Fullerene Derivatives Research Articles

Влияние водорастворимых производных фуллерена С60 на уровень окислительного стресса и на транскрипционную активность генов, регулирующих про- и антиоксидантную активность эмбриональных фибробластов легких человека, культивируемых in vitro

The paper considers the effect of two water-soluble C60 fullerene derivatives modified with amino acid residues on the level of reactive oxygen species (ROS) in cultured human cells and on the transcriptional activity of genes that regulate pro- and antioxidant activity of cells. C60 fullerene derivatives with attached serine and phenibut amino acid residues were synthesized from C60Cl6 chlorofullerenes. Human embryonic lung fibroblast cultures were used in in vitro experiments. Various concentrations of fullerene derivatives were added to the culture medium, the cells were cultured in the presence of compounds from 1 to 72 hours. The level of ROS was determined using the dye 2,7-dichlorodihydrofluorescein diacetate (DCFH-DA), which is oxidized by free radicals to form fluorescent 2,7-dichlorofluorescein (DCF), by fluorescence microscopy, flow cytometry, and using a plate reader. The level of protein expression was determined by flow cytometry using specific antibodies. The level of gene expression was assessed by real-time polymerase chain reaction. It was shown that when the studied compounds are introduced into the cellular environment, they intensively absorb reactive oxygen species due to double conjugated bonds in the framework. At the same time, fullerene derivatives contribute to the development of secondary oxidative stress in cells 24 hours after administration. This effect occurs due to the activation of the NOX4 enzyme. In the cells of human embryonic lung fibroblasts, which were injected with the studied C60 fullerene derivatives, a correlation was found between the average value of the NOX4 enzyme protein and the level of reactive oxygen species. The lack of activation of the antioxidant transcription factor NRF2 upon incubation of human embryonic lung fibroblasts in the presence of C60 fullerene derivatives contributes to the development of secondary oxidative stress in cells.

An Integrated Metal‐Free Modification Method to Construct Efficient and Durable Bulk Heterojunction Photocathode for Solar Hydrogen Production

AbstractPolymer semiconductor with bulk heterojunction (BHJ) structure has attracted increasing attention to fabricate highly efficient photoelectrode for converting solar energy and water into hydrogen, thanks to its high photocurrent output and positive onset potential beyond 0.6 V. However, BHJ‐based photoelectrodes demonstrate poor anticorrosion against irradiation in aqueous environment, thus the photoelectrochemical (PEC) stability is a very intractable problem to solve. Herein, an inside and outside integrated modification method is developed to help BHJ‐based photocathode withstand PEC erosion during hydrogen production in acidic solution. The obtained BHJ (PBDB‐T:ITIC:PC71BM)‐based photocathode with surface carbon protective layer allows sustained and fast PEC hydrogen evolution (an average photocurrent density up to 13.5 mA cm−2) for a duration up to 15 h, which is among the best results of BHJ‐based photocathodes. The internal modification with fullerene derivative of PC71BM boosts the photogenerated electron transfer to balance against relative fast hole transfer, which largely alleviates electron accumulation and improves PEC intrinsic stability as a result. The surface carbon layer effectively resists the permeation of aqueous electrolyte without hindering interfacial charge transfer. This metal‐free protective method is very promising toward construction of highly robust BHJ‐based photoelectrodes for sustainable water splitting.

The Advancement of Nanotechnology in Treating Alzheimer’s Disease

Alzheimer’s disease is a neurodegenerative disorder with high prevalence in the rapidly increasingaging population in the worldwide. It is primarily caused by the collection of beta-amyloid plaques in the brain. The aim of this study to discuss the advancement of nanotechnology that help in the diagnosis and treatment of neurodegenerative disorder. Nanotechnology has shown its superiority that can applied medicinal uses and play great potential rolein therapy of Alzheimer’s disease. This is help to increasing the efficacy and efficiency of drug delivery by penetrating and overcoming the blood-brain barrier. There is need to explore and research in order to minimize the adverse effect and potential toxicity and to improve the drug bioavailability. The available medications in the market have only ability to slow down its progression.The current advances in the treatment of Alzheimer’s disease using nanotechnology contain the regeneration of stem cells, nanomedicine, and neuroprotection. The significantmediators for neuroprotection containnanogels, fullerene, dendrimers, gold nanoparticles and diamondoid derivatives

