Interaction Of Fullerenes Research Articles

Core-Hole Excitation Spectra of the Oxides and Hydrates of Fullerene C60 and Azafullerene C59N

The interaction of fullerenes and their derivatives with environmental molecules such as oxygen or water was crucial for the rational design of low-dimensional materials and devices. In this paper, the near-edge X-ray absorption fine structure (NEXAFS), X-ray emission spectroscopy (XES) and X-ray photoelectron spectroscopy (XPS) shake-up satellites were employed to distinguish the oxides and hydrates of the fullerene C60 and azafullerene C59N families. The study includes various isomers, such as the open [5,6] and closed [6,6] isomers of C60O, C60H(OH), C60-O-C60, C60H-O-C60H, C59N(OH) and C59N-O-C59N, based on density functional theory. These soft X-ray spectra offered comprehensive insights into the molecular orbitals of these azafullerene molecular groups. The oxygen K-edge NEXAFS, carbon and oxygen K-edge XPS shake-up satellite spectra provided valuable tools for distinguishing oxides or hydrates of fullerene C60 and azafullerene C59N. Our findings could significantly benefit the development of fullerene functional molecular materials and expand the application scope of soft X-ray spectroscopy as a molecular fingerprinting tool for the fullerene family.

Высокоточные представления Ван-дер-Ваальсовских взаимодействий

This paper considers the interactions between two and three fullerenes using the methods of molecular dynamics. The results show that at a time step of one femtosecond, very high calculation accuracy can be achieved regarding the kinematic and energy parameters of the interaction. Thus, the details associated with the symmetry of the relative opposition of molecular objects are revealed, and the features and nature of the transition of two-dimensional motions of interacting objects into three-dimensional interaction of fullerenes are clarified, in particular, the interaction with the formation of a kinematic pair. The role of the initial spin of the fullerenes, which disables the transition of kinematic energy from the reservoir of translational energy into rotational energy, is also identified. This makes the formation of a kinematic pair impossible. In the general case, the triple collision of fullerenes is a complex process, in which, even in the special case of plane approximation, three phases can be distinguished: initial planar motion, multi-sheet spatial interaction of three objects, and a double spiral of interacting molecules with the linear motion of the discarded fullerene.

Density functional theory study on the interaction of C60 fullerene with PCBM

Functionalized fullerenes are known as high-performance molecules. Herein, the interaction of C60 fullerene with Phenyl-C61-butyric-acid-methyl-ester (PCBM) is investigated by means of density functional theory method to elucidate the structures and electronic states of C60-PCMB complexes. C60-PCBM blends are typically used in solar cell. Studying the electronic structure of C60-PCBM is important for elucidating the mechanism of solar cells. The intermolecular distances for C60 and PCBM dimers were calculated to be 3.70 and 2.34 Å, respectively. In C60 dimer, the five membered ring of C60 interacted with the six membered ring of neighbour C60. Two hydrogen bonds between side chains of PCBM are connected in the PCBM dimer. The binding energies were 1.4 kcal mol−1 (C60 dimer) and 2.6 kcal mol−1 (PCBM dimer). In the C60-PCBM complex, five different structures were found to be stable. The binding energies were distributed in the range 1.6–3.7 kcal mol−1. The electronic states and excitation energies of C60-PCBM complexes and the basis set superposition error were discussed on theoretical results.

Exploring Fullerene-Perovskite Interactions by Means of Density Functional Simulations

