Fullerene C60 Research Articles

Ambipolar charge transfer of larger fullerenes enabled by the modulated surface potential of h-BN/Rh(111)

A detailed understanding of how molecules interact with two-dimensional materials, particularly concerning energy level alignment and charge transfer processes, is essential to incorporate functional molecular films into next-generation 2D material-organic hybrid devices. One of the major challenges in integrating molecular films in field-effect transistors is facilitating ambipolar charge transport, which is often hindered by the large electronic gap of the organic layers. This work compares the adsorption site-dependent energy level alignment of C60, C70, and C84 fullerenes induced by the spatial variation of the electrostatic surface potential of the h-BN/Rh(111) Moiré superstructure. As the size of the fullerenes increases, the HOMO-LUMO gap shrinks. In the case of C84, we find an intrinsic charge transfer from the substrate to the fullerenes adsorbed in the Moiré pore centers, rendering them negatively charged. The electric field effect-induced charging of neutral fullerenes and discharging of intrinsically negatively charged fullerenes are investigated using scanning tunneling spectroscopy, non-contact atomic force microscopy, and Kelvin probe force spectroscopy. Our findings show that on metal-supported h-BN, the LUMO level of C84 is sufficiently close to the Fermi energy that it can be neutral or 1e− negatively charged depending on slight variations of the electrostatic potential. The findings propose a path to make ambipolar charge transfer accessible and efficient by circumventing the need to overcome the fullerenes’ electronic gap.

Occurrence of natural fullerene C60 from the iridium-rich Cretaceous-Paleogene (K-Pg) boundary layers of the Um-Sohryngkew river section, Meghalaya, India

The presence of fullerene C60 in the iridium-rich Cretaceous-Palaeogene (K-Pg) boundary layer from the Um-Sohryngkew river section of Meghalaya is reported here for the first time. Different analytical methods, including transmission electron microscopy (TEM), Raman spectroscopy, Fourier transform infrared (FT-IR), and X-ray diffraction(XRD) techniques, have been used to characterize the presence of toluene-insoluble high-pressure phase of fullerene C60 in the acid resistant carbonaceous matter extracted from the Um-Sohryngkew river section, Meghalaya, India. Strong absorption peaks at wavenumbers 1427, 1181, 574, and 525 cm−1, which are indicative of pristine fullerene C60, can be seen in the FTIR spectroscopic study. The Raman spectrum also independently confirms the presence of fullerene, by exhibiting the characteristics peaks of pristine fullerene C60. The XRD technique provides further, independent validation of fullerenes, and the XRD pattern demonstrates fullerene presence. Fullerenes, high-pressure fullerene, the amorphous phase of C60, and iridium all coexist and offer conclusive proof of impact at the Cretaceous-Palaeogene (K-Pg) boundary extinction event.

Influence of Dispersion Interactions in the Diels-Alder Reaction of Cyclopentadiene, Anthracene and Tetracene with C60: A DFT Examination

Asbtract: The activation and thermodynamic parameters of the Diels-Alder reaction of cyclopentadiene, anthracene and tetracene with C60 fullerene are estimated at the DFT level using PBE0, B3LYP and CAM-B3LYP functionals and the effect of accounting for dispersion interactions in various semi-empirical Grimme models on these parameters. Structural characteristics of the reagents, products, pre-reaction van der Waals complex, and transition state are obtained. Taking into account dispersion corrections have practically no effect on the geometric characteristics of structures with the covalent type of the bond, as well as on the structure of the transition state. Still, it has a noticeable effect only on the structure of the pre-reaction complex, in which the interparticle interaction has a van der Waals character. At the same time, taking into account dispersion corrections plays a significant role in assessing the thermodynamic and activation parameters of the reaction. An analysis of the performed calculations showed that the combination of PBE0/def2-TZVP with the D4 model for dispersion interactions could be recommended for the Diels-Alder reaction considered above.

Structure and antiradical activity of N-monosubstituted amino acid derivatives of fullerene C60 in aqueous colloidal solutions

The dimensional characteristics of nanoparticles of N-mono- substituted amino acid derivatives of fullerene C60 (AAFDs) in aqueous colloidal solutions, determined by dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS), were compared. The DLS data on the dimensional characteristics of fullerene C60 and AAFD nanoparticles, obtained at scattering angles of 90° and 173°, are close in values with a correlation coefficient of 0.89, and the SAXS data indicate that AAFDs form ordered structures in solution. Based on the results of DLS and the ability of fullerene and AAFDs to inhibit peroxyl radicals, it can be concluded that varying the concentrations of the studied compounds in the range from 10-7 to 10-3 m does not affect the degree of aggregation of their nanoparticles.

