Elimination of Multidrug-Resistant Bacteria by Transition Metal Dichalcogenides Encapsulated by Synthetic Single-Stranded DNA.

Antibiotic-resistant bacteria are a significant and growing threat to human health. Recently, two-dimensional (2D) nanomaterials have shown antimicrobial activity and have the potential to be used as new approaches to treating antibiotic resistant bacteria. In this Research Article, we exfoliate transition metal dichalcogenide (TMDC) nanosheets using synthetic single-stranded DNA (ssDNA) sequences, and demonstrate the broad-spectrum antibacterial activity of MoSe2 encapsulated by the T20 ssDNA sequence in eliminating several multidrug-resistant (MDR) bacteria. The MoSe2/T20 is able to eradicate Gram-positive Escherichia coli and Gram-positive Staphylococcus aureus at much lower concentrations than graphene-based nanomaterials. Eradication of MDR strains of methicillin-resistant S. aureus (MRSA), Enterococcus faecalis, Pseudomonas aeruginosa, Klebsiella pneumoniae, and Acinetobacter baumannii are shown to occur at at 75 µg mL-1 concentration of MoSe2/T20, and E. coli at 150 µg mL-1. Molecular dynamics simulations show that the thymine bases in the T20 sequence lie flat on the MoSe2 surface and can, thus, form a very good conformal coating and allow the MoSe2 to act as a sharp nanoknife. Electron microscopy shows the MoSe2 nanosheets cutting through the cell membranes, resulting in significant cellular damage and the formation of interior voids. Further assays show the change in membrane potential and reactive oxygen species (ROS) formation as mechanisms of antimicrobial activity of MoSe2/T20. The cellular death pathways are also examined by mRNA expression. This work shows that biocompatible TMDCs, specifically MoSe2/T20, is a potent antimicrobial agent against MDR bacteria and has potential for clinical settings.

Reaction Kinetics for the Covalent Functionalization of Two-Dimensional MoS2 by Aryl Diazonium Salts.

The two-dimensional transition-metal dichalcogenide molybdenum disulfide (MoS2) has been intensely studied in the past several years due to its exceptional electronic, optical, and chemical properties in a wide range of applications. The chemical functionalization of MoS2 allows its properties and interfacial interactions to be tuned and controlled. Recently, we reported the direct covalent functionalization of semiconducting MoS2 with aryl diazonium salts, without the use of harsh initial treatments or phase engineering. In this paper, we confirm and expand the covalent functionalization reaction model by performing a detailed study of the reaction kinetics for monolayer MoS2 functionalized by 4-nitrobenzene tetrafluoroborate (4-NBD). We find that both the Freundlich and Temkin isotherm models are good descriptors of the reaction due to the energetically inhomogeneous surface of MoS2 and the indirect adsorbate-adsorbate interactions from previously attached nitrophenyl groups, respectively. The reaction kinetics was then found to be well described using a pseudo-second-order model, showing that the order of this reaction is two. This study supports our previous work and gives us a deeper understanding of the nature of the covalent functionalization of MoS2.

Rotational superstructure in van der Waals heterostructure of self-assembled C60 monolayer on the WSe2 surface.

Hybrid van der Waals (vdW) heterostructures composed of two-dimensional (2D) layered materials and self-assembled organic molecules are promising systems for electronic and optoelectronic applications with enhanced properties and performance. Control of molecular assembly is therefore paramount to fundamentally understand the nucleation, ordering, alignment, and electronic interaction of organic molecules with 2D materials. Here, we report the formation and detailed study of highly ordered, crystalline monolayers of C60 molecules self-assembled on the surface of WSe2 in well-ordered arrays with large grain sizes (∼5 µm). Using high-resolution scanning tunneling microscopy (STM), we observe a periodic 2 × 2 superstructure in the C60 monolayer and identify four distinct molecular appearances. Using vdW-corrected ab initio density functional theory (DFT) simulations, we determine that the interplay between vdW and Coulomb interactions as well as adsorbate-adsorbate and adsorbate-substrate interactions results in specific rotational arrangements of the molecules forming the superstructure. The orbital ordering through the relative positions of bonds in adjacent molecules creates a charge redistribution that links the molecule units in a long-range network. This rotational superstructure extends throughout the self-assembled monolayer and opens a pathway towards engineering aligned hybrid organic/inorganic vdW heterostructures with 2D layered materials in a precise and controlled way.

Current and future directions in electron transfer chemistry of graphene.

The participation of graphene in electron transfer chemistry, where an electron is transferred between graphene and other species, encompasses many important processes that have shown versatility and potential for use in important applications. Examples of these processes range from covalent functionalization of graphene to modify its properties and incorporate different functional groups, to electrochemical reactions and selective etching. In this paper, we review recent developments in these areas of the electron transfer chemistry of graphene. We address recent progress on controlling covalent functionalization through chemical and physical methods, and how carefully functionalized graphene can be incorporated into composite materials with enhanced properties. We review the selective etching of graphene to form edges and nanopores, which have unique chemical and physical properties. Nanoporous graphene is promising for new membrane and filtration applications. We also discuss the electrochemistry of graphene grown by chemical vapour deposition in two-dimensional and three-dimensional geometries, which enables large surface areas and control over the distribution and concentration of edge and basal plane sites. We discuss the potential for each of these areas to have an impact in future applications such as filtration membranes, electronic devices, electrochemical electrodes, composite materials, and chemical sensors.