Boosting renewable energies is the 7th goal in the 2030 Agenda for Sustainable development whose premise is to accelerate the transition towards a low-carbon competitive economy. Sunlight is the largest exploitable resource of energy and it has promoted an extraordinary growth of photovoltaic (PV) cell technology to supply the demand. Several PV manufacturers are now working on bringing solar cell devices based on organic-inorganic hybrid perovskite (PSCs) to market due to their easy fabrication procedures, low cost, and the fast improvement of their efficiency (PCE). In order to enhance the possibility for PSCs to be competitive throughout the market, a very recent technology introduces Fullerene (C60) and its derivatives -specially [6,6]-phenyl-C61-butyric acid methyl ester (PCBM)- in PSC devices to work as electron transport layer (ETL), additives, or to control the crystal growth, either in conventional or inverted devices. The use of fullerenes have eliminated/reduced the hysteresis,[1] improved the device stability in comparison to fullerene-free standard PSCs,[2] and favors the high-scale preparation because the high-temperature step.Nevertheless, important features in the state-of-the-art fullerene-perovskite devices remain unexplored. It is known that fullerenes passivate the perovskite defects, improving the optoelectronic properties, but it has not been systematically explored to date. It is not extensively investigated the effect of binding groups of fullerenes, how fullerenes passivate the perovskite surfaces and how passivation influence surface energetics and the corresponding carrier dynamics. In this work we use periodic density functional simulations to explore the interaction of fullerenes with different perovskite surfaces, considering as well possible defects (Iodide anti-sites) and vacancies (cation vacancies). Computing the binding energy, the adsorption energy site, bandgaps, and density of states we are able to compare these relevant descriptors with the experimental efficiency, in order to find the key descriptors that govern the fullerene-perovskite interactions. In this presentation, we will show our results for APbI3 (A= methylammonium, Cs) perovskite surfaces with the most common fullerenes like C60 and PC61BM. Our simulations show different binding energies depending on the perovskite and surface vacancy and the effect on the electronic structure will be discussed.1. J. Xu, et. al., Nat. Commun. 2015,6, 7081; Y. Zhong, et. al., Adv. Funct. Mater. 2020, 1908920.2. V. Ferguson, et. al., Energy Environ. Mater. 2019, 2, 107–118; T. Gatti et. al., Nano Energy, 2017, 41, 84−100. Figure 1

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.

Vibrationally resolved deep–red circularly polarised luminescence spectra of C70 derivative through Gaussian curvature analysis of ground and excited states

Over the last years, the interaction of fullerene with circularly polarized light has attracted growing attention for potential electronic and optical applications. However, in literature there is only one example of fullerene derivative capable of emitting circularly polarized light, showing an active circularly polarized luminescence (CPL) signal in the deep-red visible region. This unique luminophore offered us the possibility to study the connection between the topological features of C70 spheroid and its chiral emission properties. In light of these considerations, we proposed a theoretical protocol that combines three different step: (1) The Ball Pivoting Algorithm for C70 surface reconstruction. (2) The discrete gaussian curvature analysis in the ground (S0) and excited states (S1). (3) The computation of the vibrationally-resolved CPL spectrum. The first step allowed us to extract useful information that linked the topological shape of C70 to the sp2 carbon network chemistry. The DFT benchmark in the second step guided us in grasping the best functional for the C70 curvature simulation in the ground state, spotlighting how B97D3 excellently succeed for this task. The curvature investigation in the first excited state showed that (for all the twenty exchange–correlation functional tested) the C70 fragment is more curved in S1 than in S0. The final step collected the topological information from the previous sections to provide a detailed overview of the theoretical factors (such as the quantum formalism, the potential energy surface description and the transition dipole moment approximation) impacting on the C70 vibrationally resolved CPL spectrum. We found that the adiabatic hessian model coupled with the Franck-Condon Herzberg-Teller approximation computed at PW6B95D3/6-311G(d,p) level provides excellent results in emulating the band-shape and position of the experimental CPL spectrum.

Probing the Interaction of NO with C60: Comparison between Endohedral and Exohedral Complexes

Recent advances in synthetic methodologies have opened new strategies for synthesizing stable metal-free electron spin systems based on fullerenes. Introducing nitric oxide (NO) inside a fullerene cage is one of the methods to attain this goal. In the present study, dispersion corrected density functional theory (B3LYP-D3) has been used to evaluate the structure, stability, and electronic properties of NO encapsulated fullerene NO@C60 and compared those with its exohedral fullerene NO.C60 analog. The calculated stabilization energy for NO@C60 is appreciably higher than NO.C60, and this difference is comprehended via the Quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) topological analyses. The delocalization of electron density of NO and the C60 cage in NO@C60 is discussed using electrostatic potential analysis. In addition, an attempt has been made to understand the different locations and orientations involving the interaction of two NO radicals and the fullerene C60. It is shown that the encapsulation of the NO dimer inside the C60 cage is an energetically unfavorable process. On the other hand, stable structures are obtained upon the physisorption of other NO on the surface of NO@C60 and NO.C60. The present work provides an in-depth understanding of the interaction of NO and C60 fullerene, its preferable position, and its orientation in both endohedral and exohedral complexes.

