Exohedral cuprofullerenes with 6-, 12-, or 24-nuclearity were obtained by utilizing fluorocarboxylic/dicarboxylic acid under solvothermal conditions. The 24-nuclear molecule presents a C60@Cu24 core-shell structure with a rhombicuboctahedron Cu24 coated on the C60 core, representing the highest nuclearity in metallofullerene. The resultant complexes show an efficient absorption of visible light as opposed to the pristine C60. TD-DFT calculations revealed the charge transfer from Cu(I) and O atoms to the fullerene moiety dominates the photophysical process.
The adsorption behavior of the amino acid, glycine (Gly), via the carboxyl, hydroxyl, and amino groups onto the surfaces of Al12N12 and Al16N16 fullerene-like cages were computationally evaluated by the combination of density functional theory (DFT) and molecular docking studies. It was found that Gly can chemically bond with the Al12N12 and Al16N16 fullerene-like cages as its amino group being more favorable to interact with the aluminum atoms of the adsorbents compared to carboxyl and hydroxyl groups. Oxygen and carbon doping were reported to reduce steric hindrance for Glycine interaction at Al site of Al12ON11/Gly and Al12CN11/Gly complexes. Interaction was further enhanced by oxygen doping due to its greater electron withdrawing effect. Herein, the Al12ON11/Gly complex where two carbonyl groups of Gly are bonded to the aluminum atoms of the Al12N12 fullerene-like cage is the most stable interaction configuration showing ∆adsH and ∆adsG values of -81.74 kcal/mol and -66.21 kcal/mol, respectively. Computational studies also revealed the frequency shifts that occurred due to the interaction process. Molecular docking analysis revealed that the Al12N12/Gly (-11.7 kcal/mol) and the Al12ON11/Gly (-9.2 kcal/mol) complexes have a good binding affinity with protein tumor necrosis factor alpha (TNF-α). TNF-α was implicated as a key cytokine in various diseases, and it has been a validated therapeutic target for the treatment of rheumatoid arthritis. These results suggest that the Al12N12/Gly complex in comparison with the Al16N16/Gly, Al12ON11/Gly, and the Al12CN11/Gly complexes could be efficient inhibitors of TNF-α.
Designing a biosensor for versatile biomedical applications is a sophisticated task and how dedicatedly functionalized fullerene (C60) can perform on this stage is a challenge for today and tomorrow's nanoscience and nanotechnology. Since the invention of biosensor, many ideas and methods have been invested to upgrade the functionality of biosensors. Due to special physicochemical characteristics, the novel carbon material "fullerene" adds a new dimension to the construction of highly sensitive biosensors. The prominent aspects of fullerene explain its outstanding performance in biosensing devices as a mediator, e.g. fullerene in organic solvents exhibits five stages of reversible oxidation/reduction, and hence fullerene can work either as an electrophile or nucleophile. Fullerene is stable and its spherical structure produces an angle strain which allows it to undergo characteristic reactions of addition to double bonds (hybridization which turns from sp(2) to sp(3)). Research activities are being conducted worldwide to invent a variety of methods of fullerene functionalization with a purpose of incorporating it effectively in biosensor devices. The different types of functionalization methods include modification of fullerene into water soluble derivatives and conjugation with enzymes and/or other biomolecules, e.g. urease, glucose oxidase, hemoglobin, myoglobin (Mb), conjugation with metals e.g. gold (Au), chitosan (CS), ferrocene (Fc), etc. to enhance the sensitivity of biosensors. The state-of-the-art research on fullerene functionalization and its application in sensor devices has proven that fullerene can be implemented successfully in preparing biosensors to detect glucose level in blood serum, urea level in urine solution, hemoglobin, immunoglobulin, glutathione in real sample for pathological purpose, to identify doping abuse, to analyze pharmaceutical preparation and even to detect cancer and tumor cells at an earlier stage. Employing fullerene-metal matrix for the detection of tumor and cancer cells is also possible by the inclusion of fullerene in single-walled carbon nanotubes (SWCNTs) known as peapods as well as in double-walled carbon nanotubes (DWCNTs), to augment the effectiveness of biosensors. This review discusses various approaches that have been reported for functionalizing fullerene (C60) derivatives and their application in different types of biosensor fabrication.
Here we use triple-cation metal-organic halide perovskite single crystals for the transistor channel of a flash memory device. Moreover, we design and demonstrate a 10 nm thick single-layer nanofloating gate. It consists of a ternary blend of two organic semiconductors, a p-type polyfluorene and an n-type fullerene that form a donor:acceptor interpenetrating network that serves as the charge storage unit, and of an insulating polystyrene that acts as the tunneling dielectric. Under such a framework, we realize the first non-volatile flash memory transistor based on a perovskite channel. This simplified, solution-processed perovskite flash memory displays unique performance metrics such as a large memory window of 30 V, an on/off ratio of 9 × 107, short write/erase times of 50 ms, and a satisfactory retention time exceeding 106 s. The realization of the first flash memory transistor using a single-crystal perovskite channel could be a valuable direction for perovskite electronics research.
