Sulfur-Doped Graphene <i>via</i> Thermal Exfoliation of Graphite Oxide in H₂S, SO₂, or CS₂ Gas

Doping of graphene with heteroatoms is an effective way to tailor its properties. Here we describe a simple and scalable method of doping graphene lattice with sulfur atoms during the thermal exfoliation process of graphite oxides. The graphite oxides were first prepared by Staudenmaier, Hofmann, and Hummers methods followed by treatments in hydrogen sulfide, sulfur dioxide, or carbon disulfide. The doped materials were characterized by scanning electron microscopy, high-resolution X-ray photoelectron spectroscopy, combustible elemental analysis, and Raman spectroscopy. The ζ-potential and conductivity of sulfur-doped graphenes were also investigated in this paper. It was found that the level of doping is more dramatically influenced by the type of graphite oxide used rather than the type of sulfur-containing gas used during exfoliation. Resulting sulfur-doped graphenes act as metal-free electrocatalysts for an oxygen reduction reaction

Electrochemistry of Transition Metal Dichalcogenides: Strong Dependence on the Metal-to-Chalcogen Composition and Exfoliation Method

Beyond MoS₂ as the first transition metal dichalcogenide (TMD) to have gained recognition as an efficient catalyst for the hydrogen evolution reaction (HER), interest in other TMD nanomaterials is steadily beginning to proliferate. This is particularly true in the field of electrochemistry, with a myriad of emerging applications ranging from catalysis to supercapacitors and solar cells. Despite this rise, current understanding of their electrochemical characteristics is especially lacking. We therefore examine the inherent electroactivities of various chemically exfoliated TMDs (MoSe₂, WS₂, WSe₂) and their implications for sensing and catalysis of the hydrogen evolution and oxygen reduction reactions (ORR). The TMDs studied are found to possess distinctive inherent electroactivities and together with their catalytic effects for the HER are revealed to strongly depend on the chemical exfoliation route and metal-to-chalcogen composition particularly in MoSe₂. Despite its inherent activity exhibiting large variations depending on the exfoliation procedure, it is also the most efficient HER catalyst with a low overpotential of −0.36 V <i>vs</i> RHE (at 10 mA cm^–2 current density) and fairly low Tafel slope of ∼65 mV/dec after BuLi exfoliation. In addition, it demonstrates a fast heterogeneous electron transfer rate with a <i>k</i>⁰_obs of 9.17 × 10^–4 cm s^–1 toward ferrocyanide, better than that seen for conventional glassy carbon electrodes. Knowledge of TMD electrochemistry is essential for the rational development of future applications; inherent TMD activity may potentially limit certain purposes, but intended objectives can nonetheless be achieved by careful selection of TMD compositions and exfoliation methods

Uranium- and Thorium-Doped Graphene for Efficient Oxygen and Hydrogen Peroxide Reduction

Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in the fields of energy generation and sensing. Metal-doped graphenes, where metal serves as the catalytic center and graphene as the high area conductor, have been used as electrocatalysts for such applications. In this paper, we investigated the use of uranium–graphene and thorium–graphene hybrids prepared by a simple and scalable method. The hybrids were synthesized by the thermal exfoliation of either uranium- or thorium-doped graphene oxide in various atmospheres. The synthesized graphene hybrids were characterized by high-resolution XPS, SEM, SEM-EDS, combustible elemental analysis, and Raman spectroscopy. The influence of dopant and exfoliation atmosphere on electrocatalytic activity was determined by electrochemical measurements. Both hybrids exhibited excellent electrocatalytic properties toward oxygen and hydrogen peroxide reduction, suggesting that actinide-based graphene hybrids have enormous potential for use in energy conversion and sensing devices

Synthesis of Strongly Fluorescent Graphene Quantum Dots by Cage-Opening Buckminsterfullerene

Graphene quantum dots is a class of graphene nanomaterials with exceptional luminescence properties. Precise dimension control of graphene quantum dots produced by chemical synthesis methods is currently difficult to achieve and usually provides a range of sizes from 3 to 25 nm. In this work, fullerene C₆₀ is used as starting material, due to its well-defined dimension, to produce very small graphene quantum dots (∼2–3 nm). Treatment of fullerene C₆₀ with a mixture of strong acid and chemical oxidant induced the oxidation, cage-opening, and fragmentation processes of fullerene C₆₀. The synthesized quantum dots were characterized and supported by LDI-TOF MS, TEM, XRD, XPS, AFM, STM, FTIR, DLS, Raman spectroscopy, and luminescence analyses. The quantum dots remained fully dispersed in aqueous suspension and exhibited strong luminescence properties, with the highest intensity at 460 nm under a 340 nm excitation wavelength. Further chemical treatments with hydrazine hydrate and hydroxylamine resulted in red- and blue-shift of the luminescence, respectively

Cytotoxic Lipopeptide Muscotoxin A, Isolated from Soil Cyanobacterium <i>Desmonostoc muscorum</i>, Permeabilizes Phospholipid Membranes by Reducing Their Fluidity

There is mounting evidence that cyanobacterial lipopeptides can kill mammalian cells, presenting a hazard to human health. Unfortunately, their mechanism of toxicity is poorly understood. We have isolated new cyclic undeca-lipopeptides muscotoxin A and B containing unique lipophilic residue 3-amino-2,5-dihydroxydecanoic acid (5-OH Ahdoa). Muscotoxin B was not used for biological studies due to its poor yield. Muscotoxin A was cytotoxic to YAC-1, Sp/2, and HeLa cancer cell lines (LC₅₀ ranged from 9.9 to 13.2 μM after 24 h of exposure), causing membrane damage and influx of calcium ions. Subsequently, we studied this lytic mechanism using synthetic liposomes with encapsulated fluorescent probes. Muscotoxin A permeabilized liposomes composed exclusively of phospholipids, demonstrating that no proteins or carbohydrates present in biomembranes are essential for its activity. Paradoxically, the permeabilization activity of muscotoxin A was mediated by a significant reduction in membrane surface fluidity (stiffening), the opposite of that caused by synthetic detergents and cytolytic lipopeptide puwainaphycin F. At 25 °C, muscotoxin A disrupted liposomes with and without cholesterol/sphingomyelin; however, at 37 °C, it was selective against liposomes with cholesterol/sphingomyelin. It appears that both membrane fluidity and organization can affect the lytic activity of muscotoxin A. Our findings strengthen the evidence that cyanobacterial lipopeptides specifically disrupt mammalian cell membranes and bring new insights into the mechanism of this effect