Theoretical study of the interaction of fullerenes with the emerging contaminant carbamazepine for detection in aqueous environments

The global increase in drug consumption exposes the growing need to develop new systems for the detection, capture, and treatment of bioactive molecules. Carbamazepine is one instance of such contaminants at the top of the ranking commonly found in sewage treatment systems. This work, therefore, presents a theoretical study of fullerene C60 and its derivatives with substitutional doping with B, Al, Ga, Si, Ge, N and P, for the detection and capture of carbamazepine is aqueous medium. Solvation effects were included by means of the Polarizable Continuum Solvent method. The results indicate that doped fullerenes are sensitive for the detection of carbamazepine both in gaseous and aquatic environments. Investigation on the intermolecular interactions between the drug and the fullerene molecule were carried out, allowing the characterization of the interactions responsible for stabilizing the adsorption of carbamazepine to the fullerenes. The theoretical survey revealed that fullerenes doped with Al, Ga, Si and Ge chemically adsorb carbamazepine whereas for the case of fullerenes doped with other heteroatoms physisorption is responsible for the molecular recognition. Relying on DFT calculations, the fullerene derivatives C59Al, C59Si and C59Ga are the most suitable to act both as a sensor and to uptake carbamazepine in aquatic environments.

Ab Initio Insight into the Interaction of Metal-Decorated Fluorinated Carbon Fullerenes with Anti-COVID Drugs.

We theoretically investigated the adsorption of two common anti-COVID drugs, favipiravir and chloroquine, on fluorinated C60 fullerene, decorated with metal ions Cr3+, Fe2+, Fe3+, Ni2+. We focused on the effect of fluoridation on the interaction of fullerene with metal ions and drugs in an aqueous solution. We considered three model systems, C60, C60F2 and C60F48, and represented pristine, low-fluorinated and high-fluorinated fullerenes, respectively. Adsorption energies, deformation of fullerene and drug molecules, frontier molecular orbitals and vibrational spectra were investigated in detail. We found that different drugs and different ions interacted differently with fluorinated fullerenes. Cr3+ and Fe2+ ions lead to the defluorination of low-fluorinated fullerenes. Favipiravir also leads to their defluorination with the formation of HF molecules. Therefore, fluorinated fullerenes are not suitable for the delivery of favipiravir and similar drugs molecules. In contrast, we found that fluorine enhances the adsorption of Ni2+ and Fe3+ ions on fullerene and their activity to chloroquine. Ni2+-decorated fluorinated fullerenes were found to be stable and suitable carriers for the loading of chloroquine. Clear shifts of infrared, ultraviolet and visible spectra can provide control over the loading of chloroquine on Ni2+-doped fluorinated fullerenes.

Gadolinium Endofullerenes.