Polarizability of Kekulene, Septulene, and Nearest Non-Planar Polycyclic Aromatic Hydrocarbons

The polarizability of polycyclic aromatic hydrocarbons (PAHs) is an important property that relates to their abundance in natural environments. To assess the differences in the mean polarizability of planar and non-planar polycyclic aromatic hydrocarbons (PAHs), we computationally studied the PAH series of circulenes (kekulene C48H24, [13]circulene C52H26, and septulene C56H28), a number of the nearest helicenes, and their “expanded” isomers. We mean under “nearest” a close number of aromatic rings: 11 (C46H26), 12 (C50H28), 13 (C54H30), and 14 (C58H32). For these PAHs, we performed the quantum chemical calculations of thermodynamic and polarizability parameters with the PBE/3ζ density functional theory method, which is widely used in the theoretical chemistry of fullerenes and PAHs. The calculated mean polarizabilities (in Å3) ranged from 80.1 for [11]helicene to 135.5 for septulene, and while the circulenes and expanded helicenes had similar values, the mean polarizability of the normal helicenes was markedly lower. In all four pairs of helical PAHs, the expanded helicene was energetically considerably more favorable than its standard helicene isomer. Herewith, the ratio of their polarizabilities was equal to 1.3.

Self-Organization of Fullerene Derivatives in Solutions and Biological Cells Studied by Pulsed Field Gradient NMR.

Fullerene derivatives are of great interest in various fields of science and technology. Fullerene derivatives are known to have pronounced anticancer and antiviral activity. They have antibacterial properties. Their properties are largely determined by association processes. Understanding the nature and properties of associates in solvents of various types will make it possible to make significant progress in understanding the mechanisms of aggregation of molecules of fullerene derivatives in solutions. Thus, this work, aimed at studying the size and stability of associates, is relevant and promising for further research. The NMR method in a pulsed field gradient was used, which makes it possible to directly study the translational mobility of molecules. The sizes of individual molecules and associates were calculated based on the Stokes-Einstein model. The lifetime of associates was also estimated. The interaction of water-soluble C60 fullerene derivatives with erythrocytes was also evaluated. The values of self-diffusion coefficients and the lifetime of molecules of their compounds in cell membranes are obtained. It is concluded that the molecules of fullerene derivatives are fixed on the cell surface, and their forward movement is controlled by lateral diffusion.

Synthesis, characterization and safety evaluation of raw materials for cyclodextrin fullerene derivatives

To further improved the water solubility of fullerene, a new cyclodextrin and fullerene derivative was synthesized in this paper. NMR, elemental analysis, spectral analysis, tunnel scanning electron microscopy and X powder diffraction were used to characterize the material. Spectral analysis showed that the assembly had a wide acromion at 343nm and a large tail band absorption in the range of 350-600nm, indicating the presence of C60. From the STM images, it can be inferred that the weak interaction between the cyclodextrin cavity and the fullerene tail-to-tail form a regular linear arrangement. X-ray shows that there have many characteristic diffraction peak of 11, such as 2θ=11.52° (d=7.68Å), 2θ=14.62° (d=6.05Å), 2θ=25.5° (d=3.49 Å), 2θ=29.62° (d=3.01Å), 2θ=31.68° (d=2.82 Å), which proved that the cyclodextrin and fullerenes formed supramolecular polymers Through chemical safety tests, the results showed that there were no risk substances, pollutants, prohibited substances and restricted substances in the samples which could affect the safety of cosmetics. Phototoxicity, eye irritation/corrosiveness, skin irritation and cytotoxicity were not detected by toxicological safety test. This study provides technical data support for the use of new cyclodextrin and fullerene derivatives as cosmetic raw materials.