Fullerene nanoemulsions were formulated in palm kernel oil esters stabilized by low amount of mixed nonionic surfactants. Pseudoternary phase diagrams were established in the colloidal system of PKOEs/Tween 80 : Span 80/water incorporated with fullerene as antioxidant. Preformulation was subjected to combination of high and low energy emulsification methods and the physicochemical characteristics of fullerene nanoemulsions were analyzed using electroacoustic spectrometer. Oil-in-water (O/W) nanoemulsions with particle sizes in the range of 70-160 nm were formed. The rheological characteristics of colloidal systems exhibited shear thinning behavior which fitted well into the power law model. The effect of xanthan gum (0.2-1.0%, w/w) and beeswax (1-3%, w/w) in the estimation of thermodynamics was further studied. From the energetic parameters calculated for the viscous flow, a moderate energy barrier for transport process was observed. Thermodynamic study showed that the enthalpy was positive in all xanthan gum and beeswax concentrations indicating that the formation of nanoemulsions could be endothermic in nature. Fullerene nanoemulsions with 0.6% or higher xanthan gum content were found to be stable against creaming and flocculation when exposed to extreme environmental conditions.
This research aims to formulate and to optimize a nanoemulsion-based formulation containing fullerene, an antioxidant, stabilized by a low amount of mixed surfactants using high shear and the ultrasonic emulsification method for transdermal delivery. Process parameters optimization of fullerene nanoemulsions was done by employing response surface methodology, which involved statistical multivariate analysis. Optimization of independent variables was investigated using experimental design based on Box-Behnken design and central composite rotatable design. An investigation on the effect of the homogenization rate (4,000-5,000 rpm), sonication amplitude (20%-60%), and sonication time (30-150 seconds) on the particle size, ζ-potential, and viscosity of the colloidal systems was conducted. Under the optimum conditions, the central composite rotatable design model suggested the response variables for particle size, ζ-potential, and viscosity of the fullerene nanoemulsion were 152.5 nm, -52.6 mV, and 44.6 pascal seconds, respectively. In contrast, the Box-Behnken design model proposed that preparation under the optimum condition would produce nanoemulsion with particle size, ζ-potential, and viscosity of 148.5 nm, -55.2 mV, and 39.9 pascal seconds, respectively. The suggested process parameters to obtain optimum formulation by both models yielded actual response values similar to the predicted values with residual standard error of <2%. The optimum formulation showed more elastic and solid-like characteristics due to the existence of a large linear viscoelastic region.
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.
The main objective of this review is to derive the salient features of previously developed ultrasound-assisted methods for hydroxylating graphene and Buckminsterfullerene (C60). The pros and cons associated to ultrasound-assisted synthesis of hydroxy-carbon nanomaterials in designing the strategical methods for the industrial bulk production are also discussed. A guideline on the statistical methods has also been considered to further provide the scopes towards the application of the previously reported methods. Irrespective of many useful methods that have been developed in order to functionalize C60 and graphene by diverse oxygenated functional groups e.g. epoxide, hydroxyl, carboxyl as well as metal/metal oxide via a combination of organic chemistry and sonochemistry, there is no report dealing exclusively on the application of ultrasonic cavitation particularly to synthesising polyhydroxylated carbon nanomaterials. On this context, this review emphasizes in investigating the critical aspects of sono-nanochemistry and the statistical approaches to optimize the variables in the sonochemical process towards a large-scale synthesis of polyhydroxylated graphene and C60.
Carbon in its single entity and various forms has been used in technology and human life for many centuries. Since prehistoric times, carbon-based materials such as graphite, charcoal and carbon black have been used as writing and drawing materials. In the past two and a half decades or so, conjugated carbon nanomaterials, especially carbon nanotubes, fullerenes, activated carbon and graphite have been used as energy materials due to their exclusive properties. Due to their outstanding chemical, mechanical, electrical and thermal properties, carbon nanostructures have recently found application in many diverse areas; including drug delivery, electronics, composite materials, sensors, field emission devices, energy storage and conversion, etc. Following the global energy outlook, it is forecasted that the world energy demand will double by 2050. This calls for a new and efficient means to double the energy supply in order to meet the challenges that forge ahead. Carbon nanomaterials are believed to be appropriate and promising (when used as energy materials) to cushion the threat. Consequently, the amazing properties of these materials and greatest potentials towards greener and environment friendly synthesis methods and industrial scale production of carbon nanostructured materials is undoubtedly necessary and can therefore be glimpsed as the focal point of many researchers in science and technology in the 21st century. This is based on the incredible future that lies ahead with these smart carbon-based materials. This review is determined to give a synopsis of new advances towards their synthesis, properties, and some applications as reported in the existing literatures.