Fullerenes-A new combining atoms of carbon atoms into the molecule, which can serve as the parent and precursor of a whole class advanced organic compounds. Unsolved problems associated with a correct understanding of the structure, transformation, and behavior of the fullerene C60 molecule, make it impossible to interpret correctly many of its physicochemical properties. Fullerenes are a new compounds of carbon atoms into a molecule that can serve as the parent and precursor of the whole class of the newest organic compounds. Unresolved problems connected with correct understanding of structure, transformation and behavior of fullerene molecule C60, do not allow to interpret many of its physico-chemical properties correctly. Since the discovery of fullerenes and the subsequent study of their properties, the interaction of fullerenes with metals is of fundamental interest. C60-building block (molecule), is similar to the atom, which can be used to create new materials. It has its physical and chemical properties, which a separate atom can't exhibit. First of all it concerns the fact that this molecule, unlike all molecules known up to the present time, has its own surface. The presence of the surface allows the fullerene molecule to behave as a molecule and as a solid nanoparticle. The dualism of the fullerene molecule allows it, unlike other carbon allotropic forms, to dissolve in various liquid mediums. The presence of the surface allows fullerene to enclose in its volume separate atoms and molecules. After the initial detection of fullerenes, multiple attempts are made to obtain, distinguish and characterize fullerenes containing metal atoms in their volume. In the present work the research of the products formed in joint arc evaporation of graphite and gadolinium is carried out. The products formed on the cathode and on the reactor walls are investigated. On the example of gadolinium-containing endofullerenes the conditions of formation of nanoproducts in plasma conditions, in solutions and at their crystallization are discussed.

Some aspects concerning the interaction of C70 fullerene with poly(L-lactic acid) (PLLA)

The equilibrium constant of the PLLA-C70 complex was determined spectrophotometrically and found at 1084 M−1, a value fully comparable with the equilibrium constant of the PLLA-C60 complex 956 M−1. In fact, both C60 and C70 share practically the same electron affinity and both are able to form charge-transfer complex with poly(L-lactic acid) (PLLA) in dichloromethane solution. The PLLA-C70 complex in CH2Cl2 solution shows also a pronounced extrinsic or induced Cotton effect when analyzed with optical rotatory dispersion (ORD) spectroscopy suggesting a kind of host-guest interaction where the helical conformation of PLLA by binding C70 internally or externally to the helical coils, is able to induce the optical activity to the achiral C70.

Assessing the DOPC-cholesterol interactions and their influence on fullerene C60 partitioning in lipid bilayers

We propose a computational Molecular Dynamic (MD) study to evaluate the interaction of C60 fullerene in contact with lipid membranes, as a function of the bilayers cholesterol content. Pure 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and DOPC/cholesterolXX (XX = 10%, 20% and 30%) membranes where investigated. An analysis involving umbrella pulling techniques to force the extraction of DOPC lipid and/or cholesterol molecules in comparison with an insertion of a fullerene C60 molecule into the lipid/cholesterol membranes was performed in order to verify the force/energy required for the C60@DOPC/cholesterol partitioning. In addition, electron spin resonance experiments using a lipid and an amphiphilic spin labels were performed to investigate the DOPC-cholesterol interactions and to mimic the C60 fullerene-membrane interactions. The spectroscopic results corroborated the MD ones and indicated that the presence of cholesterol in the lipid bilayers increased the membrane rigidity as well as the force required to C60 insertion/extraction.

Fullerene C60 containing porphyrin-like metal center as drug delivery system for ibuprofen drug.

Today, drug delivery systems based on nanostructures have become the most efficient to be studied. Recent studies revealed that the fullerenes can be used as drug carriers and transport drugs in a target cell. The aim of the present work is to study the interaction of C60 fullerene containing porphyrin-like transition metal-N4 clusters (TMN4C55, TM = Fe, Co, and Ni) with a non-steroidal anti-inflammatory drug (ibuprofen (Ibp)) by employing the method of the density functional theory. Results showed that the C60 fullerene with TMN4 clusters could significantly enhance the tendency of C60 for adsorption of ibuprofen drug. Also, our ultraviolet-visible results show that the electronic spectra of Ibp/TMN4C55 complexes exhibit a blue shift toward lower wavelengths (higher energies). It was found that the NiN4C55 fullerene had high chemical reactivity, which was important for binding of the drug onto the carrier surface. In order to gain insight into the binding features of Ibp/TMN4C55 complexes, the atoms in molecules analysis was also performed. Our results exhibit the electrostatic features of the Ibp/TMN4C55 bonding. Consequently, this study demonstrated that the TMN4C55 fullerenes could be used as potential carriers for delivery of Ibp drug in the nanomedicine domain. Graphical Abstract The TMN4C55 (TM=Fe, Co, and Ni) fullerenes could be used as potential carriers for delivery of ibuprofen drug in the nanomedicine domain.