Spectroscopic study of aqueous solutions of fullerene C60 mono-derivatives

Current spectral study of aqueous solutions of N-substituted fullerene C60 mono-derivatives of amino acid potassium salts showed that their solutions obey the Bouguer–Lambert–Beer law. On the basis of circular dichroism data, the optical activity was discovered not only for adducts with chiral amino acids but also for those with achiral molecules.

Ubiquitous fullerenes: A detection of C60 and C70 under sonolysis of aqueous graphite colloidal suspensions

For the first time, the molecular bands of the C2 species were detected in the single-bubble sonoluminescence spectra of aqueous colloidal suspensions of graphite nanoparticles (≤ 50 nm) obtained by ultrasonic dispergation upon multi-bubble sonolysis. The registration of these bands indicates that graphite nanoparticles enter the moving cavitation bubble together with solution microdroplets, where they are decomposed in the nonequilibrium plasma that occurs during ultrasonic vibrations into small fragments, including C2 radicals. Based on the conventional mechanism for the formation of fullerenes at the arc-discharge synthesis, starting from C2, under plasma conditions, we suggest that these framework molecules are synthesized in a cavitation bubble during single-bubble sonolysis of graphite nanoparticles. Indeed, the presence of the C60 and C70 fullerenes was registered in the accumulated sonolysis products of samples of suspensions of graphite nanoparticles with the chromatographic and mass-spectrometric techniques.

Amplifying the dielectric constant of shellac by incorporating natural clays for organic field effect transistors (OFETs).

We demonstrate in this work the practical use of uniform mixtures of a bioresin shellac and four natural clays, i.e. montmorillonite, sepiolite, halloysite and vermiculate as dielectrics in organic field effect transistors (OFETs). We present a thorough characterization of their processability and film forming characteristic, surface characterization, elaborate dielectric investigation and the fabrication of field effect transistors with two classic organic semiconductors, i.e. pentacene and fullerene C60. We show that low operating voltage of approximately 4 V is possible for all the OFETs using several combinations of clays and shellac. The capacitance measurements show an improvement of the dielectric constant of shellac by a factor of 2, to values in excess of 7 in the uniform mixtures of sepiolite and montmorillonite with this bioresin.

Edge-selective covalent passivation of black phosphorus nanosheets by fullerene C70 toward enhanced antimicrobial performance

In the fight against bacterial infection, conventional antibiotic treatment encounters the formidable challenges of drug resistance and sluggish development. Non-metallic two-dimensional (2D) nanomaterials such as black phosphorus (BP) have emerged as promising non-antibiotic antimicrobial candidates due to its peculiar physiochemical properties, but face hurdles including low ambient stability and limited antibacterial activity, hindering its widespread utilization in disinfection. Herein, few-layer BP nanosheets (BPNSs) were covalently passivated by edge-selectively grafting fullerene C70 via a one-step solid-state mechanochemical route, and for the first time the covalently functionalized BPNSs is employed in disinfection. Fullerene edge-selective covalent passivation not only effectively overcomes the obstacles of poor ambient stability, but also substantially enhances the antibacterial activities of BPNSs. The BPNSs-C70 hybrid (denoted as BPNSs-C70) was applied as a novel non-metallic and non-antibiotic nano-antibacterial agent. Under 660 nm visible light irradiation, BPNSs-C70 demonstrates high generation capacity of reactive oxygen species (ROS), resulting in boosted in vitro and in vivo antibacterial efficacies against methicillin-resistant Staphylococcus aureus (MRSA) relative to the pristine BPNSs with exceptional biocompatibility. The significantly enhanced antibacterial performance of BPNSs-C70 is attributed to the synergistically improved singlet oxygen (1O2) and hydroxyl radicals (•OH) generation originated from the intramolecular electron transfer from BPNSs to C70.

Selective Encapsulation and Chiral Induction of C60 and C70 Fullerenes by Axially Chiral Porous Aromatic Cages.