A novel method for the rapid modification of fullerene for subsequent enzyme attachment to create a potentiometric biosensor is presented. Urease was immobilized onto the modified fullerene nanomaterial. The modified fullerene-immobilized urease (C60-urease) bioconjugate has been confirmed to catalyze the hydrolysis of urea in solution. The biomaterial was then deposited on a screen-printed electrode containing a non-plasticized poly(n-butyl acrylate) (PnBA) membrane entrapped with a hydrogen ionophore. This pH-selective membrane is intended to function as a potentiometric urea biosensor with the deposition of C60-urease on the PnBA membrane. Various parameters for fullerene modification and urease immobilization were investigated. The optimal pH and concentration of the phosphate buffer for the urea biosensor were 7.0 and 0.5 mM, respectively. The linear response range of the biosensor was from 2.31 × 10-3 M to 8.28 × 10-5 M. The biosensor's sensitivity was 59.67 ± 0.91 mV/decade, which is close to the theoretical value. Common cations such as Na+, K+, Ca2+, Mg2+ and NH4+ showed no obvious interference with the urea biosensor's response. The use of a fullerene-urease bio-conjugate and an acrylic membrane with good adhesion prevented the leaching of urease enzyme and thus increased the stability of the urea biosensor for up to 140 days.
Phytoremediation has been applied as a promising and cost-effective technique for removing nutrient pollutants from wastewater. In this study, the effect of fullerene C60 was assessed on enhancing the phytoremediation efficiency of teak plants over a period of 1 month. Teak plants were supplied with fullerene C60 (0, 25, or 50 mg L-1) and fed daily with two types of urea plant wastewater (with and without adding optimum ratio of phosphorus and potassium). The required volume of wastewater by the teak plants, nitrogen removal percentage, plant growth parameters (plant height, number of leaves, leaf surface area, and dry biomass), and nutrient content was recorded throughout the study. The results showed that addition of 25 mg L-1 fullerene C60 to urea plant wastewater could increase water uptake and nitrogen recovery of the teak plants. Plant growth and nutrient contents of teak plants were also increased in the presence of 25 mg L-1 fullerene C60. However, addition of 50 mg L-1 fullerene C60 to the wastewater decreased the values for water uptake and nitrogen recovery. The findings indicated that addition of proper amount of fullerene C60 to the teak-based remediation system can increase the efficiency of the plants for nitrogen removal.
Despite the fact that intrinsic oxidative stress is inevitable, the extrinsic factor such as ultraviolet radiation enhances reactive oxygen species (ROS) generation resulting in premature skin aging. Nanoemulsion was loaded with fullerene, a strong free radical scavenger, and its efficacy to provide protection and regenerative effect against ROS-induced collagen breakdown in human skin was studied. Stable fullerene nanoemulsions were formulated using high shear homogenization and ultrasonic dispersion technique. An open trial was conducted using fullerene nanoemulsion on skin twice a day for 28 days. The mean collagen score significantly increased (P<0.05) from 36.53±4.39 to 48.69±5.46 with 33.29% increment at the end of the treatment. Biophysical characteristics of skin revealed that skin hydration was increased significantly (P<0.05) from 40.91±7.01 to 58.55±6.08 corneometric units (43.12% increment) and the water was able to contain within the stratum corneum without any increased in transepidermal water loss. In the in vitro safety evaluation, fullerene nanoemulsion showed no acute toxicity on 3T3 fibroblast cell line for 48h and no indication of potential dermal irritation. Hence, the fullerene nanoemulsion may assist in protecting collagen from breakdown with cosmeceutical benefit.
Coal combustion and the disposal of combustion wastes emit enormous quantities of nano-sized particles that pose significant health concerns on exposure, particularly in unindustrialized countries. Samples of fresh and weathered class F fly ash were analysed through various techniques including X-ray fluorescence (XRF), X-ray diffraction (XRD), focused ion beam scanning electron microscopy (FIB-SEM), field-emission gun scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM) coupled with energy dispersive x-ray spectroscopy (EDS), and Raman Spectroscopy. The imaging techniques showed that the fresh and weathered coal fly ash nanoparticles (CFA-NPs) are mostly spherical shaped. The crystalline phases detected were quartz, mullite, ettringite, calcite, maghemite, hematite, gypsum, magnetite, clay residues, and sulphides. The most abundant crystalline phases were quartz mixed with Al-Fe-Si-K-Ti-O-amorphous phases whereas mullite was detected in several amorphous phases of Al, Fe, Ca, Si, O, K, Mg, Mn, and P. The analyses revealed that CFA-NPs are 5-500 nm in diameter and encapsulate several potentially hazardous elements (PHEs). The carbon species were detected as 5-50 nm carbon nanoballs of graphitic layers and massive fullerenes. Lastly, the aspects of health risks related to exposure to some detected ambient nanoparticles are also discussed.