Porphyrin-like porous nanomaterials as drug delivery systems for ibuprofen drug

In recent years, nanomaterial-based drug delivery carriers have become some of the most attractive to be studied. The purpose of this study is to investigate the interaction of C60 fullerene, carbon nanotube and graphene having porphyrin-like FeN4 clusters with a non-steroidal anti-inflammatory drug (ibuprofen) by means of the density functional theory. Results showed that the graphene with FeN4 clusters could remarkably increase the tendency of graphene for adsorption of ibuprofen drug. Also, our ultraviolet–visible results show that the electronic spectra of the complexes exhibit a blue shift toward lower wavelengths (higher energies). It was found that Ibp/FeN4-graphene had high chemical reactivity, which was important for binding of the drug onto the target site. In order to go further and gain insight into the binding features of considered systems with ibuprofen drug, the Atoms in Molecules analysis was performed. Our results determine the electrostatic features of the Ibp/FeN4-graphene bonding. Consequently, the results demonstrated that the FeN4-graphene could be used as potential carriers for the delivery of ibuprofen drug.

Antagonistic Interactions between Benzo[a]pyrene and Fullerene (C60) in Toxicological Response of Marine Mussels.

This study aimed to assess the ecotoxicological effects of the interaction of fullerene (C60) and benzo[a]pyrene (B[a]P) on the marine mussel, Mytilus galloprovincialis. The uptake of nC60, B[a]P and mixtures of nC60 and B[a]P into tissues was confirmed by Gas Chromatography–Mass Spectrometry (GC–MS), Liquid Chromatography–High Resolution Mass Spectrometry (LC–HRMS) and Inductively Coupled Plasma Mass Spectrometer (ICP–MS). Biomarkers of DNA damage as well as proteomics analysis were applied to unravel the interactive effect of B[a]P and C60. Antagonistic responses were observed at the genotoxic and proteomic level. Differentially expressed proteins (DEPs) were only identified in the B[a]P single exposure and the B[a]P mixture exposure groups containing 1 mg/L of C60, the majority of which were downregulated (~52%). No DEPs were identified at any of the concentrations of nC60 (p < 0.05, 1% FDR). Using DEPs identified at a threshold of (p < 0.05; B[a]P and B[a]P mixture with nC60), gene ontology (GO) and Kyoto encyclopedia of genes and genomes (KEGG) pathway analysis indicated that these proteins were enriched with a broad spectrum of biological processes and pathways, including those broadly associated with protein processing, cellular processes and environmental information processing. Among those significantly enriched pathways, the ribosome was consistently the top enriched term irrespective of treatment or concentration and plays an important role as the site of biological protein synthesis and translation. Our results demonstrate the complex multi-modal response to environmental stressors in M. galloprovincialis.

Model of Interaction of Fullerene С60 with Epitaxial Graphene

Equations for the potential and force of interaction of fullerene C60 with epitaxial graphene adsorbed on a thick substrate were derived using the Lennard-Jones pair potential. The nature of this interaction is mainly determined by the fullerene–graphene system, while the substrate makes a critical contribution to the attraction force at long distances between fullerene and graphene. A numerical simulation of the incidence of the fullerene molecule on epitaxial graphene was performed. The molecule oscillates near the surface; the character of this motion depends on the initial conditions and interaction parameters. An equation for the specific adhesion energy of graphene was obtained.