Optical fiber humidity sensor with C60-THAM as molecule receptors

This study proposed a high sensitivity optical fiber relative humidity sensor (OFHS). Besides, a fullerene derivative, C 60 -THAM, was synthesized and firstly reported as a molecule receptor in the OFHS. Compared with the widely researched carbon-based materials in OFHS, the C 60 -THAM film has abundant amino dangling bonds, hence emerges naturally as excellent receptors for water molecules. Besides, a cascaded Fabry-Perot interferometer (FPI) was fabricated in the core of single-mode fiber (SMF) without surface damage by femtosecond laser. In the OFHS, the relative humidity (RH) was measured by the Vernier effect. The working principle of the OFHS was analyzed through calculation and simulation. In the experiment, C 60 -THAM was coated on the plant fiber end. The sensitivity of the sensor is about 0.42 nm/RH as the relative humidity change from 30% to 65% while the optical-matter reaction length is only about 150 nm. Moreover, the sensor exhibited a stable performance as the RH was decreasing from 65% to 30%. The OFHS in this work is fast response and the response time for the rising and decay process was about 2.2 s and 3.2 s respectively. • A fullerene derivative, C 60 -THAM, was synthesized and its application in the fiber humidity sensor was researched. • The humidity sensor is fast response and the rising and decay time is about 2.2 s and 3.2 s respecitively. • The sensitivity is 0.42 nm/RH as the humidity change from 30% to 65% while the optical-matter reaction length is 150 nm.

Modelling the electric field in non-fullerene organic solar cells: The effect of 1-chloronaphthalene additive

In this work, a perylene derivative was used as electron acceptor in organic solar cells and the morphology was optimized by using the 1-chlronaphthalene (CN) as additive. The power dissipation was simulated along the structure of OPV devices taking into count the interference occurring in stacked thin films under normal incidence by using the transfer matrix method (TMM). The TMM model has been used to simulate the electric field in organic solar cells having fullerene derivatives as electron acceptor. In opposite to the fullerenes, the perylene derivative also contributes to the photocurrent and, its optical and electrical features changed upon CN additive. Therefore, the monitoring through ellipsometry and TMM modelling contribute to understand the behaviour of the electromagnetic wave inside the device, providing insights about proper optimizations that can be performed in order to increase the G(x) rate and the Jsc parameter. This model takes into count the experimental values of refractive index n and extinction coefficient k acquired from the D:A film to simulate the spatial distribution of the electric field and provide valuable information about photovoltaic parameters. The results pointed out that chemical or physical modifications are required to improve the PDIC5 acceptor distribution along the bulk, as well as changes on the crystallinity, which can be achieved with the use of CN as additive.

Fullerene‐Based Inverted Perovskite Solar Cell: A Key to Achieve Promising, Stable, and Efficient Photovoltaics

AbstractFullerene is one of the most critical materials that are widely used to improve and examine the inverted perovskite solar cells (PSCs, p‐i‐n structure). Fullerenes are known to improve the stability, lower the hysteresis, and increase the power conversion efficiency of the PSCs. Fullerene and its derivatives are often used in constructing effective PSCs. Several properties and performance of fullerenes are the key bases for testing and making effective alternatives that can improve the performance of PSCs. This review summarizes some of the most important fullerenes (i.e., fullerene and its derivatives) that are employed in inverted (p‐i‐n) PSCs and their physical properties that can overcome the well‐known shortcomings in perovskite materials. The current density–voltage hysteresis in PSC and the fullerenes role in lowering the hysteresis are discussed. Moreover, fullerenes are also reviewed as electron transport layer, cathode buffer layer, and additives for perovskites. Enhanced stability by using fullerene derivatives is illustrated. Additionally, fullerenes in flexible and tandem PSCs as well as advantages and disadvantages of fullerenes are briefly discussed. Finally, an overview of the fullerene future in PSCs is discussed with alternative nonfullerene materials used in PSC.

