting of hydrophilic poly(ethylene oxide) (PEO) by utilizing the radical-trapping nature of C₆₀ fullerene was investigated. Macroazo initiators containing a poly(ethylene oxide) unit, known as Azo-PEO, were prepared at various molecular weights by the reaction of 4,4′-azobis(4-cyanopentanoyl chloride) with poly(ethylene glycol) methyl ether. PEO radicals formed by thermal decomposition of Azo-PEO were successfully trapped by C₆₀ fullerene to give PEO-grafted C₆₀ fullerene. Their structures were confirmed by FT-IR spectroscopy, size exclusion chromatography, UV-vis spectroscopy, and differential scanning calorimetry. When Azo-PEO with low-molecular weight was reacted with C₆₀ fullerene, a bis-adduct, C₆₀-(PEO)₂, and a tetrakis-adduct, C₆₀-(PEO)₄, were formed. In contrast, in reactions with Azo-PEO of higher molecular weight, only the bis-adduct was formed, and no formation of the tetrakis-adduct was observed. The structure of bis-adduct was found to be 1,4-type. The solubility of C₆₀ fullerene in water, THF, methanol, and other conventional organic solvents was remarkably improved by grafting of PEO. In addition, the thermal stability of PEO was dramatically increased by grafting onto C₆₀ fullerene.     

Electrochemical properties of two-component polymers of palladium and pyrrolidine and piperazine derivatives of C60

Redox-active films have been generated via electrochemical reduction in a solution containing palladium(II) acetate and [C₆₀]fullerene, or derivatives of C₆₀. The C₆₀ derivatives include piperazine (piperazine-C₆₀), pyrrolidine (CH₃-pyr-C₆₀), and a pyrrolidine salt, [(CH₃)₂-pyr-C₆₀]⁺ attached to the fullerene unit. In these films, fullerene moieties are covalently bonded to palladium atoms to form a polymeric network. The polymer yields involving the piperazine and pyrrolidine derivatives of C₆₀ are significantly lower than the yield of the C₆₀/Pd film. The CH₃-pyr-C₆₀/Pd and [(CH₃)₂-pyr-C₆₀]⁺/Pd films are electrochemically active in the negative potential region due to the reduction of the fullerene moiety. Reduction of the CH₃-pyr-C₆₀/Pd film is accompanied by the transport of supporting electrolyte cations from the solution into the film. In the first reduction step of the [(CH₃)₂-pyr-C₆₀]⁺/Pd film, both cations and anions of the supporting electrolyte are involved. The piperazine-C₆₀/Pd film exhibits electrochemical activity at both negative and positive potentials. In the negative potential region, reduction of the fullerene cage takes place. Oxidation of the piperazine moiety is responsible for the observed current in the positive potential range. Here, the oxidation process of this polymer is significantly influenced by the presence of metallic palladium particles in the film.     

Advances in Polymer/Fullerene Nanocomposite: A Review on Essential Features and Applications

This review deals with progress in studies of polymer- and fullerene (mainly C₆₀)-based nanocomposite. Doping of polymeric materials with fullerenes is a significant research spot; however, the synthesis of polymer/fullerene nanocomposite is still in its infancy. In this regard, conventional, synthetic as well as conducting polymers have been doped with C₆₀ adopting various synthesis strategies. The combination of unique properties of fullerene with functional polymers has led to remarkable mechanical, thermal, electrical, optical, and photovoltaic properties of the final materials. Technical relevance of polymer/fullerene nanocomposite is also reviewed in this article considering photovoltaic, optical and temperature sensors, photoconductivity, and antimicrobial application.     