Interaction of polyhydroxy fullerenes with ferrihydrite: adsorption and aggregation

The rapid development of nanoscience and nanotechnology, with thousands types of nanomaterials being produced, will lead to various environmental impacts. Thus, understanding the behaviors and fate of these nanomaterials is essential. This study focused on the interaction between polyhydroxy fullerenes (PHF) and ferrihydrite (Fh), a widespread iron (oxyhydr)oxide nanomineral and geosorbent. Our results showed that PHF were effectively adsorbed by Fh. The adsorption isotherm fitted the D-R model well, with an adsorption capacity of 67.1mg/g. The adsorption mean free energy of 10.72kJ/mol suggested that PHF were chemisorbed on Fh. An increase in the solution pH and a decrease of the Fh surface zeta potential were observed after the adsorption of PHF on Fh; moreover, increasing initial solution pH led to a reduction of adsorption. The Fourier transform infrared spectra detected a red shift of C–O stretching from 1075 to 1062cm−1 and a decrease of Fe–O bending, implying the interaction between PHF oxygenic functional groups and Fh surface hydroxyls. On the other hand, PHF affected the aggregation and reactivity of Fh by changing its surface physicochemical properties. Aggregation of PHF and Fh with individual particle sizes increasing from 2nm to larger than 5nm was measured by atomic force microscopy. The uniform distribution of C and Fe suggested that the aggregates of Fh were possibly bridged by PHF. Our results indicated that the interaction between PHF and Fh could evidently influence the migration of PHF, as well as the aggregation and reactivity of Fh.

Effect of Microwave Radiation on the Band Structure and Electronic Parameters of the Heterosystems with Fullerenes

The results of a complex study of C60/Si heterosystems are presented in this work: the crystal structure and composition of the films, internal mechanical stresses, electronic parameters of the film and the film-substrate interface, and the effect of external influences (ultraviolet irradiation, thermal annealing, gamma and microwave irradiation). The advantage of microwave treatment over others is established: the absence of fullerene decomposition, the removal of internal mechanical stresses in the heterosystem, and the improvement of its electronic parameters. Methods for remove the decomposition of C60 molecules under the influence of other treatments have been developed. To eliminate the interaction of fullerenes with oxygen, it was proposed to perform thermal annealing and UV irradiation in vacuum, and in the case of g-irradiation, apply a protective coating on the surface of the film (GeOx or SiOx). In solar cells with C6 films in the polymer matrix on Si, a significant advantage of titanium contacts in comparison with gold is established, especially after microwave treatment. Contact resistance decreased as a result of hybridization of 3d-orbitals of titanium and 2p-orbitals of fullerenes with the formation of ТіхС60 carbides and radiation-stimulated diffusion of metals, which increases the contact area.

DFT and TD-DFT theoretical studies on photo-induced electron transfer process on [Cefamandole].C60 nano-complex

The C60 fullerene displays a considerable electronegativity. It has a unique photophysical and electrochemical behavior that can be used as a suitable drug carrier. In the present study, the interaction of C60 fullerene as an electron recipient with the Cefamandole antibiotic was investigated in both ground and excited states using DFT and TD-DFT methods. The study of the interaction of C60 and Cefamandole via electron localization function (ELF) and reduced density gradient (RDG) revealed that the complex formation is of van der Waals type. The data from natural bonding orbitals (NBO) analysis also confirmed the interaction type. The study of absorption and emission spectrum via CAM-B3LYP in the TD-SCF state showed that the emission peak of C60 fullerene in the 591.73nm after the complex formation results in the extinction of this emission spectrum due to charge transfer (CT) from chelator to fluorophore. The photoinduced electron transfer (PET) process was investigated using the electron hole theory.

The Role of Super-Atom Molecular Orbitals in Doped Fullerenes in a Femtosecond Intense Laser Field

The interaction of gas phase endohedral fullerene Ho3N@C80 with intense (0.1–5 × 1014 W/cm2), short (30 fs), 800 nm laser pulses was investigated. The power law dependence of Ho3N@C80q+, q = 1–2, was found to be different from that of C60. Time-dependent density functional theory computations revealed different light-induced ionization mechanisms. Unlike in C60, in doped fullerenes, the breaking of the cage spherical symmetry makes super atomic molecular orbital (SAMO) states optically active. Theoretical calculations suggest that the fast ionization of the SAMO states in Ho3N@C80 is responsible for the n = 3 power law for singly charged parent molecules at intensities lower than 1.2 × 1014 W/cm2.