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Toxicological Assessment of Melamine-Functionalized Graphene Oxide and Carbon Nanotubes Using Zebrafish Models.

Graphene oxide (GO) and carbon nanotube (CNT)-based nanomaterials have attracted significant interest in various industrial and biomedical applications due to their unique physicochemical properties; however, concerns about their potential toxicity, especially when modified with additives like melamine (M), remain largely unresolved. This study investigates the toxicological effects and underlying mechanisms of graphene oxide-melamine (GO-M) and carbon nanotube-melamine (CNT-M) nanoparticles in zebrafish (Danio rerio) embryos and larvae. To this end, developmental toxicity, phenotypic and behavioral changes, as well as histopathological and immunofluorescence alterations, were evaluated following acute exposure to GO-M and CNT-M nanoparticles at concentrations of 5, 10, and 20 mg/L. Results showed that both nanoparticles delayed larval hatching, particularly at higher concentrations (10 and 20 mg/L). Malformations were observed at 20 mg/L in the GO-M group and at 10 and 20 mg/L in the CNT-M group. Additionally, significant changes in larval length and eye area were observed at all concentrations for both nanoparticles. Behavioral assessments revealed that CNT-M exposure at 10 and 20 mg/L significantly impaired head sensorimotor reflexes, while all concentrations affected tail reflexes. In contrast, GO-M exposure did not significantly alter sensorimotor responses. These findings suggest differential toxic mechanisms and neurobehavioral effects of GO-M and CNT-M nanoparticles during early zebrafish development.

Animals↗

Degradation of a graphene-reinforced polyamide by fungi: When culture conditions matter.

The large-scale production, marketing and disposal of polymer-based graphene products can lead to the dispersal of graphene-enriched plastic particles into terrestrial ecosystems, where they might accumulate if not degraded by organisms. The objective of this work is to test the degradability and compatibility of one polyamide-6 polymer reinforced with reduced graphene-oxide (PA6-rGO) and its base constituents (polyamide-6, PA6; reduced graphene oxide, rGO) using mono- and co-cultures of two lignin-degrading fungi (Bjerkandera adusta and Morchella esculenta) grown under different nutrient conditions. Fungal (co-)cultures were exposed to pure rGO or abraded powders of PA6 and PA6-rGO in two different liquid media, and monitored over time for biomass growth, H2O2 production, and activity of two lignolytic enzymes (i.e., Laccase, Lac, and Lignin peroxidase, LiP). The changes in polyamide structure were evaluated by proton nuclear magnetic resonance and mass spectrometry, and changes in rGO were evaluated by Raman spectroscopy. The materials had no effect on fungal growth. PA6 increased Lac secretion only in low nutrient medium, while PA6-rGO slightly suppressed LiP activity. Only M. esculenta promoted polyamides oxidation when cultured in a low nutrient medium, as evidenced by a change in mass distribution values (m/z: 400-420) and the appearance of a new resonance peak (at 5.37 ppm). Lignolytic exudates in co-cultures low in nutrients caused a greater change in rGO, as shown by the increase in the ID/IG ratio. The degradation of rGO, PA6 and PA6-rGO depended on culture conditions.

Graphite↗

The oxidized soot surface: theoretical study of desorption mechanisms involving oxygenated functionalities and comparison with temperature programed desorption experiments.

The desorption mechanism for oxygenated functionalities on soot is investigated by quantum mechanical calculations on functionalized polycyclic aromatic hydrocarbon (PAH) models and compared with recently published temperature programed desorption-mass spectrometry results. Substituents on PAHs of increasing size (up to 46 carbon atoms in the parent PAH) are chosen to reproduce the local features of an oxidized graphenic soot platelet. Initially, the study is carried out on unimolecular fragmentation (extrusion, in some cases) processes producing HO, CO, or CO2, in model ketones, carboxylic acids, lactones, anhydrides, in one aldehyde, one peroxyacid, one hydroperoxide, one secondary alcohol, and one phenol. Then, a bimolecular process is considered for one of the carboxylic acids. Furthermore, some cooperative effect which can take place by involving two vicinal carboxylic groups (derived from anhydride hydrolysis) is investigated for other four bifunctionalized models. The comparison between the computed fragmentation (desorption) barriers for the assessed mechanisms and the temperature at which maxima occur in TPD spectra (for HO, CO, or CO2 desorption) offers a suggestion for the assignment of these maxima to specific functional groups, i.e., a key to the description of the oxidized surface. Notably, the computations suggest that (1) the desorption mode from a portion of a graphenic platelet functionalized by a carboxylic or lactone groups is significantly dependent from the chemical and geometric local environment. Consequently, we propose that (2) not all carboxylic groups go lost at the relatively low temperatures generally stated, and (3) lactone groups can be identified as producing not only CO2 but also CO.