Water-Soluble,Alanine-Modified Fullerene C60 Promotes the Proliferation and Neuronal Differentiation of Neural Stem Cells

As carbon-based nanomaterials, water-soluble C₆₀ derivatives have potential applications in various fields of biomedicine. In this study, a water-soluble fullerene C₆₀ derivative bearing alanine residues (Ala-C₆₀) was synthesized. The effects of Ala-C₆₀ on neural stem cells (NSCs) as seed cells were explored. Ala-C₆₀ can promote the proliferation of NSCs, induce NSCs to differentiate into neurons, and inhibit the migration of NSCs. Most importantly, the Ala-C₆₀ can significantly increase the cell viability of NSCs treated with hydrogen peroxide (H₂O₂). The glutathioneperoxidase (GSH-Px) and superoxide dismutase (SOD) activities and glutathione (GSH) content increased significantly in NSCs treated even by 20 μM Ala-C₆₀. These findings strongly indicate that Ala-C₆₀ has high potential to be applied as a scaffold with NSCs for regeneration in nerve tissue engineering for diseases related to the nervous system.     

Effects of Three Different Doses of Inter-Alpha Inhibitor Proteins on Severe Hypoxia–Ischemia-Related Brain Injury in Neonatal Rats

Hypoxia–ischemia (HI)-related brain injury is an important cause of morbidity and long-standing disability in newborns. We have previously shown that human plasma-derived inter-alpha inhibitor proteins (hIAIPs) attenuate HI-related brain injury in neonatal rats. The optimal dose of hIAIPs for their neuroprotective effects and improvement in behavioral outcomes remains to be determined. We examined the efficacy of 30, 60, or 90 mg/kg of hIAIPs administered to neonatal rats after exposure to HI for 2 h. Postnatal day 7 (P7) Wistar rats were exposed to either sham-surgery or unilateral HI (right carotid artery ligation, 2 h of 8% O₂) brain injury. A placebo, 30, 60, or 90 mg/kg of hIAIPs were injected intraperitoneally at 0, 24 and 48 h after HI (n = 9–10/sex). We carried out the following behavioral analyses: P8 (righting reflex), P9 (negative geotaxis) and P10 (open-field task). Rats were humanely killed on P10 and their brains were stained with cresyl violet. Male extension/contraction responses and female righting reflex times were higher in the HI placebo groups than the sham groups. Female open-field exploration was lower in the HI placebo group than the sham group. hIAIPs attenuated these behavioral deficits. However, the magnitude of the responses did not vary by hIAIP dose. hIAIPs reduced male brain infarct volumes in a manner that correlated with improved behavioral outcomes. Increasing the hIAIP dose from 30 to 90 mg/kg did not further accentuate the hIAIP-related decreases in infarct volumes. We conclude that larger doses of hIAIPs did not provide additional benefits over the 30 mg/kg dose for behavior tasks or reductions in infarct volumes in neonatal rats after exposure to severe HI.     

Influence of electron concentration and temperature on fullerene formation in a carbon plasma

The influence of electron concentration in ionized carbon vapor on C₆₀ fullerene formation was theoretically investigated. By considering C₆₀ molecule assembly at one or two intermediate stages of cluster collision we determined the plasma parameters (temperature and electron concentration) optimal for the fullerene synthesis. The estimations made showed that waves of electron concentration in plasma changed the rate of C₆₀ fullerene assembling.     

Electrochemical quartz crystal microbalance studies of thin-solid films of higher fullerenes: C76, C78 and C84

Thin-solid films of higher fullerenes, viz. C₇₆, C₇₈ and C₈₄, were prepared by the drop coating technique and characterized by simultaneous cyclic voltammetry and piezoelectric microgravimetry with the use of an electrochemical quartz crystal microbalance. Properties of the films were compared with those reported earlier for the C₆₀ and C₇₀ thin-solid films. The effect of nature of the counter cation on electrochemical properties of the films has been probed by employing acetonitrile solutions of two different 0.1 M supporting electrolytes, namely tetra(n-butyl)ammonium (TBA⁺) hexafluorophosphate and potassium hexafluorophosphate. Stability of the films with respect to dissolution depends on the fullerene oxidation state as well as on the nature of both the fullerene in the film and the counter cation in the supporting electrolyte. The TBA⁺ counter cation ingress to the film for compensation of the negative charge of the reduced fullerene is accompanied by the acetonitrile solvent intake. The number of acetonitrile molecules per TBA⁺ counter cation entering the film is higher the higher the fullerene. Also, the Langmuir films of higher fullerenes were prepared at the air-water interface and the film morphology was characterized by the Brewster angle microscopy.     

