Search Results (110)

Germanium (Ge) incorporation profoundly modifies the structural and electronic characteristics of carbon fullerenes, giving rise to a diverse landscape of substitutional, exohedral, and endohedral Ge–fullerene architectures. Although experimental studies demonstrate that Ge can be introduced into fullerene matrices through nuclear recoil implantation and arc-discharge synthesis, only exohedral germylated derivatives have been structurally confirmed to date. Substitutional germanium-doped fullerene (Ge-C₆₀) species remain experimentally elusive, with available evidence relying largely on radiochemical signatures and indirect spectroscopic data. In contrast, computational investigations provide a detailed and coherent picture of germanium doping across fullerene sizes, showing that Ge induces significant cage distortion, breaks local symmetry, narrows the highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) gap, and enhances charge localization at the dopant site. These electronic perturbations strongly increase the affinity of Ge-doped fullerenes for external guest molecules, leading to enhanced adsorption energies and distinct optical and transport responses in exohedral complexes. Theoretical studies of endohedral systems further indicate that Ge atoms or small clusters could form stable encapsulated species with unique electronic properties. Collectively, current evidence positions germanium-doped fullerenes as electronically versatile nanostructures with potential applications in sensing, optoelectronics, catalysis, and nanomedicine, while highlighting the need for definitive experimental synthesis and structural validation of substitutional Ge-fullerene derivatives. Full article

Fullerenes are promising drug candidates, but they are virtually insoluble in water. Surface hydroxylation of fullerenes and their encapsulation in nanocarrier systems, such as dendrimers, can be used to increase their solubility. However, hydroxylated fullerene (hydroxyfullerene, fullerenol) has lower bioactivity than fullerene. Our previous research showed that fullerene is encapsulated by the Lys-2Gly dendrimer. This study demonstrates, for the first time, that hydroxylated fullerenes C₆₀(OH)n with n = 12, 24, 36 form complexes with the same dendrimer. All these fullerenols are encapsulated near the dendrimer’s center, similar to fullerene. Surprisingly, the complex’s structure remains stable even at the maximal hydroxylation (n = 36), despite a significant reduction in hydrophobicity of the fullerene surface. We demonstrated that this stability results from an increase in the number of hydrogen bonds between the dendrimer and the fullerenol with increasing n. Thus, we established that the mechanism of complex formation changes from hydrophobic interactions to hydrogen bonding as hydroxylation increases. This means that simultaneous partial hydroxylation of the fullerene and encapsulation within a water-soluble dendrimeric nanocarrier enhances its solubility in water. This combined approach enables the use of less hydroxylated fullerene derivatives to achieve desired solubility while maintaining higher biological activity. Full article

Fullerenols are polyhydroxylated derivatives of fullerene (C₆₀(OH)_n) with antioxidant, antiviral, and antibacterial properties and potential biomedical applications due to their solubility and biocompatibility. However, comprehensive assessment of their cytotoxicity is required, particularly regarding their effects on immune system cells. This study investigated the effects of fullerenol C₆₀(OH)₂₄ (MST-Nano, St. Petersburg, Russia) on the viability, apoptosis, and metabolism of THP-1 human monocytic leukemia cells. Cells were treated with concentrations ranging from 0.25 to 1000 µg/mL and incubated for 24, 48, and 72 h. Viability, apoptosis, and nanoparticle association were assessed by flow cytometry; glycolysis and mitochondrial respiration were measured after 24 h on a Seahorse XFe96 analyzer (Agilent Technologies, Santa Clara, CA, USA). Results showed that the effects of fullerenol depend on concentration and exposure time. At 24 h, 750 µg/mL increased viability, while 1000 µg/mL induced apoptosis. After 48 and 72 h, apoptosis increased at concentrations ≥750 µg/mL, with reduced viability. Nanoparticle association correlated with concentration and inversely correlated with viability but was independent of incubation time. Metabolic analysis revealed decreased glycolysis at 750 µg/mL after 24 h, while mitochondrial respiration was unaffected. Thus, our study demonstrated that fullerenol nanoparticles were safe for the THP-1 monocytic cell line up to 500 µg/mL. Full article