Journal Article↗

Functionalized single graphene sheets derived from splitting graphite oxide.

A process is described to produce single sheets of functionalized graphene through thermal exfoliation of graphite oxide. The process yields a wrinkled sheet structure resulting from reaction sites involved in oxidation and reduction processes. The topological features of single sheets, as measured by atomic force microscopy, closely match predictions of first-principles atomistic modeling. Although graphite oxide is an insulator, functionalized graphene produced by this method is electrically conducting.

Electric Conductivity↗

Effects of gas adsorption on the electrical conductivity of single-wall carbon nanohorns.

We present significant electrical conductivity responses of the pelletized as-prepared and oxidized (ox-) single-wall carbon nanohorns (SWNHs) on adsorption of CO(2) and O(2). The morphological and pore structures of both pelletized SWNHs were examined by transmission electron microscopy (TEM) and nitrogen adsorption isotherm, leading to explicit evidences of the formation of nanoscale windows on the wall by oxidation. The SWNH and ox-SWNH induced a semiconducting behavior, strongly responded to CO(2) and O(2) adsorptions, and each exhibited n-type- and p-type-like conductivities. The electrical conductivity increase and decrease for CO(2) and O(2) adsorption, respectively, were observed for SWNH, whereas ox-SWNH showed a marked electrical conductivity drop on CO(2) adsorption and almost no change on O(2) adsorption. The dramatically different electrical conductivity response of ox-SWNH is presumed to be ascribed to the annihilation of pentagons in the single graphene wall by oxidation.

Adsorption↗

Engineering copper ferrite (CuFe2O4) nanocomposites for enhanced eco-friendly photocatalysis: a systematic critical review on mechanisms, performance, and environmental applications.

Water pollution caused by organic and inorganic contaminants, particularly dyes and pharmaceuticals, represents a major environmental challenge. Advanced oxidation processes based on photocatalysts have emerged as efficient and sustainable approaches for water and wastewater treatment. Copper ferrite (CuFe2O4) is considered a promising photocatalyst owing to its narrow bandgap, visible-light activity, chemical stability, and magnetic properties. Despite extensive experimental investigations, a comprehensive systematic comparison of CuFe2O4-based photocatalysts under diverse operational conditions has remained limited. In this study, a systematic review following PRISMA guidelines was conducted using studies published between January 2014 and November 2025 indexed in Scopus, PubMed, Web of Science, and ScienceDirect. From an initial pool of 397 studies, 98 articles met the inclusion criteria. Key parameters - including pollutant type, pH, catalyst dosage, initial pollutant concentration, irradiation time, light source, and degradation efficiency - were quantitatively compared to identify performance trends and operational optima. The results demonstrate that CuFe2O4-based nanocomposites, particularly heterojunction, Z-scheme, and S-scheme architectures combined with TiO2, g-C3N4, graphene, and metal oxides, achieve high degradation efficiencies (often >90 %) for a wide range of organic pollutants and selected inorganic contaminants (e.g., Cr(VI)). Enhanced charge separation and suppressed electron-hole recombination were identified as the primary factors contributing to improved photocatalytic activity. In addition, the intrinsic magnetic properties of these nanocomposites enable facile catalyst recovery and reuse. In conclusion, CuFe2O4-based nanocomposites, especially those incorporating advanced heterojunction architectures, emerge as highly efficient and magnetically recoverable photocatalytic platforms for sustainable water and wastewater treatment, with strong potential for scalable implementation and real-wastewater applications.

Catalysis↗

Controlled oxidative cutting of single-walled carbon nanotubes.

The oxidation reaction of piranha solutions with purified HiPco carbon nanotubes was measured as a function of temperature. At high temperatures, piranha is capable of attacking existing damage sites, generating vacancies in the graphene sidewall, and consuming the oxidized vacancies to yield short, cut nanotubes. Increased reaction time results in increasingly shorter nanotubes. However, significant sidewall damage occurs as well as selective etching of the smaller diameter nanotubes. On the other hand, room-temperature piranha treatments show the capability of cutting existing damage sites with minimal carbon loss, slow etch rates, and little sidewall damage. Combined with a method of introducing controlled amounts of damage sites, these room-temperature piranha solutions have the potential to yield an efficient means of creating short, cut nanotubes.

Journal Article↗

Solution properties of graphite and graphene.