Fullerene Rosette: Two-Dimensional Interactive Nanoarchitectonics and Selective Vapor Sensing

The simplicity of fullerenes as assembled components provides attractive opportunities for basic understanding in self-assembly research. We applied in situ reactive methods to the self-assembly process of C₆₀ molecules with melamine/ethylenediamine components in solution, resulting in a novel type of fullerene assemblies, micron-sized two-dimensional, amorphous shape-regular objects, fullerene rosettes. ATR–FTIR spectra, XPS, and TGA results suggest that the melamine/ethylenediamine components strongly interact and/or are covalently linked with fullerenes in the fullerene rosettes. The broad peak for layer spacing in the XRD patterns of the fullerene rosettes corresponds roughly to the interdigitated fullerene bilayer or monolayer of modified fullerene molecules. The fullerene rosettes are made from the accumulation of bilayer/monolayer assemblies of hybridized fullerenes in low crystallinity. Prototype sensor systems were fabricated upon immobilization of the fullerene rosettes onto surfaces of a quartz crystal microbalance (QCM), and selective sensing of formic acid was demonstrated as preliminary results for social-demanded toxic material sensing. The QCM sensor with fullerene rosette is categorized as one of the large-response sensors among reported examples. In selectivity to formic acids against basic guests (formic acid/pyridine >30) or aromatic guests (formic acid/toluene >110), the fullerene rosette-based QCM sensor also showed superior performance.     

Formation of fullerenes by pyrolysis of 1,2′-binaphthyl and 1,3-oligonaphthylene

High-temperature pyrolysis of two fullerene precursors - 1,2′-binaphthyl and 1,3-oligonaphthyl - has been investigated. An oligomer of naphthalene with the appropriate orientation of fragments, which contains all 60 carbon atoms, 12 of 20 six-membered rings and 71 of 90 carbon-carbon bonds required to form the C₆₀ fullerene cage was synthesized in a three-step synthesis from naphthalene. The formation of fullerene during pyrolysis was confirmed by MALDI-TOF and HPLC analysis of the toluene extract obtained from the raw soot. It was found that the toluene extract contains free C₆₀ fullerene but the main share of fullerenes exists in the form of their derivatives. The yield of free C₆₀ was estimated as 0.1% by HPLC but the overall yield of C₆₀ seems to be higher and was estimated as ≈1%.     

Synthesis of C60 Fullerene-Silica Hybrid Nano Structures

We have recently demonstrated a procedure for the synthesis of silica nanometer and micrometer particles under modest conditions. Here we report the synthesis of C₆₀ fullerene-silica hybrid nanometer sized materials via sol-gel processing at neutral pH and under ambient conditions. The C₆₀ fullerene, when functionalized, was water-soluble and also able to facilitate the formation of silica structures from an aqueous silica precursor. This C₆₀ fullerene had similar functionality to the cationically charged polymers, which have been reported earlier to act as catalysts/templates for silicification. The resulting organic-inorganic hybrid was studied using SEM, EDS and UV/Vis spectroscopy. These hybrid materials may have applications in areas such as optical devices, semiconductors, chemical sensors, catalysis and in the medical field. The results presented in this study may be useful in developing a process for the synthesis of novel organic-inorganic nanometer sized materials and for the biomimetic synthesis of silica.     

Synthesis and characterization of polyethylene/C<Subscript>60</Subscript> fullerene structures by photoluminescence

Fullerene C₆₀ has attracted attention due to its special chemical and physical properties. However, its poor solubility and processability arise difficulties in practical applications. These problems may be surpassed by grafting C₆₀ on polymers. This study presents the synthesis of the polyethylene/maleic anhydride copolymers and C₆₀ structures and their characterization by photoluminescence. The synthesis of the material is based upon the reaction of fullerene C₆₀ with amino groups containing in the polymer chains. In the first step, some polyethylene (PE)/maleic anhydride (MA) copolymers having 1, 3, 6 and 10 wt.% anhydride groups were reacted with an amine compound. The following step consists in the reaction of C₆₀ with the amine groups. A proof that the structures synthesized contain C₆₀ is given by the photoluminescence spectra.     