To overcome the negative effects of the biochemical application of nano-substances in medicine (toxicity problem), using the example of fullerene C₆₀’s first derivative (fullerenol, FD-C₆₀), we show that their biophysical effect is possible through non-covalent hydrogen bonds when around FD-C₆₀ water layers are formed. SD-C₆₀ (Zeta potential is −43.29 mV) is much more stable than fullerol (Zeta potential is −25.85 mV), so agglomeration/fragmentation of the fullerol structure, due to instability, can cause toxic effects. When fullerol in solution was exposed to an oscillatory magnetic field with Re (real) part [250/−92 mT, H(ωt) = Acos(ωt)], water layers around FD-C₆₀ (fullerenol) are formed according to the Penrose process of 3D tiling formation, and the second derivative, SD-C₆₀ (or 3HFWC), is self-organized. However, when Im (imaginary) part [250/−92 mT, H(ωt) = Bisin (ωt)] of the external magnetic field is applied in addition to SD-C₆₀, ordered water chains and bubbling of water (“micelle”) are formed as a third derivative (TD-C₆₀). Fullerol (FD-C₆₀) interacts with biological structures biochemically, while the second (SD-C₆₀) and third (TD-C₆₀) derivatives act biophysically via non-covalent hydrogen bond oscillation. SD-C₆₀ and TD-C₆₀ significantly increased water solubility and reduced toxicity. The paper explains the synthesis of SD-C60 and TD-C60 from FD-C60 (fullerol) as a precursor by the influence of an oscillatory magnetic field (“Yin-Yang” principle) on hydrogen bonds in order to create water layers around fullerol. Examples of biomedical applications (cancer and Alzheimer’s) of this synergetic complex are given. This study shows that the “Yin-Yang” machinery, based on the nanophysics of C₆₀ molecules and non-covalent hydrogen bonds, is possible. The first attempt has been composed to synthesize nanomaterial for biophysical vibrational nanomedicine. Full article

A direct non-catalytic synthesis of a new water-soluble polynitro-hydroxylated fullerene derivative, C₆₀(NO₂)₁₈(OH)₂, was carried out using a mixture of concentrated nitric and sulfuric acids. The resulting poly-nitro adduct was comprehensively characterized by elemental C-H-N analysis, energy-dispersive X-ray spectroscopy, infrared (IR) and electron spectroscopy, nuclear magnetic resonance (NMR), high-performance liquid chromatography (HPLC), and thermogravimetric analysis (TGA). A detailed investigation of the physicochemical properties of aqueous solutions of C₆₀(NO₂)₁₈(OH)₂ demonstrated that the synthesized compound is a previously undescribed mixed polynitro-hydroxyl adduct of light fullerene C₆₀, featuring a high degree of nitration (18 nitro groups per fullerene core). The composition and structure of the adduct were confirmed by spectroscopic and refractometric analyses. In terms of redox behavior, the compound exhibits significant reducing and antioxidant properties. These physicochemical characteristics suggest the potential of C₆₀(NO₂)₁₈(OH)₂ for further development as a biocompatible nanomaterial suitable for medical applications. Full article

Fullerenes, a unique allotrope of carbon, have captured significant attention in multiple scientific fields. As a non-destructive characterization technique, Raman spectroscopy has proven indispensable for investigating fullerenes and their derivatives, offering detailed insights into their vibrational properties. This review discusses the broad utility of Raman spectroscopy in revealing the structural and physicochemical characteristics of fullerenes—from the iconic C₆₀ molecule to an array of its derivatives—highlighting its capacity to detect functionalization-induced changes in molecular structure and electronic properties, while also assessing environmental influences such as solvent effects and temperature variations. Particular emphasis is placed on advanced Raman-based techniques, including enhanced Raman spectroscopy, surface-enhanced Raman spectroscopy (SERS), and tip-enhanced Raman spectroscopy (TERS), for the characterization of fullerenes and their derivatives. These cutting-edge methods offer high sensitivity and ultra-high spatial resolution, greatly expanding the scope of fullerene research and delivering deeper insights into their structural and functional properties. Full article

Fullerene C₆₀ is by far the most studied of all allotropic modifications of carbon. Chemical modification of the double bond over the years has led to the emergence of a variety of fullerene derivatives. These derivatives have now found numerous applications in medicine, materials and supramolecular chemistry, and as efficient electron acceptors in organic photovoltaic devices. The main method for the functionalization of C₆₀ fullerenes, which makes it possible to obtain its derivatives in a preparative volume, is the Bingel–Hirsch reaction. But this method makes it possible to obtain fullerocyclopropanes containing only carboxyl substituents at the bridging carbon atom. Therefore, in order to obtain new materials, we began to study the interaction with organic carbonates in combination with Grignard reagents in the presence of Ti-containing complex catalysts. We hope that replacing the olefin in the Kulinkovich reaction with a C₆₀ fullerene molecule will lead to new and hard-to-find functionalization products of the latter. Organic carbonates were chosen as the object of study due to the fact that they are used in the industry as solvents for natural and synthetic resins, cellulose ethers, dispersants, blowing agents, emulsifiers, absorbents of hydrogen sulfide and carbon dioxide, starting materials for the industrial synthesis of fibers and plastics, as well as plasticizers, pharmaceuticals and plant protection products. Full article