Grain Boundary and Buried Interface Suturing Enabled by Fullerene Derivatives for High-Performance Perovskite Solar Module

Grain Boundary and Buried Interface Suturing Enabled by Fullerene Derivatives for High-Performance Perovskite Solar Module

Multifunctional Ionic Fullerene Additive for Synergistic Boundary and Defect Healing of Tin Perovskite to Achieve High-Efficiency Solar Cells.

A series of new ionic fullerene derivatives (C60-RNH3-X; X = Cl, Br, or I) were designed especially for using as additives for tin perosvkite (TPsk, with chemical formula of FA0.98EDA0.01SnI3) to form TPsk-C60-RNH3-X bulk heterojunction (BHJ) films. Inverted tin-perovskite solar cells (TPSCs) based on BHJ TPsk-C60-RNH3-Br absorber achieved the highest power conversion efficiency up to 11.74% with very high FF of 73%, without current hysteresis and stable in a glovebox. The designed spherical ionic fullerene halide additive, sitting in the grain boundaries of the TPsk film, can not only improve the quality of the TPsk film and change the valence band energy to match better with the PEDOT:PSS hole transporter but also be a carrier transporting connector between tin-perovskite grains, the defects/traps passivation/healing agent by interacting with Sn2+ ions and filling the halogen vacancies. The functions of the ionic fullerene halide additive were revealed with XRD patterns, SEM images, element mapping, UPS spectra, infrared spectra, AFM, and SCLC data. Being able to passivate newly generated defects during device operation or sitting on the shelf is an important step to improve the long-term stability of TPSCs. If a passivation agent can move dynamically during cell operation or storage to heal the defects of perovskite, the instability problem of TPSCs can be alleviated. The spherical ionic fullerene halide could be one of the ideal passivation agents satisfying this purpose.

Strategies for Enhancing the Dielectric Constant of Organic Materials.

High dielectric constant organic semiconductors, often obtained by the use of ethylene glycol (EG) side chains, have gained attention in recent years in the efforts of improving the device performance for various applications. Dielectric constant enhancements due to EGs have been demonstrated extensively, but various effects, such as the choice of the particular molecule and the frequency and temperature regime, that determine the extent of this enhancement require further understanding. In this work, we study these effects by means of polarizable molecular dynamics simulations on a carefully selected set of fullerene derivatives with EG side chains. The selection allows studying the dielectric response in terms of both the number and length of EG chains and also the choice of the group connecting the fullerene to the EG chain. The computed time- and frequency-dependent dielectric responses reveal that the experimentally observed rise of the dielectric constant within the kilo/megahertz regime for some molecules is likely due to the highly stretched dielectric response of the EGs: the initial sharp increase over the first few nanoseconds is followed by a smaller but persistent increase in the range of microseconds. Additionally, our computational protocol allows the separation of different factors that contribute to the overall dielectric constant, providing insights to make several molecular design guides for future organic materials in order to enhance their dielectric constant further.

Paracetamol adsorption on C60 fullerene and its derivatives: In silico insights

Fullerene-C60 and its heteroatom decorated forms have been widely investigated as drug delivery vehicles and for sensor applications. Further, in the literature carboxylated or carboxylic derivatives of fullerenes have found a special place for biological applications due to their promising water-soluble properties. In the scope of this study, we examined the interaction between paracetamol (acetaminophen) which is a widely prescribed drug to manage acute and chronic pain conditions and C60, silicon doped fullerene (SiC59) and (1,2-methanofullerene C60)-61-carboxylic acid (C60-CH-COOH) using density functional theory calculations. Stability evaluations, electronic and structural properties were carried out by analyzing binding energies, frontier molecular orbitals and natural bond orbitals. It was found that silicon doping on the surface of C60 enhanced the adsorption strength of paracetamol and SiC59 is quite sensitive to the presence of paracetamol drug molecule.