Fullerene C60 Supported on Silica and γ-Alumina Catalyzed Photooxidations of Alkenes

Deposition of fullerene C₆₀ (2% w/w) on silica and -alumina provokes a two orders-of-magnitude increase of its activity for the liquid-phase photooxidation of 2-methyl-2-heptene. Kinetic studies concerning the above photooxidation showed a first-order dependence of the reaction rate on the alkene concentration. The corresponding reaction-rate constant was found to be higher in the case where -alumina was used as carrier. The nature of the carrier does not influence the mechanism and the selectivity of the reaction. High dispersion of the supported fullerene is achieved on the surface of the carriers, which increase the fullerene light absorbance especially in the visible range.     

Strain-Relief Patterns and Kagome Lattice in Self-Assembled C60 Thin Films Grown on Cd(0001)

We report an ultra-high vacuum low-temperature scanning tunneling microscopy (STM) study of the C₆₀ monolayer grown on Cd(0001). Individual C₆₀ molecules adsorbed on Cd(0001) may exhibit a bright or dim contrast in STM images. When deposited at low temperatures close to 100 K, C₆₀ thin films present a curved structure to release strain due to dominant molecule–substrate interactions. Moreover, edge dislocation appears when two different wavy structures encounter each other, which has seldomly been observed in molecular self-assembly. When growth temperature rose, we found two forms of symmetric kagome lattice superstructures, 2 × 2 and 4 × 4, at room temperature (RT) and 310 K, respectively. The results provide new insight into the growth behavior of C₆₀ films.     

Exploring the Bioactive Potentials of C60-AgNPs Nano-Composites against Malignancies and Microbial Infections

At present, the potential role of the AgNPs/endo-fullerene molecule metal nano-composite has been evaluated over the biosystems in-vitro. The intra-atomic configuration of the fullerene molecule (C₆₀) has been studied in-vitro for the anti-proliferative activity of human breast adenocarcinoma (MDA-MB-231) cell lines and antimicrobial activity against a few human pathogens that have been augmented with the pristine surface plasmonic electrons and antibiotic activity of AgNPs. Furthermore, FTIR revealed the basic vibrational signatures at ~3300 cm⁻¹, 1023 cm⁻¹, 1400 cm⁻¹ for O-H, C-O, and C-H groups, respectively, for the carbon and oxygen atoms of the C₆₀ molecule. NMR studies exhibited the different footprints and magnetic moments at ~7.285 ppm, explaining the unique underlying electrochemical attributes of the fullerene molecule. Such unique electronic and physico-chemical properties of the caged carbon structure raise hope for applications into the drug delivery domain. The in-vitro dose-dependent application of C₆₀ elicits a toxic response against both the breast adenocarcinoma cell lines and pathogenic microbes. That enables the use of AgNPs decorated C₆₀ endo fullerene molecules to design an effective anti-cancerous drug delivery and antimicrobial agent in the future, bringing a revolutionary change in the perspective of a treatment regime.     

Theoretical calculations of the structure and UV-vis absorption spectra of hydrated C60 fullerene

A combined Monte Carlo simulation with semiempirical quantum mechanics calculations has been performed to investigate the structure of hydrated fullerene (C₆₀HyFn) and the influence of hydration on its UV-vis spectra. The statistical information of the C₆₀ fullerene aqueous solution (C₆₀FAS) is obtained from NPT ensemble including one C₆₀ fullerene immerses in 898 water molecules. To obtain an efficient ensemble average, the auto-correlation function of the energy has been calculated. The analyzed center-of-mass pair-wise radial distribution function indicates that, on average, there are 65 and 151 water molecules around the first and second hydration shells, respectively, of a single C₆₀ molecule. To calculate the average UV-vis transition energies of C₆₀HyFn, only the statistically uncorrelated configurations are used in the quantum mechanical calculations (INDO/CIS). These involve hundreds of supramolecular structures containing one C₆₀ fullerene surrounded by the first hydration shell. The calculated average transitions at 268 and 350 nm are in very good agreement with the experimental prediction.     