Nowadays, the development of devices based on organic materials is an interesting research challenge. The performance of such devices is strongly influenced by material selection, material properties, design, and the manufacturing process. Usually, buckminsterfullerene (C60) is employed as electron transport material in organic photovoltaic (OPV) devices due to its high mobility. However, considering its low solubility, there have been many attempts to replace it with more soluble non-fullerene compounds. In this study, bulk heterojunction thin films with various compositions of zinc phthalocyanine (ZnPc), a perylene diimide derivative, or C60 were prepared by matrix-assisted pulsed laser evaporation (MAPLE) technique to assess the influence of C60 replacement on fabricated heterostructure properties. The investigations revealed that the optical features and the electrical parameters of the organic heterostructures based on this perylene diimide derivative used as an organic acceptor were improved. An increase in the J_SC value (4.3 × 10⁻⁴ A/cm²) was obtained for the structures where the perylene diimide derivative acceptor entirely replaced C60 compared to the J_SC value (7.5 × 10⁻⁸ A/cm²) for the heterostructure fabricated only with fullerene. These results are encouraging, demonstrating the potential of non-fullerene compounds as electron transport material in OPV devices. Full article

The hybrid system BiVO₄/g-C₃N₄ is a prospective photocatalyst because of the favorable mutual alignment of the energy bands of both semiconductors. However, the path of the photocatalytic process is still unclear because of contradictory information in the literature on whether the mechanism of charge carrier separation at the BiVO₄/g-C₃N₄ interface is band-to-band or Z-scheme. In this work, we clarified this issue by comparative photocatalytic studies with the use of systems without a mediator and with different kinds of mediators including Au nanoparticles, fullerene derivatives, and the Fe³⁺/Fe²⁺ redox couple. Additionally, the charge transfer dynamics at the BiVO₄/g-C₃N₄ and BiVO₄/mediator/g-C₃N₄ interfaces were investigated by time-resolved photoluminescence (TRPL) measurements, while the influence of the mediator on the surface recombination of the charge carriers was verified by intensity-modulated photocurrent spectroscopy (IMPS). We proved that the charge carrier separation at the BiVO₄/g-C₃N₄ interface occurs according to the mechanism typical for a heterojunction of type II, while the incorporation of the mediator between BiVO₄ and g-C₃N₄ leads to the Z-scheme mechanism. Moreover, a very strong synergetic effect on caffeine (CAF) degradation rate was found for the system BiVO₄/Au/g-C₃N₄ in the presence of Fe³⁺ ions in the CAF solution. Full article

Among C₆₀’s diverse functionalities, its potential application in CO₂ sequestration has gained increasing interest. However, the processes involved are sensitive to the molecule’s electronic structure, aspects of which remain debated and require greater precision. To address this, we performed structural optimization of fullerene C₆₀ using the QM MP2/6–31G* method. The nonplanarity of the optimized icosahedron is characterized by two types of dihedral angles: 138° and 143°. The 120 dihedrals of 138° occur between two hexagons intersecting at C–C bonds of 1.42 Å, while the 60 dihedrals of 143° are observed between hexagons and pentagons at C–C bonds of 1.47 Å. NBO analysis reveals less pyramidal sp^1.78 hybridization for carbons at the 1.42 Å bonds and more pyramidal sp^2.13 hybridization for the 1.47 Å bonds. Electrostatic potential charges range from −0.04 a.u. to 0.04 a.u. on the carbon atoms. Second-order perturbation analysis indicates that delocalization interactions in the C–C bonds of 1.42 Å (143.70 kcal/mol) and 1.47 Å (34.98 kcal/mol) are 22% and 38% higher, respectively, than those in benzene. MP2/Def2SVP calculations yield a correlation energy of 13.49 kcal/mol per electron for C₆₀, slightly higher than the 11.68 kcal/mol for benzene. However, the results from HOMO-LUMO calculations should be interpreted with caution. This study may assist in the rational design of fullerene C₆₀ derivatives for CO₂ reduction systems. Full article

Bulk heterojunction solar cells are among the most promising organic solar cells (OSCs). One of the two important parts of OSCs are acceptors, and the development of the design and synthesis of non-fullerene acceptors involves an electron-deficient heterocyclic central core and anchor acceptor malonitrile derivatives of 3-methylene-2,3-dihydro-1H-inden-1-ones. In this communication, an intermediate for the synthesis of this compound, 1-(dicyanomethylene)-3-hydroxy-1H-indene-2-carboxylic acid, was prepared by the Perkin reaction of 2-(3-oxoisobenzofuran-1(3H)-ylidene)malononitrile with tert-butyl acetoacetate in the presence of acetic anhydride and triethylamine. The structure of the newly synthesized compound was established by means of elemental analysis, high-resolution mass spectrometry, ¹H NMR, ¹³C NMR and IR spectroscopy, and mass spectrometry. Full article