Chiral induction has been an important topic in chemistry, not only for its relevance in understanding the mysterious phenomenon of spontaneous symmetry breaking in nature but also due to its critical implications in medicine and the chiral industry. The induced chirality of fullerenes by host-guest interactions has been rarely reported, mainly attributed to their chiral resistance from high symmetry and challenges in their accessibility. Herein, we report two new pairs of chiral porous aromatic cages (PAC), R-PAC-2, S-PAC-2 (with Br substituents) and R-PAC-3, S-PAC-3 (with CH3 substituents) enantiomers. PAC-2, rather than PAC-3, achieves fullerene encapsulation and selective binding of C70 over C60 in fullerene carbon soot. More significantly, the occurrence of chiral induction between R-PAC-2, S-PAC-2 and fullerenes is confirmed by single-crystal X-ray diffraction and the intense CD signal within the absorption region of fullerenes. DFT calculations reveal the contribution of electrostatic effects originating from face-to-face arene-fullerene interactions dominate C70 selectivity and elucidate the substituent effect on fullerene encapsulation. The disturbance from the differential interactions between fullerene and surrounding chiral cages on the intrinsic highly symmetric electronic structure of fullerene could be the primary reason accounting for the induced chirality of fullerene.

Fullerene C60: Dielectric and elastic properties of E8 nematic liquid crystal

This study presents a comprehensive analysis of the impact of Fullerene C60 doping on the dielectric and elastic behavior of E8 coded nematic liquid crystals. By investigating the underlying mechanisms, we unveil how Fullerene C60 can effectively modify the properties of nematic liquid crystals, particularly their dielectric and elastic characteristics. Through the analysis of Cole-Cole plots and semicircle plots, we gain valuable insights into the suitability of an equivalent electronic circuit model, thereby holding promise for liquid crystal-based devices with improved performance and functionality in electrical circuit applications. Furthermore, our results demonstrate that the presence of Fullerene C60 induces higher splay elastic constant (K11) values in doped nematic liquid crystals, attributed to an increase in the sample's threshold voltage. Moreover, the presence of Fullerene C60 fosters strong elastic interactions in the liquid crystal system due to surface anchorage, resulting in an elevation of its elastic energy.

Protective role of fullerenol and arginine C60 fullerene against copper toxicity in cucumber

Copper (Cu), when in excess, is one of the most toxic and hazardous metals to all living organisms, including plants. Engineered nanomaterials have the potential for increasing crop protection. However, the protective role of fullerenes (carbon-based nanoparticles with wide application in various areas) against Cu toxicity in plants is, so far, understudied. The present study investigated whether fullerenes can potentially alleviate Cu toxicity in plants (Cucumis sativus L.). Two water-soluble fullerene C60 derivatives were examined: fullerenol [C60(OH)22–24] and arginine-functionalized fullerene [C60(C6H13N4O2)8H8], under controlled conditions using hydroponics. Plants treated with 15 μM of Cu exhibited typical symptoms of Cu toxicity: impaired growth, leaf chlorosis, reduced photosynthetic activity, nutritional imbalances, and enhanced lipid peroxidation. These symptoms were alleviated in the presence of fullerene derivatives with arginine C60 having the more pronounced effect. Improved cucumber Cu tolerance was attributable to Cu buffering in the root zone (roots and medium), which caused a dramatic decline in Cu transport towards leaves and the elimination of oxidative damage. The Cu removal efficacy of arginine C60 was much greater than that of fullerenol. These fullerenes acted in a dose-dependent manner and removed Cu selectively without significant modification of the bioavailability of other essential nutrients. Treatment with free arginine did not affect Cu immobilization or Cu toxicity. These results suggest that the surface chemistry of the fullerene core is important for the protection of plants under excessive Cu conditions. The information offered a new approach to preparing promising practical materials for alleviating Cu toxicity in plants with potential application in fields.

Evaluation of the efficiency of intersystem crossing to a triplet state of fullerene in complexes with amino acids

The important photophysical process that determines the efficiency of photosensitizers is saturation of a triplet state by intersystem crossing during light absorption. In the present work, C60 fullerene complexes with amino acids glycine, lysine, methionine and threonine were studied as promising photosensitizers. All these complexes, for which the calculations were done, demonstrate high values of rate constants of transition to triplet states and a high probability of the ability to generate reactive oxygen species through excitation in the visible spectrum. The carboxyl groups of amino acids that are not involved in electronic excitation can be used as the component of specific DNA aptamers for conjugation to photoactive complexes for a tumor-targeting drug delivery system.