Optical Properties and Light-Induced Charge Transfer in Selected Aromatic C60 Fullerene Derivatives and in Their Bulk Heterojunctions with Poly(3-Hexylthiophene).

Fullerene derivatives offer great scope for modification of the basic molecule, often called a buckyball. In recent years, they have been the subject of numerous studies, in particular in terms of their applications, including in solar cells. Here, the properties of four recently synthesized fullerene C60 derivatives were examined regarding their optical properties and the efficiency of the charge transfer process, both in fullerene derivatives themselves and in their heterojunctions with poly (3-hexylthiophene). Optical absorption, electron spin resonance (ESR), and time-resolved photoluminescence (TRPL) techniques were applied to study the synthesized molecules. It was shown that the absorption processes in fullerene derivatives are dominated by absorption of the fullerene cage and do not significantly depend on the type of the derivative. It was also found by ESR and TRPL studies that asymmetrical, dipole-like derivatives exhibit stronger light-induced charge transfer properties than their symmetrical counterparts. The observed inhomogeneous broadening of the ESR lines indicated a large disorder of all polymer–fullerene derivative blends. The density functional theory was applied to explain the results of the optical absorption experiments.

Effect of Fullerene Derivatives on the Lifetime Characteristics and the Stability of Inverted Perovskite Solar Cells

This contribution demonstrates the effects of mole ratio, concentration of perovskite components and fullerene derivatives used as electron transport layer (ETL) on the stability and performances of inverted perovskite solar cells (PSCs). C60, C70, PC61BM and PC71BM are selected as ETL materials. Methylammonium iodide (MAI):Lead (II) iodide (PbI2):Lead(II) chloride (PbCl2) are used to form MAPb2I2Cl which is a mixed halogen perovskite structure. The fabricated perovskite device containing PCBM with optimized concentration and mole ratio gives high power conversion efficiency (PCE) of 9.07% with an open-circuit voltage (Voc) of 0.91 V, short circuit current density of 14.1 mA/cm2, and fill factor of 0.71. The lifetime characteristics and the stability are found significantly dependent on the fullerene type. The devices containing PC61BM and PC71BM are able to maintain 50% and 30% of its initial performances, respectively, even after 1100 hours. Overall, the obtained results represent an important step understanding the impacts on the p-i-n type perovskite lifetimes.

From radicals destabilization to stable fullerenol nanoaggregates

• Fullerenol radicals were prepared with C60 and KOH in DMF under nitrogen atmosphere. • Radicals oxidation promoted by air contributes to increasing modification degree. • Nanoparticles are formed after the oxidation of fullerenol radicals. • Electrostatic and solvation interactions provide stability for nanoparticles in DMF. • Concentrated dispersions of fullerenols in DMF are lyophilic and stable. Fullerenols are fullerene derivatives enriched on hydroxyl groups that are obtained usually as nanoparticles nanoaggregates dispersed in water. These materials are used in energy-related and biological applications, and they have been reported as radical scavengers, antioxidants and stable radicals. However, most synthesis demand highly toxic solvents to dissolve precursor fullerene, potentially dangerous reagents such as hydrogen peroxide, and prolonged reactions. Herein, a novel and faster procedure for fullerenol preparation based on the reaction between fullerene C 60 and potassium hydroxide in a polar solvent is reported. Initially, fullerenol radicals are formed, followed by air oxidation that promotes charge loss and simultaneous clustering into nanoparticles nanoaggregates with diameters up to 90 nm. Dried fullerenol has about 12 oxygenated groups per C 60 . Then, an aqueous dispersion was prepared with dispersed material having lyophobic behavior but maintaining the modification degree. This low-modified fullerenol remains dispersed indefinitely in an organic medium due to electrostatic and solvation colloidal interactions arising from functional groups. As a result, stable organic dispersions with concentrations up to 10 mg mL −1 were obtained. This work opens new possibilities on fullerenol preparation and new perspectives concerning achieving the achievement of stable colloids of carbon nanomaterials due to the unprecedented stability and mass concentration of the reported fullerenol dispersions.