Optimization of Synthesis Parameters for Mesoporous Shell Formation on Magnetic Nanocores and Their Application as Nanocarriers for Docetaxel Cancer Drug

In this work, Fe₃O₄@SiO₂ nanoparticles were coated with mesoporous silica shell by S⁻N⁺I⁻ pathway by using anionic surfactant (S⁻) and co-structure directing agent (N⁺). The role of co-structure directing agent (CSDA) is to assist the electrostatic interaction between negatively charged silica layers and the negatively charged surfactant molecules. Prior to the mesoporous shell formation step, magnetic cores were coated with a dense silica layer to prevent iron oxide cores from leaching into the mother system under any acidic circumstances. However, it was found that both dense and mesoporous coating parameters affect the textural properties of the produced mesoporous silica shell (i.e., surface area, pore volume and shell thickness). The synthesized Fe₃O₄@SiO₂@m-SiO₂ (MCMSS) nanoparticles have been characterized by low-angle X-ray diffraction, transmission electron microscopy (TEM), and N₂ adsorption-desorption analysis, and magnetic properties. The synthesized particles had dense and mesoporous silica shells of 8–37 nm and 26–50 nm, respectively. Furthermore, MCMSS possessed surface area of ca. 259–621 m²·g⁻¹, and pore volume of ca. 0.216–0.443 cc·g⁻¹. MCMSS showed docetaxcel cancer drug storage capacity of 25–33 w/w% and possessed control release from their mesochannels which suggest them as proper nanocarriers for docetaxcel molecules.     

Effects of fullerene addition on the carbonization of synthetic naphthalene isotropic pitch

The toluene soluble fraction of fullerene soot, consisting of C₆₀ and C₇₀ and other fullerenes, was co-carbonized with synthesized isotropic pitch derived from naphthalene. Mixtures of fullerene and pitch gave carbons in higher yield than expected from their single carbonizations at fullerene contents <30 wt%. The fullerenes suppressed the expansion of the pitch during carbonizations, and changed the optical textures of resultant carbons. At levels of addition of fullerenes <30 wt%, no fullerenes could be detected in resultant carbons by spectroscopy, but were detected as spheres of ca. 10–20 nm diameter in the carbons by TEM. It is considered that fullerenes remove hydrogen from the naphthenic structures of the pitch and so alter carbonization characteristics. Hydrogenation breaks the spheroidal fullerene framework.     

Enhanced open-circuit voltage of two side chain conjugated polythiophene derivatives blended with indene-C60 bisadduct

Two side chain conjugated polythiophene copolymer: poly[3-(5′-octylthienylenevinyl) thiophene]-thiophene (P1) and poly{3-[4-(2-ethyl-hexyloxy)-phenylvinyl]-thiophene}-thiophene (P2) were synthesized. Polymer photovoltaic solar cells using P1 and P2 as donor and a high LUMO energy level fullerene derivative indene-C₆₀ bisadduct (IC₆₀BA) as acceptor were demonstrated. The polymer solar cells (PSCs) based P1/IC₆₀BA and P2/IC₆₀BA showed enhanced open circuit voltage (V_oc) of 0.89 and 0.88 V respectively, in comparison with that of P1/PC₆₁BM and P2/PC₆₁BM as 0.58 and 0.56 V, respectively. The improved V_oc of IC₆₀BA as acceptor in PSCs is benefited from the higher LUMO energy levels of the C₆₀ derivatives. The power conversion efficiency of the PSCs based on P1/IC₆₀BA and P2/IC₆₀BA were 0.32% and 0.35%, respectively.