Therapeutic potential of CX (X = 48, 60, and 70) fullerenes as drug delivery carriers for ifosfamide anti-cancer drug

Ifosfamide (ISF) has been known as an anticancer drug. It attacks fast growing cancer cells and unfortunately, it also attacks other quickly growing cells such as hair roots. Therefore, it is essential to find a method for delivering of this drug to the targeted tumor cells to reduce its side effects. To this aim, here, we applied a new kind of fullerenes to this purpose and introduce a new strategy based on the drug release in cancer cells. We studied the interaction of C48, C60, and C70 fullerenes with this drug using density functional theory calculations. Based on the results, the pure fullerenes are not suitable for the drug delivery of ISF because of a weak interaction. We found that Al doping into the C48, C60, and C70 leads to an increase in the ISF adhesion energy of from −4.3, −4.8, and − 5.3 kcal/mol to −28.2, −29.1, and − 30.7 kcal/mol, respectively. This shows that Al atom significantly increases the drug loading capacity and reactivity of fullerenes, making them more suitable for drug delivery. We introduced a drug release mechanism in cancerous tissues with a low pH. The strategy is based on the protonation of ISF, which separated it from the fullerene surface. The interaction mechanism of ISF with the fullerene changes from covalent to H-bonding in the acidic environment of cancerous cells. We also showed that the water solvent has a negligible effect on the adsorption process.

Effect of black phosphorus modified by fullerene C60 on the self-lubricating properties of PEEK-based composite coatings

Poly-ether-ether-ketone (PEEK) has many excellent properties for being used as self-lubricating coatings. In order to further improve the friction performance, black phosphorus (BP) was used as filler to prepare BP/PEEK composite coating. BP-C60 was formed by modification of BP edge by fullerene C60 to solve the problem of BP oxidation, so that BP still existed in the sintered PEEK coating. Then, the effects of C60 and BP-C60 on the tribological properties of PEEK coating were studied, and the results showed that the wear rate and friction coefficient of BP-C60/C60/PEEK composite coating were significantly reduced. This was attributed to the synergistic effect of BP and C60, which enhanced the stability of BP and reduced coating porosity.

EVALUATION OF THE POTENTIAL NEUROACTIVITY IN THE BRAIN NERVE TERMINALS OF THE C60 FULLERENE PLANETARY DUST COMPONENT

A study of the infrared spectrum of the environment of the planetary nebula Tc 1 revealed the radiation of cold and neutral fullerenes C60 and C70. The results of the analysis of infrared spectra obtained using the Hubble space telescope conclusively proved the existence of C60+ fullerene in the interstellar medium. These large carbon-containing molecules can form and exist in the interstellar medium and are candidates to explain many diffuse interstellar absorption bands. In this study, the potential neuroactivity of the C60 fullerene as a planetary dust component was assessed in the isolated rat brain nerve terminals. It was shown that C60 fullerene in the unirradiated state at concentrations of 0.05—0.25 mg/ml did not change the extracellular levels of excitatory neurotransmitter L-[ 14C]glutamate and inhibitory neurotransmitter [ 3H]GABA in the preparations of rat brain nerve terminals. An increase in fullerene C60 concentrations up to 0.5 and 1.00 mg/ml was accompanied by an increase in the extracellular levels of L-[ 14C]glutamate and [3 H]GABA in the preparations of nerve terminals. Therefore, fullerene C60 did not cause signs of acute neurotoxicity in the brain nerve terminals within the concentration range of 0.05—0.25 mg/ml. However, given that C60 undergoes photooxidation, it can be expected that it may acquire neurotoxic properties in situ.

Histamine sensing by boron and silicon doped C60 fullerenes: A first principles investigation

The present study reports adsorption mechanism of histamine on the surfaces of pure, B- or Si-doped fullerenes. The adsorption of histamine on pure and doped fullerenes has been investigated through density functional theory calculations in the terms of stability, geometry, work function, electronic properties, and density of state spectra. The magnitude of adsorption energies has been computed to be −1.66, −35.29, and −37.43 kcal/mol for histamine corresponding to the most favorable adsorption configurations respectively. The band gap analysis revealed that the electrical conductivity of pure fullerene remains nearly constant even after histamine adsorption. However, the doping of boron and silicon leads to the decrease of the band gap after histamine adsorption resulting increment in the electrical conductivity which infers that boron and silicon doped fullerenes are more sensitive towards histamine adsorption than pure fullerene. Moreover, the NBO calculations showed charge transfer of 0.008, 0.409, and 0.272e from histamine to pure, boron and silicon doped fullerenes in the most favorable adsorption configurations, respectively.

Computational Energy Spectra of the H2O@C70 Endofullerene.