Oxidized Carbon-Based Spacers for Pressure-Resistant Graphene Oxide Membranes.

In this study, we report the influence of carbon-based spacer-oxidized derivatives of fullerenes (fullerenols) C60(OH)26–32 and graphene oxide nanoribbons on the performance and pressure stability of graphene-oxide-based composite membranes. The impact of the intercalant shape and composition on the permeance of the selective layers for water vapors has been studied under pressure gradients. It is shown that the insertion of ball-shaped fullerenols between graphene oxide nanoflakes allows a suppression in irreversible permeance loss to 2–4.5% and reversible permeance loss to <25% (at 0.1 MPa), while retaining large H2O/N2 selectivities of up to ~30,000. The demonstrated approach opens avenues for the highly effective stabilization of GO membranes at elevated pressures for industrial-scale dehumidification.

The Impact of the Presence of Aromatic Rings in the Substituent on the Performance of C60/C70 Fullerene-Based Acceptor Materials in Photovoltaic Cells

In this work, a series of C60/C70 fullerene derivatives bearing non-aromatic and mono-, bi-, tri- and tetracyclic aryl-substituents was synthesized according to the modified Bingel method and characterized using spectral methods: ESI-MS, 1H NMR, 13C NMR, UV–Vis, FT-IR and cyclic voltammetry (CV). HOMO and LUMO energy levels and the band gaps for optimized structures of reported fullerene derivatives were determined according to the DFT functionals, B3LYP 6-31G(d) and PBE/6-311G(d,p). Results obtained from CV and UV–Vis measurements, which showed very good agreement, were compared to calculated theoretical values also revealing satisfactory level of compliance of the obtained results. We have studied the impact of presence and number of aromatic rings in malonate substituent of C60/C70 fullerene derivatives employed as acceptor materials on performance of BHJ solar cells prepared using PTB7-Th as donor material. We successfully prepared solar cells based on all the synthesized compounds, and the highest performance of the obtained photovoltaic devices was observed for fullerene derivatives bearing monocyclic and bicyclic aromatic moieties. The obtained voltage was about 0.8 V and current density was above 10 mA/cm2. Optical studies showed absorption edges at 1.9 eV and 1.8 eV for C60 and C70 derivatives, respectively, with absorption coefficients comparable to C60/C70 PCBM samples. Photocurrent spectroscopy showed 20–40% quantum efficiency. Long-term ageing measurements showed T80 time between 105 days and 115 days for derivatives with phenyl and naphthalene substituents. Taking into account that synthesis of reported fullerene derivatives is very convenient, the reported compounds are very promising materials for construction of BHJ solar cells.

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.

Efficient Exciton Dislocation and Ultrafast Charge Extraction in CsPbI3 Perovskite Quantum Dots by Using Fullerene Derivative as Semiconductor Ligand.

CsPbI3 quantum dots (QDs) are of great interest in new-generation photovoltaics (PVs) due to their excellent optoelectronic properties. The long and insulative ligands protect their phase stability and enable superior photoluminescence quantum yield, however, limiting charge transportation and extraction in PV devices. In this work, we use a fullerene derivative with the carboxylic anchor group ([SAM]C60) as the semiconductor ligand and build the type II heterojunction system of CsPbI3 QDs and [SAM]C60 molecules. We find their combination enables obvious exciton dislocation and highly efficient photogenerated charge extraction. After the introduction of [SAM]C60, the exciton-binding energy of CsPbI3 decreases from 30 meV to 7 meV and the fluorescence emission mechanism also exhibits obvious changes. Transient absorption spectroscopy visualizes a ~5 ps electron extraction rate in this system. The findings gained here may guide the development of perovskite QD devices.