Covalent derivatization of the acidic functional groups in oxidized graphite with octadecylamine renders graphite soluble in common organic solvents. Atomic force microscopic characterization of the soluble species supports the idea that the solutions consist of single and few layer graphene sheets, and we report the first solution properties of graphite.

Journal Article↗

A study of the reaction of oxygen with graphite: model chemistry.

A considerable amount of research has been directed towards the mechanism of oxidation of graphite as a model reaction system and because of its industrial importance. A number of recent studies have been concerned with ab initio molecular orbital calculations on graphite including model chemistry and the reactions with molecular oxygen. This study is concerned with oxidation steps involving the attachment of molecular oxygen to the graphene, the formation of carbon monoxide and, in particular, the subsequent oxidation reactions.

Journal Article↗

Structural and Energetic Nonuniformities of Pyrocarbon-Mineral Adsorbents.

Several series of pyrocarbon-mineral adsorbents (carbosils) were studied using the nitrogen adsorption method to compute structural and energetic parameters within the scope of overall adsorption isotherm approximation applying a regularization procedure with consideration for surface heterogeneity. A portion of pyrocarbon deposits (graphene clusters) fills mesopores of the oxide supports, but another portion represents relatively large nonporous pyrocarbon globules formed on the outer surfaces of the oxide matrices. Contributions of these two types of pyrocarbon deposits depend on the nature of oxide matrices and carbonized precursors. The characteristics of pyrocarbon formed on the silica (silica gel, fumed silica) surfaces differ from those for deposits prepared on the surfaces of titania/silica and alumina/silica or by the pyrolysis of metal acetylacetonates (Zr(AcAc)(4), TiO(AcAc)(2), Ni(AcAc)(2), Zn(AcAc)(2), Cr(AcAc)(3), Co(AcAc)(2)) on mesoporous silica gel. The structural and energetic characteristics estimated using the adsorption method with consideration for the adsorbent heterogeneity are fruitful for comparative analysis of the (1)H NMR spectra of water adsorbed on carbosils from the gas phase or unfrozen in the aqueous suspensions at T < 273 K. Copyright 2001 Academic Press.

Journal Article↗

Extending the nitrogen-heterosuperbenzene family: the spectroscopic, redox, and photophysical properties of "half-cyclized" N-1/2HSB and Its Ru(II) complex.

Oxidative cyclodehydrogenation is an important process in the formation of the new graphene, N-(1)/(2)HSB 2. This heteropolyaromatic results from the FeCl(3)-catalyzed oxidative cyclodehydrogenation of 1,2-dipyrimidyl-3,4,5,6-tetra-(4-tert-butylphenyl)benzene. Three new C-C bonds are formed that lock the two pyrimidines in a molecular platform comprising eight fused aromatic rings flanked by two remaining "uncyclized" phenyl rings. Mechanistically intriguing is the fact that N-HSB 1, the product of six C-C bond fusions, is co-synthesized with its "half-cyclized" daughter in this reaction. 1 and 2 have the same bidentate N-atom arrangement. This facilitates formation of the heteroleptic Ru(II) complexes, [Ru(bpy)(2)(2)](PF(6))(2) 4 and [Ru(bpy)(2)(1)](PF(6))(2) 3, which differ in the size and planarity of their aromatic ligands. The new ligand 2 and its complex 4 are characterized by (1)H NMR, IR, ESI-MS, and accurate mass methods. 2 exhibits photophysical properties that are consistent with a reduction of the pi/pi framework, a concomitant increase in the energy of the LUMO, and a blue-shift of the solvent-dependent fluorescence (lambda(em) = 474 nm, phi(F) = 0.55, toluene) as compared to its parent. Complex 4 absorbs throughout the visible region and borders on near-IR emitter character, exhibiting a slightly blue-shifted (3)MLCT emission (868 nm, CH(3)CN) as compared to that of [Ru(bpy)(2)(1)](PF(6))(2) 3 (880 nm, CH(3)CN). Electrochemical analyses permit further elucidation of the intermolecular interactions of 3 and 4. These and the concentration and temperature-dependent NMR spectra of 4 confirm it to be nonaggregating, a direct result of the two uncyclized and rotatable phenyl rings in 2.

Journal Article↗

Defect studies on as-synthesized and purified carbon nanostructures produced by arc-discharge in solution process.

Carbon nanostructures are synthesized using a novel arc-discharge in solution process. A multitude of defects on nanotubes and nanostructures is found. Evidence of these defects in as-synthesized carbon nanostructures is explored using high-resolution transmission electron microscopy (HRTEM). Tri-, tetra-, penta-, hexa-, heptagonal, toroidal, oval, and spherical nanoshells are found in HRTEM investigation along with carbon nanotubes, carbon nanohorns, carbon rods, nanoporous carbon, dislodged graphene sheets, and amorphous carbon. Purifications are carried out through two oxidation methods to eliminate the amorphous carbon. Several different defects caused by oxidations are also found in purified samples.