A water molecule confined inside the C70 fullerene wasquantum-mechanically described using a computational approachwithin the MCTDH framework. Such procedure involvesthe development of a full-dimensional coupled hamiltonian, with an exact kinetic energy operator, including allrotational, translational and vibrational degrees of freedomof the endofullerene system. In turn, through an effectivepairwise potential model, the ground and rotationally excitedstates of the encapsulated H2O inside the C70 cagewere calculated, and traced back to the isotropic case ofthe H2O@C60 endofullerene in order to understand the nature and physical origin of the symmetry breaking observedexperimentally in the latter system. Moreover, the computationalscheme used here allows to study the quantizationof the translational movement of the encapsulated watermolecule inside theC70fullerene, and to investigate theconfinement effects in the vibrational energy levels of theH2O@C70 system.

Fullerene C60 protects against 7,12-dimethylbenz [a] anthracene (DMBA) induced-pancreatic damage via NF-κB and Nrf-2/HO-1 axis in rats.

The objective of this investigation was to investigate the protective effects of fullerene C60 nanoparticle against pancreatic damage experimentally induced by 7,12-dimethylbenz [a] anthracene (DMBA) in female rats. Fullerene C60 nanoparticle was administered to rats 5 times a week by oral gavage (o.g) at 1.7mg/kg bw 7days after DMBA administration. 60 Wistar albino female rats divided to four groups; Groups: (1) Control group: Fed with standard diet; (2) Fullerene C60 group: Fullerene C60 (1.7mg/kg bw); (3) DMBA group: DMBA (45mg/kg bw); (4) Fullerene C60+DMBA group: Fullerene C60 (1.7mg/kg bw) and DMBA (45mg/kg bw). Lipid peroxidation malondialdehyde (MDA), catalase activity (CAT) and glutathione (GSH) levels in pancreatic tissue were determined by spectrophotometer. Protein expression levels of p53, HO-1, p38-α (MAPK), Nrf-2, NF-κB and COX-2 in pancreatic tissue were determined by western blotting technique. In our findings, compared to the group given DMBA, MDA levels and p38-α, NF-κB and COX-2 levels decreased, CAT activity, GSH level, total protein density and p53, HO-1, Nrf-2 levels in the groups given fullerene C60 nanoparticle an increase in expression levels was observed. Our results showed that fullerene C60 nanoparticle may be more beneficial in preventing pancreatic damage.

Study of the Application of Recycled Gold Nanoparticles in Coatings for Eyewear Lenses

The surface plasmon resonance of gold nanoparticles causes visible light absorption and scattering effects that may be used in optical coatings for eliminating blue light emission from display monitors, for blocking UV light, and for decorative applications. This study examines the achievement of functional properties provided by gold nanoparticles in a commercially established C60 fullerene-coated eyewear product. The gold nanoparticles used were sourced from recycling rapid lateral flow tests (LFIA), which use gold nanoparticles as test markers. After the gold’s recovery, Ultrasonic Spray Pyrolysis (USP) with freeze-drying was used for the synthesis of new gold nanoparticles, to be used in optical coatings. The gold nanoparticles were examined with SEM, TEM, DLS, zeta potential, BET, and Vis-NIR for characterising their shapes and sizes, as is required for determination of the surface plasmon resonance effect. After applying the newly produced gold nanoparticles with fullerene C60 in a combined coating for eyewear lenses, the absorption and transmission of the lenses were determined for establishing changes in the coating’s functionality. The results show that enhancing the fullerene C60 coating with gold nanoparticles improves light absorption and reflectance for blue and UV light further, which may be evaluated as beneficial for the eyewear user, as the reduction in eye strain is increased due to the coating.

OPTICAL PROPERTIES OF CARBON CONTAINING NANOCOMPOSITE FILMS BASED ON THE POLYSTYRENE-FULLERENE C60 SYSTEM

Carbon-based nanocomposites have attracted significant attention due to their unique properties and potential for use in various technological applications. In this study, experimental investigations were conducted to determine the spectral properties of carbon-containing nanocomposite polymer films based on polystyrene (PS) with fullerene C60 nanoadditives. The results indicate that the incorporation of fullerene nanoparticles into the PS matrix enhances the optical properties of the material. Specifically, the optical density of the samples increases, the absorption coefficient increases, and the width of the bandgap decreases with an increase in carbon additive concentration. These findings suggest that fullerene-based nanocomposites are promising materials for optoelectronic and nanotechnological applications. The results of this work contribute to the growing body of research on carbon-based nanocomposites and their potential for use in a range of fields, including electronics, energy storage, and sensing applications. The enhanced optical properties of fullerene-based nanocomposites suggest that they may be particularly useful for developing novel optoelectronic devices and sensors. Overall, this study highlights the potential of fullerene-based nanocomposites as a versatile and promising material platform for various technological applications.