Currently, lithium-ion batteries have an increasingly urgent need for high-performance electrolytes, and additives are highly valued for their convenience and cost-effectiveness features. In this work, the feasibilities of fullerenes and fluorinated fullerenes as typical bis(fluorosulfonyl)imide/1,2-dimethoxymethane (LiFSI/DME) electrolyte additives are rationally evaluated based on density functional theory calculations and molecular dynamic simulations. Interestingly, electronic structures of C₆₀, C₆₀F₂, C₆₀F₄, C₆₀F₆, 1-C₆₀F₈, and 2-C₆₀F₈ are found to be compatible with the properties required as additives. It is noted that that different numbers and positions of F atoms lead to changes in the deformation and electronic properties of fullerenes. The F atoms not only show strong covalent interactions with C cages, but also affect the C-C covalent interaction in C cages. In addition, molecular dynamic simulations unravel that the addition of trace amounts of C₆₀F₄, C₆₀F₆, and 2-C₆₀F₈ can effectively enhance the Li⁺ mobility in LiFSI/DME electrolytes. The results expand the range of applications for fullerenes and their derivatives and shed light on the research into novel additives for high-performance electrolytes. Full article

Ternary organic solar cells contain a single three-component photoactive layer with a wide absorption window, achieved without the need for multiple stacking. However, adding a third component into a well-known binary blend can influence the energetics, optical window, charge carrier transport, crystalline order and conversion efficiency. In the form of binary blends, the low-bandgap regioregular polymer donor poly(3-hexylthiophene-2,5-diyl), known as P3HT, is combined with the acceptor PC₆₁BM, an inexpensive fullerene derivative. Two different non-fullerene acceptors (ITIC and eh-IDTBR) are added to this binary blend to form ternary blends. A systematic comparison between binary and ternary systems was carried out as a function of the thermal annealing temperature of organic layers (100 °C and 140 °C). The power conversion efficiency (PCE) is improved due to increased fill factor (FF) and open-circuit voltage (V_oc) for thermal-annealed ternary blends at 140 °C. The transport properties of electrons and holes were investigated in binary and ternary blends following a Space-Charge-Limited Current (SCLC) protocol. A favorable balanced hole–electron mobility is obtained through the incorporation of either ITIC or eh-IDTBR. The charge transport behavior is correlated with the bulk heterojunction (BHJ) morphology deduced from atomic force microscopy (AFM), contact water angle (CWA) measurement and 2D grazing-incidence X-ray diffractometry (2D-GIXRD). Full article

We have developed novel polynomials called delta polynomials, which are, in turn, derived from the characteristic and matching polynomials of graphs associated with polycyclic aromatic compounds. Natural logarithmic aromatic indices are derived from these delta polynomials, which are shown to provide new insights into the aromaticity of polycyclic aromatic compounds, including the highly symmetric C₆₀ buckminsterfullerene, several other fullerenes, graphene, kekulene series and other cycloarenes, such as polycyclic circumcoronaphenes and coronoids. The newly developed aromatic index yields a value of 6.77 for graphene, 6.516865 for buckminsterfullerene C₆₀(I_h), 5.914023 for kekulene (D_6h symmetry), 6.064420 for coronene (D_6h), 6.137828 for circumcoronene (D_6h), 6.069668 for dicronylene and so forth. Hence, the novel scaled logarithmic aromatic delta indices developed here appear to provide good quantitative measures of aromaticity, especially when they are used in conjunction with other aromatic indicators. Full article

In order to maximally reduce the toxicity of fullerenol (the first derivative of C₆₀, FD-C₆₀), and increase its biomedical efficiency, the second derivative SD-C₆₀ (3HFWC, Hyper-Harmonized Hydroxylated Fullerene Water Complex) was created. Several different methods were applied in the comparative characterization of FD-C₆₀ and SD-C₆₀ with the same OH groups in their core. FD-C₆₀ as an individual structure was about 1.3 nm in size, while SD-C₆₀ as an individual structure was 10–30 nm in size. Based on ten physicochemical methods and techniques, FD-C₆₀ and SD-C₆₀ were found to be two different substances in terms of size, structure, and physicochemical properties; FD-C₆₀, at 100 °C, had endothermic characteristics, while SD-C₆₀, at 133 °C, had exothermic characteristics; FD-C₆₀ did not have water layers, while SD-C₆₀ had water layers; the zeta potential of FD-C₆₀ was −25.85 mV, while it was −43.29 mV for SD-C₆₀. SD-C₆₀ is a promising substance for use in cosmetics and pharmaceuticals. Full article