Carbon↗

Self-assembled hexa-peri-hexabenzocoronene graphitic nanotube.

An amphiphilic hexa-peri-hexabenzocoronene self-assembles to form a pi-electronic, discrete nanotubular object. The object is characterized by an aspect ratio greater than 1000 and has a uniform, 14-nanometer-wide, open-ended hollow space, which is an order of magnitude larger than those of carbon nanotubes. The wall is 3 nanometers thick and consists of helical arrays of the pi-stacked graphene molecule, whose exterior and interior surfaces are covered by hydrophilic triethylene glycol chains. The graphitic nanotube is redox active, and a single piece of the nanotube across 180-nanometer-gap electrodes shows, upon oxidation, an electrical resistance of 2.5 megohms at 285 kelvin [corrected]. This family of molecularly engineered graphite with a one-dimensional tubular shape and a chemically accessible surface constitutes an important step toward molecular electronics.

Journal Article↗

Quantum chemical prediction of reaction pathways and rate constants for dissociative adsorption of CO(x) and NO(x) on the graphite (0001) surface.

We present predictions of reaction rate constants for dissociative adsorption reactions of CO(x) (x = 1, 2) and NO(x) (x = 1, 2) molecules on the basal graphite (0001) surface based on potential energy surfaces (PES) obtained by the integrated ONIOM(B3LYP:DFTB-D) quantum chemical hybrid approach with dispersion-augmented density functional tight binding (DFTB-D) as low level method. Following an a priori methodology developed in a previous investigation of water dissociative adsorption reactions on graphite, we used a C(94)H(24) dicircumcoronene graphene slab as model system for the graphite surface in finite-size molecular structure investigations, and single adsorbate molecules reacting with the pristine graphene sheet. By employing the ONIOM PES information in RRKM theory we predict reaction rate constants in the temperature range between 1,000 and 5,000 K. We find that among CO(x) and NO(x) adsorbate species, the dissociative adsorption reactions of CO(2) and both radical species NO and NO(2) are likely candidates as a cause for high temperature oxidation and erosion of graphite (0001) surfaces, whereas reaction with CO is not likely to lead to long-lived surface defects. High temperature quantum chemical molecular dynamics simulations (QM/MD) at T = 5,000 K using on-the-fly DFTB-D energies and gradients confirm the results of our PES study.

Journal Article↗

Adsorption of single-ring organic compounds to wood charcoals prepared under different thermochemical conditions.

Environmental black carbon (BC) is believed to be an important adsorbent of organic pollutants. In this study, we examined the effects of changes in surface properties and adsorbate structure. A series of apolar compounds (cyclohexane, 1,2-dichlorobenzene, 1,4-xylene, 1,2,3,5-tetramethylbenzene, 1,3,5-triethylbenzene) and a series of polar compounds (o-cresol, 4-nitrotoluene, 2,4-dinitrotoluene, and 2,4,6-trinitrotoluene) were sorbed from aqueous solution to maple wood char prepared under five thermochemical conditions. Two chars were prepared in air at 340 degrees C (C340) and 400 degrees C (C400). A subsample of C400 was treated with H2 in the presence of a supported Pt catalyst at 500 degrees C (C400-H) to remove surface O. Another was treated under N2 at 500 degrees C (C400-N) to serve as a control for C400-H. The reduced C400-H was further oxidized in air at 340 degrees C to reintroduce O (C400-H-A). The five chars vary in O content (26.1, 22.3, 4.2, 20.8, and 18.6 wt %, respectively) but show only minor differences in surface area and pore size distribution on the basis of N2 and CO2 adsorption analysis. These chars provide a basis for rationalizing sorption intensity as a function of sorbate molecular structure and surface chemistry. The following conclusions were drawn. (1) Polar interactions with surface O functional groups are not a significant driving force for adsorption. (2) When isotherms are adjusted for solute hydrophobicity (n-hexdecane-water partition coefficient), sorption intensity of the polar compounds is greater than that of the apolar compounds, possibly because of pi-pi EDA interactions of the polar compounds with the basal plane of the graphene sheets. (3) The largest test compounds show steric exclusion from a portion of the adsorption space available to the other compounds. (4) Removal of O functionality by hydrogenation enhances sorption intensity of polar and apolar compounds, alike by reducing competitive adsorption by water molecules.

Adsorption↗